Patent Application
20140037911
The present invention relates to removable pressure sensitive adhesive sheets. Specifically, the present invention relates to a removable pressure-sensitive adhesive sheet that has superior visual quality, less suffers from adhesive strength increase with time, and is highly resistant to scratches and static electrification.
Optical members (optical materials) may be represented by optical films such as polarizing plates, retardation films, and anti-reflective films. In production or working processes of them, surface-protecting films are laminated on the surface of the optical members for the purpose typically of preventing surface flaws and stains, improving cutting workability, or suppressing cracking (see Patent Literature (PTL) 1 and 2). Removable pressure-sensitive adhesive sheets are generally used as the surface-protecting films. The removable pressure-sensitive adhesive sheets each include a plastic film substrate and, on a surface thereof, a removable pressure-sensitive adhesive layer.
Solvent-borne acrylic pressure-sensitive adhesives have been used as pressure-sensitive adhesives to form the pressure-sensitive adhesive layer (see PTL 1 and 2). These solvent-borne acrylic pressure-sensitive adhesives contain organic solvents that may adversely affect the coating working environment. To prevent the adverse effect, attempts have been made to substitute water-dispersible acrylic pressure-sensitive adhesives for the solvent-borne acrylic pressure-sensitive adhesives (see PTL 3 to 5).
Such surface-protecting films should exhibit sufficient adhesiveness during affixation to the optical member. They should also have excellent removability because they will be removed after usage typically in production processes to give optical members. To have excellent removability, the surface-protecting films require not only small release force (easiness to release), but also such a property as to be resistant to increase in adhesive strength (release force) with time after the application to an adherend such as an optical member. This property is also referred to as “resistance to adhesive strength increase.”
To obtain the properties such as easiness to release and resistance to adhesive strength increase, a water-insoluble crosslinking agent is effectively used in a pressure-sensitive adhesive (or in a pressure-sensitive adhesive composition) to form a pressure-sensitive adhesive layer. Exemplary known pressure-sensitive adhesive compositions using a water-insoluble crosslinking agent include water-dispersible removable acrylic pressure sensitive adhesive compositions containing an oil-soluble crosslinking agent (see PTL 6 and 7).
However, water-dispersible acrylic pressure-sensitive adhesive compositions using a water-insoluble crosslinking agent as with the above-mentioned pressure-sensitive adhesive compositions often suffer from visual defects such as “dimples” on the pressure-sensitive adhesive layer surface, in which the defects occur during the formation of the pressure-sensitive adhesive layer. This is because large particles of the water-insoluble crosslinking agent remain without sufficient dispersion in the pressure sensitive adhesive composition and cause the visual defects. The water-insoluble crosslinking agent, particularly when used to form a pressure-sensitive adhesive layer of a surface-protecting film, may therefore disadvantageously impede the inspection of the adherend with the surface-protecting film. To reduce or eliminate dimples caused by the water-insoluble crosslinking agent, a leveling agent is typically used.
A water-dispersible acrylic pressure-sensitive adhesive composition, when containing a surfactant such as the leveling agent or an emulsifier, generally exhibits poor defoaming activity. Bubbles, if contained in a coating composition to form a pressure-sensitive adhesive layer, may remain in the resulting pressure-sensitive adhesive layer formed by applying the composition using a coating head. The remained bubbles disadvantageously form dimples in the pressure-sensitive adhesive layer surface to cause the pressure-sensitive adhesive layer to have a poor appearance, or cause the pressure-sensitive adhesive layer to suffer from thickness variation (uneven thickness), or remain as bubble defects in the pressure-sensitive adhesive layer even after drying. An antifoaming agent is effectively used for better defoaming activity. However, the antifoaming agent, when added, disadvantageously causes crawling. A solid nucleating agent such as silica, when contained as the antifoaming agent, disadvantageously acts as foreign matter and causes the coating (applied layer) to have an inferior appearance.
Under such present circumstances, no pressure-sensitive adhesive layer has been obtained, which pressure-sensitive adhesive layer is formed from a water-dispersible acrylic pressure-sensitive adhesive composition, has adhesiveness and removability (particularly resistance to adhesive strength increase) at satisfactory levels, less suffers from “dimples” and other visual defects, and exhibits superior visual quality.
In a use typically as a surface-protecting film (particularly as a surface-protecting film for an optical member), stains on the adherend surface disadvantageously adversely affect the optical properties of the optical member. The stains are caused typically by so-called “adhesive residue” where the pressure-sensitive adhesive remains on the adherend (e.g., optical member) surface after the pressure-sensitive adhesive sheet is removed. The stains are also caused by the transfer (migration) of a component from the pressure-sensitive adhesive layer to the adherend surface. To prevent these, strong demands are made on the pressure-sensitive adhesive and the pressure-sensitive adhesive layer to less stain the adherend,
When a pressure-sensitive adhesive sheet is used as a surface-protecting film, the surface-protecting film requires such a property as to be resistant to scratches on the surface (substrate surface). This property is hereinafter also referred to as “scratch resistance.” This is because, if scratches are present in the surface (substrate surface) of the surface-protecting film, it is difficult to determine whether any scratches are derived from the surface-protecting film or from the adherend (e.g., optical member) to be visually inspected. An exemplary technique for better scratch resistance of a backside of a surface-protecting is a technique of providing a hard surface layer (top coat layer) on the backside of the surface-protecting film. The “backside” herein refers to a surface (substrate side surface) of the surface-protecting film, namely, the opposite side to a surface (a pressure-sensitive adhesive layer surface) to be applied to the adherend.
However, the surface-protecting film bearing the coat layer on the backside thereof, when applied to an adherend and is observed as intact from the backside, appears cloudy wholly or partially, and this disadvantageously causes poor visibility of the adherend surface. The observation is performed typically in a bright room admitting outside light, or under a fluorescent lamp in a bright room. In addition, the top coat layer, if having a variation or deviation in thickness, suffers from a difference in reflectance from one region to another and appears relatively cloudy in a thick region. This disadvantageously causes further poorer visibility of the adherend surface.
To prevent this, a demand has been made to provide a surface-protecting film that has a top coat layer having superior scratch resistance on the backside (substrate surface) thereof, less appears cloudy wholly or partially, and exhibits a good appearance.
Surface-protecting films, particularly when used typically in working or transportation processes of static-sensitive products such as liquid crystal cells and semiconductor devices, require such properties as to be resistant to static electrification (antistatic properties).
Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive sheet as follows. The pressure-sensitive adhesive sheet includes a transparent film substrate having a top coat layer; and an acrylic pressure-sensitive adhesive layer present on at least one side of the substrate, has superior visual quality, less suffers from adhesive strength increase with time, and is highly resistant to scratches and static electrification. The superior “visual quality” refers to that the pressure sensitive adhesive sheet less suffers from visual defects, such as dimples and bubble defects, in the pressure-sensitive adhesive layer and less appears cloudy.
After intensive investigations to achieve the object, the present inventors have found that a specific pressure-sensitive adhesive sheet is highly resistant to scratches and static electrification, has superior visual quality, and exhibits satisfactory resistance to adhesive strength increase; in which the pressure-sensitive adhesive sheet includes a transparent film substrate and, on at least one side thereof, an acrylic pressure-sensitive adhesive layer, the transparent film substrate has a top coat layer having a specific configuration with an average thickness and a thickness variation being controlled, the acrylic pressure sensitive adhesive layer is formed from a water-dispersible acrylic pressure-sensitive adhesive composition, and the composition includes, as components, an acrylic emulsion polymer derived from constitutive monomers in a specific formulation, and a polypropylene glycol (PPG)/polyethylene glycol (PEG) block copolymer having a specific structure (or a derivative of the copolymer). The present invention has been made based on these findings.
Specifically, the present invention provides a pressure-sensitive adhesive sheet including a transparent film substrate; and an acrylic pressure-sensitive adhesive layer present on or above at least one side of the transparent film substrate. In the pressure-sensitive adhesive sheet, the transparent film substrate includes a base layer made from a resinous material; and a top coat layer present on or above a first face of the base layer; the top coat layer is formed from a polythiophene, an acrylic resin, and a melamine crosslinking agent and has an average thickness Dave of from 2 to 50 nm and a thickness variation ΔD of 40% or less; the acrylic pressure-sensitive adhesive layer is formed from a water-dispersible removable acrylic pressure-sensitive adhesive composition; the composition includes an acrylic emulsion polymer (A) and a compound (B) represented by Formula (I); the acrylic emulsion polymer (A) is derived from constitutive monomers including a (meth)acrylic alkyl ester and a carboxyl-containing unsaturated monomer as essential constitutive monomers, where the constitutive monomers include the (math) acrylic alkyl ester in a content of 70 to 99.5 percent by weight and the carboxyl-containing unsaturated monomer in a content of 0.5 to 10 percent by weight based on the total amount of the entire constitutive monomers; and the acrylic emulsion polymer (A) is polymerized with a reactive emulsifier containing at least one radically polymerizable functional group per molecule, where Formula (I) is expressed as follows:
R1O—(PO)a-(EO)b—(PO)c—R2 (I)
wherein each of R1 and R2 independently represents a straight or branched chain alkyl group or hydrogen atom; PO represents oxypropylene group; EO represents oxyethylene group; and each of “a”, “b”, and “c” independently denotes a positive integer, where EO(s) and POs are added in a block manner.
The resinous material constituting the base layer in the pressure-sensitive adhesive sheet may include a poly(ethylene terephthalate) or a poly(ethylene naphthalate) as a principal resinous component.
In the pressure-sensitive adhesive sheet, the water-dispersible removable acrylic pressure-sensitive adhesive composition may further include a water-insoluble crosslinking agent (C) having two or more carboxyl-reactive functional groups per molecule, which carboxyl-reacting functional groups are capable of reacting with carboxyl group.
The pressure-sensitive adhesive sheet may serve as a surface-protecting film for an optical member.
The pressure-sensitive adhesive sheet according to the present invention, as having the transparent film substrate, is highly resistant to scratches and static electrification and less appears cloudy. The pressure-sensitive adhesive sheet according to the present invention, as having the acrylic pressure-sensitive adhesive layer, less suffers from visual defects such as dimples and bubble defects, has removability and adhesiveness at satisfactory levels, and, particularly, is resistant to increase in adhesive strength to the adherend with time. The pressure-sensitive adhesive sheet according to the present invention, as having the configuration as described above, has particularly superior visual quality, enables easy visual inspection of an adherend (e.g., optical member) with the pressure-sensitive adhesive sheet, and can contribute to better inspection accuracy. For these reasons, the pressure-sensitive adhesive sheet according to the present invention is useful particularly in the surface protection of an optical film.
A pressure-sensitive adhesive sheet according to an embodiment of the present invention has a transparent film substrate and, on at least one side thereof, an acrylic pressure-sensitive adhesive layer. As used herein the term “pressure-sensitive adhesive sheet” also refers to and includes one in the form of a tape, i.e., a “pressure sensitive adhesive tape.” A surface of the pressure sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) in the pressure-sensitive adhesive sheet according to the present invention is also referred to as an “adhesive face.”
The pressure-sensitive adhesive sheet according to the present invention may be a double-coated pressure-sensitive adhesive sheet having adhesive faces as both surfaces thereof, or a single-coated pressure-sensitive adhesive sheet having an adhesive face as only one surface thereof. Above all, the pressure-sensitive adhesive sheet is preferably a single-coated pressure-sensitive adhesive sheet when used in the surface protection of an adherend. Specifically, in a preferred embodiment, the pressure-sensitive adhesive sheet according to the present invention is a pressure-sensitive adhesive sheet (single-coated pressure-sensitive adhesive sheet) having a transparent film substrate and, on one side thereof, an acrylic pressure-sensitive adhesive layer. In a more preferred embodiment from the viewpoint of antistatic properties (resistance to static electrification), the pressure-sensitive adhesive sheet (single-coated pressure-sensitive adhesive sheet) has a structure having one surface serving as a surface of the after-mentioned top coat layer surface; and the other surface serving as an adhesive face.
Transparent Film Substrate
The transparent film substrate in the pressure-sensitive adhesive sheet according to the present invention has at least a base layer made from a resinous material; and the top coat layer provided on or above a first face of the base layer. The transparent film substrate may have a structure (layered structure) having the top coat layer on only one side (first face) of the base layer, or a structure (layered structure) having the top coat layer on both sides (first face and second face) of the base layer. In a preferred embodiment, the transparent film substrate has a structure having the top coat layer on only one side (first face) of the base layer, i.e., a layered structure of [(base layer)/(top coat layer)].
Base Layer
The base layer of the transparent film substrate is a transparent molded article that is formed from a resinous material and is in the form of a film (thin film). Specifically, the base layer is preferably any of resin films formed by molding various resinous materials into films. The resinous material constituting the base layer is preferably, but not limited to, such a resinous material as to form a resin film excellent in one or more of properties such as transparency, mechanical strength, thermal stability, water shielding properties, and isotropy. Specifically, the resinous material is preferably one containing, as a principal component (resinous component), any resin selected typically from polyester polymers such as poly(ethylene terephthalate)s (PETs), poly(ethylene naphthalate)s, and poly(butylene terephthalate)s; cellulosic polymers such as diacetyl cellulose and triacetyl cellulose; polycarbonate polymers; and acrylic polymers such as poly(methyl methacrylate)s. The principal component refers to a principal component of the resinous material, such as a component that constitutes 50 percent by weight or more of the total weight (100 percent by weight) of the resinous material. The resinous material is more preferably one containing a poly(ethylene terephthalate) or a polyethylene naphthalate) as a principal component. Examples of the resinous material for use herein further include styrenic polymers such as polystyrenes and acrylonitrile-styrene copolymers; olefinic polymers such as polyethylenes, polypropylenes, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; vinyl chloride polymers; amide polymers such as nylon 6, nylon 6,6, and aromatic polyamides; imide polymers; sulfonic polymers; poly(ether sulfone) polymers; poly(ether ether ketone) polymers; poly(phenylene sulfide) polymers; poly(vinyl alcohol) polymers; polyoxymethylene polymers; and epoxy polymers. The base layer may also be made from a blend of two or more of the polymers. The base layer preferably has minimum anisotropy in optical properties such as phase difference. Particularly when used as a surface-protecting film for an optical member, it is useful to minimize the optical anisotropy of the base layer. The base layer may have a single-layer structure, or a multilayer structure including two or more layers having different compositions. In a preferred embodiment, the base layer has a single-layer structure.
Where necessary, the base layer may further contain any of additives such as antioxidants, ultraviolet absorbers, antistatic component, plasticizers, and colorants (e.g., pigments and dyestuffs).
The first face (surface on which a top coat layer is to be provided) of the base layer may have been subjected to any of known or customary surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation, acid treatment, base treatment, and primer coating. The surface treatment is performed typically for better adhesion between the base layer and the top coat layer. Among them, preferred is such a surface treatment as to introduce a polar group, such as hydroxyl group (—OH group), into the first face of the base layer.
The second face of the base layer may have also been subjected to a surface treatment as above. The second face is generally the surface on which an acrylic pressure sensitive adhesive layer is to be formed. The surface treatment is performed typically for better adhesion between the transparent film substrate and the acrylic pressure-sensitive adhesive layer (for better anchoring capability of the acrylic pressure-sensitive adhesive layer).
The base layer may have any thickness suitably selectable according to the intended use and purpose, but has a thickness of preferably from 10 to 200 μm, more preferably from 15 to 100 μm, and furthermore preferably from 20 to 70 μm. This range is preferred for the balance of the strength and workability (e.g., handleability) with other properties such as cost and facilitation of visual inspection.
The base layer may have a refractive index not critical, but preferably from 1.43 to 1.6 and more preferably from 1.45 to 1.5 from the Viewpoint of visual quality.
The base layer may have a total luminous transmittance in the visible light region not critical, hut, from the viewpoint of visual quality, preferably from 80% to 97% and more preferably from 85% to 95% as determined according to JIS K7361-1.
The base layer may have an arithmetic mean surface roughness (Ra) not critical, but preferably from 0.001 to 1 μm and more preferably from 0.01 to 0.7 μm on the second face. The second face is generally the surface on which an acrylic pressure-sensitive adhesive layer is to be formed. The base layer, if having an arithmetic mean surface roughness on the second face of more than 1 μm, may cause the coated surface (adhesive face) to have inferior thickness accuracy. The base layer in this case may also cause the acrylic pressure-sensitive adhesive layer to have insufficient anchoring capability to the transparent film substrate, because the pressure-sensitive adhesive fails to migrate into the space between surface asperities of the transparent film substrate, resulting in a smaller contact area between the pressure-sensitive adhesive layer and the transparent substrate. These are because the acrylic pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to the present invention has a high solvent-insoluble content. In contrast, the base layer, if having the arithmetic mean surface roughness of less than 0.001 μm, may have poor handleability or be difficult to be produced industrially.
Top Coat Layer
The top coat layer of the transparent film substrate in the pressure-sensitive adhesive sheet according to the present invention is a surface layer arranged on at least the first face of the base layer and includes at least a polythiophene, an acrylic resin, and a melamine crosslinking agent as essential components. The pressure-sensitive adhesive sheet according to the present invention, as having the top coat layer, can exhibit any of various functions such as scratch resistance, antistatic properties, solvent resistance, printability, and ink adhesion. The pressure sensitive adhesive sheet according to the present invention, when having the function or functions, is preferably usable particularly in the surface protection of an optical film.
The acrylic resin in the top coat layer serves as a basic component (base resin) contributing to the film-formation of the top coat layer and is a resin containing an acrylic polymer as a base polymer. The “base polymer” refers to a principal component among polymer components, namely, a component constituting 50 percent by weight or more of the total amount of the polymer components. Specifically, the acrylic polymer is contained in the acrylic resin in a content of 50 percent by weight or more (e.g., from 50 to 100 percent by weight), preferably from 70 to 100 percent by weight, and more preferably from 90 to 100 percent by weight, based on the total weight (100 percent by weight) of the acrylic resin.
The “acrylic polymer” refers to a polymer containing, as a principal monomer component, a monomer having at least one (meth)acryloyl group in molecule (per molecule). A monomer of this type is hereinafter also referred to as an “acrylic monomer.” Specifically, the acrylic monomer is present in a content of 50 percent by weight or more of the total weight (100 percent by weight) of monomer components constituting the acrylic polymer. As used herein the term “(meth)acryloyl group” refers to acryloyl group and/or methacryloyl group (either one or both of acryloyl group and methacryloyl group).
The acrylic resin can be any of acrylic resins of various types, such as thermosetting acrylic resins, ultraviolet-curable acrylic resins, electron-beam-curable acrylic resins, and two-component acrylic resins. Each of different acrylic resins may be used alone or in combination. Among them, preferably employed is such an acrylic resin as to form a top coat layer that has excellent scratch resistance (e.g., being evaluated as good (G) in the scratch resistance evaluation in “Evaluations” mentioned later) and satisfactorily transmits light. The acrylic resin in the top coat layer can also be grasped as a binder (binder resin) for the polythiophene (antistatic component).
The acrylic polymer serving as a base polymer of the acrylic resin is preferably, but not limited to, an acrylic polymer containing methyl methacrylate (MMA) as a principal monomer component (monomeric component) and more preferably a copolymer of methyl methacrylate with one or more other monomers (of which acrylic monomers other than methyl methacrylate are preferred). Methyl methacrylate may be copolymerized to form the acrylic polymer in a percentage not critical, but preferably 50 percent by weight or more (e.g., from 50 to 90 percent by weight) and more preferably 60 percent by weight or more (e.g., from 60 to 85 percent by weight) based on the total weight (100 percent by weight) of entire monomer components constituting the acrylic polymer.
The other monomers to be copolymerized with methyl methacrylate to form the acrylic polymer are exemplified by, but not limited to, (meth)acrylic alkyl esters other than methyl methacrylate, of which preferably exemplified are (math) acrylic alkyl esters whose alkyl moiety being a straight or branched chain alkyl group; and (meth)acrylic alkyl esters (cycloalkyl(meth)acrylates) whose alkyl moiety being an alicyclic alkyl group (cycloalkyl group).
The (meth)acrylic alkyl esters whose alkyl moiety being a straight or branched chain alkyl group are exemplified by, but not limited to, alkyl acrylates (acrylic alkyl esters) whose alkyl moiety having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, n-butyl acrylate (BA), and 2-ethylhexyl acrylate (2EHA); and alkyl methacrylates (methacrylic alkyl esters) whose alkyl moiety having 2 to 6 carbon atoms, such as ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. The (meth)acrylic alkyl esters whose alkyl moiety being an alicyclic alkyl group are exemplified by, but not limited to, cycloalkyl acrylates whose cycloalkyl moiety having 5 to 7 carbon atoms, such as cyclopentyl acrylate and cyclohexyl acrylate; and cycloalkyl methacrylates with a cycloalkyl moiety having 5 to 7 carbon atoms, such as cyclopentyl methacrylate and cyclohexyl methacrylate (CHMA).
In a preferred embodiment, the acrylic polymer is one derived from monomer components including at least methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA). In this embodiment, cyclohexyl methacrylate may be copolymerized in a percentage not critical, but typically preferably 25 percent by weight or less (e.g., from 0.1 to 25 percent by weight) and more preferably 15 percent by weight or less (e.g., from 0.1 to 15 percent by weight) based on the total weight (100 percent by weight) of entire monomer components constituting the acrylic polymer.
In another preferred embodiment, the acrylic polymer is one derived from monomer components including at least methyl methacrylate (MMA) and at least one of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA). In this embodiment, n-butyl acrylate and/or 2-ethylhexyl acrylate may be copolymerized in a percentage (in a total percentage of the two monomers when both of them are to be copolymerized) not critical, but typically preferably 40 percent by weight or less (e.g., from 1 to 40 percent by weight), more preferably from 10 to 40 percent by weight, furthermore preferably 30 percent by weight or less (e.g., from 3 to 30 percent by weight), and particularly preferably from 15 to 30 percent by weight, based on the total weight (100 percent by weight) of entire monomer components constituting the acrylic polymer.
In a particularly preferred embodiment, the acrylic polymer is one derived from monomer components including substantially methyl methacrylate (MMA), cyclohexyl methacrylate (CHMA), and at least one of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA). Specifically, preferred is an acrylic polymer derived from monomer components including MMA, CHMA, and at least one of BA and 2EHA in a total sum of contents (total content) of 52 percent by weight or more based on the total weight (100 percent by weight) of entire monomer components constituting the acrylic polymer.
Any of other monomers may be copolymerized with the above monomers to form the acrylic polymer within ranges not significantly adversely affecting advantageous effects of the present invention. The other monomers are exemplified by carboxyl-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; acid-anhydride-containing monomers such as maleic anhydride and itaconic anhydride; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and α-methylstyrene; amido-containing monomers such as acrylamide and N,N-dimethylacrylamide; amino-containing monomers such as aminoethyl(meth)acrylate and N,N-dimethylaminoethyl(meth)acrylate; imido-containing monomers such as cyclohexylmaleimide; epoxy-containing monomers such as glycidyl(meth)acrylate; (meth)acryloylmorpholine; vinyl ethers such as methyl vinyl ether; and hydroxyl-containing monomers such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxypentyl(meth)acrylate, hydroxyhexyl(meth)acrylate, hydroxyoctyl(meth)acrylate, hydroxydecyl(meth)acrylate, hydroxylauryl(meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, N-methylol(meth)acrylamide, vinyl alcohol, allyl alcohol, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. Such “other monomer(s)” may be copolymerized in a percentage (in a total percentage when two or more other monomers are used) not critical, but preferably 20 percent by weight or less, more preferably 10 percent by weight or less, furthermore preferably 5 percent by weight or less, and most preferably 3 percent by weight or less. Substantially no “other monomer” may be copolymerized. Typically, the content of other monomers may be 0.1 percent by weight or less based on the total weight (100 percent by weight) of entire monomers constituting the acrylic polymer.
In a preferred embodiment, the acrylic polymer is derived from copolymerization components including substantially no monomers containing an acidic functional group (acidic-functional-group-containing monomers), such as acrylic acid and methacrylic acid. Specifically, the content of acidic-functional-group-containing monomers is preferably 0.1 percent by weigh; or less based on the total amount of entire monomer components constituting the acrylic polymer. The top coat layer, when employing, as components, a melamine crosslinking agent in combination with the acrylic polymer containing substantially no acidic-functional-group-containing monomer, can readily have higher hardness and exhibit better adhesion to the base layer. As used herein the term “acidic functional group” refers to a functional group capable of becoming acidic, such as carboxyl group or acid anhydride group. This is also true for the following description.
The acrylic polymer is preferably derived from copolymerization components including a monomer having at least one hydroxyl group (hydroxyl-containing monomer). The hydroxyl-containing monomer, when copolymerized, can help the top coat layer to have better adhesion to the base layer.
The acrylic resin constituting the top coat layer may further include one or more other resinous components (except polythiophenes) in addition to the acrylic polymer. The other resinous components may be present in a content of less than 50 percent by weight based on the total weight (100 percent by weight) of the acrylic resin.
The polythiophene in the top coat layer is a component (antistatic component) having the function of preventing the static electrification of the pressure-sensitive adhesive sheet according to the present invention. The pressure-sensitive adhesive sheet according to the present invention, as including the polythiophene in the top coat layer, is highly resistant to static electrification (has excellent antistatic properties) and is preferably usable particularly as a surface-protecting film for use typically in a working or transportation process of static-sensitive articles such as liquid crystal cells and semiconductor devices.
In addition, the polythiophene is highly hydrophobic, less absorbs moisture even in a high-humidity environment (under humid conditions), and less causes clouding of the transparent film substrate (more specifically, clouding of the top coat layer). In contrast, a hygroscopic substance (e.g., an ammonium salt), if used as an antistatic component in the top coat layer, often causes clouding of a substrate (more specifically, clouding of a top coat layer) in a high-humidity environment.
Examples of the polythiophene include not only polymers of unsubstituted thiophene, but also polymers of a substituted thiophene such as 3,4-ethylenedioxythiophene. Among them, preferred from the viewpoint of antistatic properties is a polymer of 3,4-ethylenedioxythiophene, i.e., a poly(3,4-ethylenedioxythiophene).
The polythiophene may have a weight-average molecular weight (Mw) in terms of a polystyrene standard not critical, but preferably 40×104 or less (e.g., from 0.1×104 to 40×104) and more preferably from 0.5×104 to 30×104. The polythiophene, if having a weight-average molecular weight Mw of more than 40×104, may suffer from insufficient compatibility to cause poor visual duality and/or insufficient solvent resistance in some combinations with other components constituting the top coat layer. In contrast, the polythiophene, if having a weight-average molecular weight Mw of less than 0.1×104, may cause insufficient scratch resistance.
The polythiophene may be used in an amount (content in the top coat layer) not critical, but preferably from 10 to 200 parts by weight, more preferably from 25 to 150 parts by weight, and furthermore preferably from 40 to 120 parts by weight, per 100 parts by weight of the acrylic polymer in the top coat layer. The polythiophene, if used in an amount of less than 10 parts by weight, may cause the top coat layer side surface of the transparent film substrate to have an excessively high surface resistivity, and this may invite insufficient antistatic properties. In contrast, the polythiophene, if used in an amount of more than 200 parts by weight, may readily cause the top coat layer to have a large thickness variation. ΔD and thereby cause the pressure-sensitive adhesive sheet to appear partially cloudy, resulting in inferior visual quality. In this case, the polythiophene may suffer from insufficient compatibility to cause poor visual quality and/or insufficient solvent resistance in some combinations with other components constituting the top coat layer.
In an embodiment, the top coat layer is formed by a process of preparing a liquid composition (top coat layer coating composition); applying the liquid composition to the base layer surface; and drying or curing the applied composition, as described later. In this embodiment, preferably employed to prepare the composition is a solution or dispersion of the polythiophene in water (aqueous polythiophene solution or dispersion). The aqueous polythiophene solution or dispersion can be prepared by dissolving or dispersing a polythiophene having a hydrophilic functional group in water. The polythiophene just mentioned above can be synthetically prepared typically by copolymerizing a monomer having at least one hydrophilic functional group per molecule. The hydrophilic functional group is exemplified by sulfa group, amino group, amido group, imino group, hydroxyl group, mercapto group, hydrazino group, carboxyl group, quaternary ammonium group, sulfuric ester group (—O—SO3H), and phosphoric ester groups (e.g., —O—PO(OH)2). Each of these hydrophilic functional groups may form a salt. The aqueous polythiophene solution is also available as any of commercial products typically under the trade names of “Denatron” Series (from Nagase ChemteX Corporation).
Of such aqueous polythiophene solutions, particularly preferred is an aqueous polythiophene solution containing a polystyrenesulfonate (PSS) for stable antistatic properties. In the solution, a PSS can be present as a dopant doped to the polythiophene. The aqueous PSS-containing polythiophene solution may have a ratio of the polythiophene to the polystyrenesulfonate[polythiophene:polystyrenesulfonate] not critical, but preferably from 1:5 to 1:10. The aqueous PSS-containing polythiophene solution may have a total sum of contents (total content) of the polythiophene and polystyrenesulfonate not critical, but preferably from 1 to 5 percent by weight. The aqueous PSS-containing polythiophene solution is also available as any of commercial products typically under the trade name of “Baytron” from H.C. Stark Co., LLC. The aqueous PSS-containing polythiophene solution, when used, may contain a polythiophene and a polystyrenesulfonate in a total amount not critical, but preferably from 10 to 200 parts by weight, more preferably from 25 to 150 parts by weight, and furthermore preferably from 40 to 120 parts by weight, per 100 parts by weight of the acrylic polymer in the top coat layer.
The top coat layer, as employing the acrylic resin as a base resin in combination with the polythiophene as an antistatic component, can give a transparent film substrate having a low surface resistivity even when the top coat layer has a small thickness. A better result can be obtained particularly when employing, as the acrylic resin, an acrylic resin mainly including an acrylic polymer derived from copolymerization components including substantially no acidic-functional-group-containing monomer.
The melamine crosslinking agent in the top coat layer has the function of crosslinking the acrylic polymer to develop at least one advantageous effect selected from better scratch resistance, better solvent resistance, better ink adhesion, and lower frictional coefficient (of which better scratch resistance is preferred). The melamine crosslinking agent is a compound having a melamine structure. The melamine crosslinking agent is exemplified by methylolmelamines such as monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine; and alkoxyalkylmelamines including alkoxymethylmelamines such as methoxymethylmelamine, ethoxymethylmelamine, propoxymethylmelamine, butoxymethylmelamine, hexa(methoxymethyl)melamine, hexa(ethoxymethyl)melamine, hexa(propoxymethyl)melamine, hexa(butoxymethyl)melamine, hexa(pentyloxymethyl)melamine, and hexa(hexyloxymethyl)melamine, as well as alkoxybutylmelamines such as methoxybutylmelamine, ethoxybutylmelamine, propoxybutylmelamine, and butoxybutylmelamine.
The melamine crosslinking agent is also available as any of commercial products typically under the trade names of “CYMEL 202”, “CYMEL 212”, “CYMEL 232”, “CYMEL 235”, “CYMEL 253”, “CYMEL 266”, “CYMEL 267”, “CYMEL 270”, “CYMEL 272”, “CYMEL 285”, “CYMEL 300”, “CYMEL 301”, “CYMEL 30”, “CYMEL 327”, “CYMEL 350”, “CYMEL 370”, “CYMEL 701”, “CYMEL 703”, and “CYMEL 771” (each from Cytec Industries Inc.); the trade names of “NIKALAC MW-30”, “NIKALAC MW-30M”, “NIKALAC MW-30HM”, “NIKALAC MW-45”, “NIKALAC MW-390”, “NIKALAC MX 270”, “NIKALAC MX-302”, “NIKALAC MX-706”, and “NIKALAC MX-750” (each from Sanwa Chemical Co., Ltd.).
The melamine crosslinking agent may be used in an amount (content in the top coat layer coating composition) not critical, but preferably from 5 to 100 parts by weight, more preferably from 10 to 80 parts by weight, and furthermore preferably from 20 to 50 parts by weight, per 100 parts by weight of the acrylic polymer in the top coat layer. The melamine crosslinking agent, if used in an amount of less than 5 parts by weight, may cause insufficient scratch resistance. In contrast, the melamine crosslinking agent, if used in an amount of more than 100 parts by weight, may cause insufficient printability. The melamine crosslinking agent in this case may suffer from insufficient compatibility to cause poor visual quality and/or insufficient solvent resistance in some combinations with other components constituting the top coat layer.
As is described above, the combination use of the melamine crosslinking agent with the acrylic polymer including substantially no acidic-functional-group-containing monomer, the acrylic polymer serving as a principal component of the acrylic resin, may readily allow the top coat layer to have higher hardness and to have better adhesion to the base layer.
In a preferred embodiment, the top coat layer further contains a lubricant so as to allow the pressure-sensitive adhesive sheet according to the present invention to exhibit better scratch resistance. The lubricant can be any of known or customary lubricants, of which fluorochemical and silicone lubricants are preferably employed. Among them, silicone lubricants (silicone-based lubricants) are preferred. The silicone lubricants are exemplified by polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, and polymethylalkylsiloxanes. Exemplary lubricants for use herein also include lubricants including a fluorochemical compound or silicone compound having an aryl group and/or an aralkyl group. These lubricants particularly improve the printability and are also called “printability-imparting lubricants.” Exemplary lubricants further include lubricants (reactive lubricants) including a fluorochemical compound or silicone compound having at least one crosslinkable reactive group.
The lubricant may be used in an amount not critical, but preferably from 5 to 90 parts by weight, more preferably from 1.0 to 70 parts by weight, furthermore preferably 15 parts by weight or more (e.g., from 15 to 50 parts by weight), particularly preferably 20 parts by weight or more, and most preferably 25 parts by weight or more, per 100 parts by weight of the acrylic polymer in the top coat layer. The lubricant, if used in an amount of less than 5 parts by weight, may fail to contribute to satisfactory scratch resistance. In contrast, the lubricant, if used in an amount of more than 90 parts by weight, may cause insufficient printability or may cause the top coat layer (consequently, the transparent film substrate and the pressure-sensitive adhesive sheet) to have inferior visual quality.
The lubricant probably bleeds out to the top coat layer surface, imparts lubricity to the surface, and thus reduces the frictional coefficient. The lubricant, when used suitably, can therefore contribute to better scratch resistance through reduction in frictional coefficient. The lubricant can uniformize the surface tension of the top coat layer coating composition and can also help the top coat layer to have lower nonuniformity in thickness (higher uniformity in thickness) and to less suffer from interference fringes (consequently to have better visual quality). Such better visual quality is significant particularly in a surface-protecting film for an optical member. In an embodiment, the acrylic resin constituting the top coat layer is an ultraviolet-curable acrylic resin. In this embodiment, a fluorochemical or silicone lubricant is preferably added to the top coat layer coating composition. When the composition is applied to the base layer and dried, the lubricant bleeds out at the coating surface (interface with the atmosphere), and this suppresses curing inhibition by oxygen during ultraviolet irradiation and allows the ultraviolet-curable acrylic resin to be cured sufficiently even in an outermost surface of the top coat layer.
The top coat layer may contain any of additives according to necessity, within ranges not adversely affecting advantageous effects of the present invention. The additives are exemplified by antistatic components other than polythiophenes, antioxidants, colorants (e.g., pigments and dyestuffs), viscosity-adjusting agents thixotropic agents and thickeners), film-forming aids, and catalysts (e.g., an ultraviolet-induced polymerization initiator in a composition containing an ultraviolet-curable acrylic resin).
The antistatic components other than polythiophenes can be known or customary antistatic components and are exemplified by, but not limited to, organic or inorganic electroconductive materials, and various antistatic agents.
The organic electroconductive materials are exemplified by, but not limited to, electroconductive polymers other than polythiophenes, such as polyanilines, polypyrroles, polyethyleneimines, and allylamine polymers. Each of different electroconductive polymers may be used alone or in combination. Each of the organic electroconductive materials may be used in combination with any of other antistatic components such as inorganic electroconductive materials and antistatic agents.
The polyanilines are also available as commercial products typically under the trade name of “aqua-PASS” (from Mitsubishi Rayon Co., Ltd., an aqueous solution of a poly(anilinesulfonic acid)).
The inorganic electroconductive materials are exemplified by, but not limited to, tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, copper iodide, ITO (indium oxide/tin oxide), and ATO (antimony oxide/tin oxide).
The top coat layer of the transparent film substrate in the pressure-sensitive adhesive sheet according to the present invention may be formed by a technique that is not critical, but is exemplified by a technique of dissolving or dispersing the acrylic resin, polythiophene, melamine crosslinking agent, and optional additives in a suitable solvent to give a liquid composition (top coat layer coating composition); and applying the liquid composition to a base layer surface. More specifically, preferably employed is a technique of applying the liquid composition to the base layer surface, drying the applied composition, and, where necessary, performing a curing treatment (e.g., a heat treatment or ultraviolet irradiation) to form the top coat layer.
The liquid composition (top coat layer coating composition) may have a solids content (NV; non-volatile content) not critical, but preferably 5 percent by weight or less (e.g., from 0.05 to 5 percent by weight), more preferably 1 percent by weight or less (e.g., from 0.1 to 1 percent by weight), furthermore preferably 0.5 percent by weight or less, and particularly preferably 0.3 percent by weight or less. The liquid composition, if having a solids content of more than 5 percent by weight, may fail to form a thin and uniform top coat layer (namely, with a small thickness variation ΔD). This is because typically of excessively high viscosity of the liquid composition and resulting variation in drying time from one region to another. A lower limit of the solids content of the liquid composition is not critical, but preferably 0.05 percent by weight and more preferably 0.1 percent by weight. The liquid composition, if having a solids content of less than 0.05 percent by weight, may cause a coating (layer) to be susceptible to crawling and thereby invite a larger thickness variation ΔD in some materials of the base layer and some surface conditions.
The solvent constituting the liquid composition (top coat layer coating composition) is preferably one that can stably dissolve or disperse therein components constituting the top coat layer, such as the acrylic resin, polythiophene, and melamine crosslinking agent. The solvent for use herein can be an organic solvent, water, or a mixture of them. The organic solvent is selected typically from esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone, and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aromatic hydrocarbons such as toluene and xylenes; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, and cyclohexanol; and glycol ethers. Each of these organic solvents may be used alone or in combination. Among them, preferred are solvents containing a glycol ether as a principal component (e.g., a solvent containing 50 percent by weight or more of a glycol ether).
The glycol ether is preferably at least one selected from the group consisting of alkylene glycol monoalkyl ethers and dialkylene glycol monoalkyl ethers. Specifically, these are exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol-mono-2-ethylhexyl ether.
The top coat layer has an average thickness D of from 2 to 50 nm, preferably from 2 to 30 nm, more preferably from 2 to 20 nm, and furthermore preferably from 2 to 10 nm. A top coat layer having an average thickness Dave of more than 50 nm causes a transparent film substrate to appear wholly cloudy and often causes the transparent film substrate (consequently a pressure-sensitive adhesive sheet having the transparent film substrate) to have inferior visual quality. In contrast, a top coat layer having an average thickness Dave of less than 2 nm is difficult to be formed uniformly.
The average thickness Dave of the top coat layer can be determined by measuring thicknesses of the top coat layer at five different measurement points arranged at regular intervals along a straight line crossing the top coat layer (typically, a straight line crossing the top coat layer in the width direction); and averaging the thicknesses at the five measurement points to give an arithmetic mean. Of the measurement points, two adjacent measurement points are desirably at a distance of 2 cm or longer (preferably 5 cm or longer) from each other.
The thickness of the top coat layer (thickness of the top coat layer at each measurement point) can be measured typically by observing a cross section of the transparent film substrate (or of the pressure-sensitive adhesive sheet) with a transmission electron microscope (TEM). Specifically, the measurement may be performed typically by preparing a sample from the transparent film substrate (or the pressure-sensitive adhesive sheet), staining the sample with a heavy metal to make the top coat layer distinguishable, embedding the stained sample in a resin, slicing the embedded sample ultrathin to give a cross section, and observing the cross section with the TEM. The obtained data can be utilized as the thickness of the top coat layer. Typically, a transmission electron microscope Model “H-7650” supplied by Hitachi, Ltd. can be used as the TEM.
In Examples described later, the thickness (average thickness within the field of view) of the top coat layer was actually measured by obtaining a cross-sectional image at an accelerating voltage of 100 kV and a 60000-fold magnification, converting the image to a binary code, and dividing the cross-sectional area of the top coat layer by the sample length in the field of view.
The heavy-metal staining may be omitted when the top coat layer is sufficiently distinguishable even in observation without any heavy-metal staining.
Alternatively, the thickness of the top coat layer may be determined by calculation using a calibration curve plotted based on correlations between the thickness determined by TEM and values obtained by various other thickness measuring devices (e.g., surface profile gauges, interferometric thickness gauges, infrared spectrometers, and various X-ray diffractometers).
The top coat layer has a thickness variation ΔD of from 40% or less (e.g., from 0% to 40%), preferably 30% or less, more preferably 25% or less, and furthermore preferably 20% or less.
The thickness variation ΔD of the top coat layer may be determined by measuring thicknesses of the top coat layer at five different measurement points arranged at regular intervals along a straight line crossing the top coat layer (typically, a straight line crossing the Lop coat layer in the width direction); dividing the difference between the maximum value Dmax and the minimum value Dmin of the measured thicknesses by the average thickness Dave; and defining the resulting value as the thickness variation ΔD [i.e., ΔD (%)=(Dmax−Dmin)/Dave×100]. Of the measurement points, two adjacent measurement points are desirably at a distance of 2 cm or longer (preferably 5 cm or longer) from each other. The thickness of the top coat layer at each measurement point can for example be directly measured by TEM observation or can be determined by determining a value with a suitable thickness gauge and converting the value to a thickness based on the calibration curve, as described above.
More specifically, the average thickness Dave and the thickness variation ΔD of the top coat layer can be determined in accordance with the thickness measurement method outlined in Examples.
The top coat layer, as having a thickness variation ΔD of 40% or less, less appears streaky or uneven due to partial clouding and brings good visual quality. Specifically, with a decreasing thickness variation ΔD can bring better visual quality. The top coat layer, when having a small thickness variation ΔD, also advantageously contributes to the formation of a transparent film substrate having a small average thickness Dave and a low surface resistivity.
The top coat layer may have an X-ray intensity variation ΔI not critical, but preferably 40% or less (e.g., from 0% to 40%), more preferably 30% or less, furthermore preferably 25% or less, and particularly preferably 20% or less, as determined by X-ray fluorescence (XRF) analysis. The X-ray intensity variation ΔI may be determined by measuring X-ray intensities I through XRF analysis at five different measurement points arranged at regular intervals along a straight line crossing the top coat layer (typically, a straight line crossing the top coat layer in the width direction); dividing the difference between the maximum value Imax and the minimum value Imin of the measured intensities by the average X-ray intensity Iave; and defining the resulting value as the X-ray intensity variation ΔI [ΔI (%)=(Imax−Imin)/Iave×100]. Of the measurement points, two adjacent measurement points are desirably at a distance of 2 cm or longer (preferably 5 cm or longer) from each other.
The “average X-ray intensity Iave” herein refers to an arithmetic mean of the X-ray intensities I at the five measurement points. The X-ray intensity is generally indicated in kcps (number (kilo counts) per second of X-ray photons entering through a receiving slit). Specifically, the average intensity Iave and the X-ray intensity variation ΔI can be measured typically in accordance with the X-ray intensity variation measurement method outlined in Examples. The top coat layer, when having an X-ray intensity variation ΔI of 40% or less, may less appear streaky or uneven due to partial clouding and readily bring good visual quality. In general, the X-ray intensity variation ΔI decreases with a decreasing thickness variation ΔD. The top coat layer, when having a small intensity variation ΔI, may therefore advantageously contribute to the formation of a transparent film substrate having a small average thickness Dave and a low surface resistivity.
An element to be analyzed by the XRF analysis can be any of XRF-analyzable elements contained in the top coat layer. Of such atoms, preferably employed for the XRF analysis are sulfur atom (e.g., sulfur atom (S) derived from a polythiophene contained in the top coat layer), silicon atom (e.g., silicon atom (Si) derived from a silicone lubricant contained in the top coat layer), and tin atom (e.g., tin atom (Sn) derived from tin oxide particles as a filler contained in the top coat layer). In a preferred embodiment, the top coat layer has an X-ray intensity variation ΔI of 40% or less as determined by sulfur atom XRF analysis. In another preferred embodiment, the to coat layer has an X-ray intensity variation ΔI of 40% or less as determined by silicon atom XRF analysis.
The XRF analysis can be performed typically in a manner as follows. Specifically, a commercially available XRF analyzer is preferably employed. Any of suitable dispersive crystal can be selected, of which a Ge crystal is typically preferably employed. The output settings and other conditions can be suitably selected in accordance with the used instrument. Usually, a sufficient resolution can be obtained with an output of about 70 mA at 50 kV. More specifically, the XRF analysis conditions outlined in Examples can be preferably employed.
In a preferred embodiment for higher measurement accuracy, an element preferred to be analyzed has an X-ray intensity per area corresponding to a 30 mm diameter circle of about 0.01 kcps or more (more preferably 0.03 kcps or more, typically from 0.05 to 3.00 kcps) under predetermined XRF analysis conditions.
The transparent film substrate in the pressure-sensitive adhesive sheet according to the present invention is a substrate that is transparent. Specifically, the transparent film substrate may have a total luminous transmittance in the visible light region not critical, but preferably from 80% to 97% and more preferably from 85% to 95% as determined according to JIS K7361-1. The transparent film substrate may have a haze not critical, but preferably from 1.0% to 5.0% and more preferably from 2.0% to 3.5% as determined according to JIS K7136. The transparent film substrate, if having a total luminous transmittance and/or a haze out of the above-specified range, may readily impede accurate visual inspection of the adherend.
The transparent film substrate may have a thickness not critical, but preferably from 10 to 150 μm and more preferably from 30 to 100 μm. The transparent film substrate, if having a thickness of less than 10 μm, may fail to effectively protect the optical member from scratches. In contrast, the transparent film substrate, if having a thickness of more than 150 μm, may invite higher cost.
Acrylic Pressure-Sensitive Adhesive Layer
The acrylic pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) in the pressure sensitive adhesive sheet according to the present invention is formed from (derived from) a water-dispersible acrylic pressure-sensitive adhesive composition (water-dispersible removable acrylic pressure-sensitive adhesive composition) containing an acrylic emulsion polymer (A) and a compound (B) as essential components. This composition is hereinafter also referred to as a “pressure-sensitive adhesive composition for use in the present invention.” In a preferred embodiment, the pressure-sensitive adhesive composition for use in the present invention further contains a water-insoluble crosslinking agent (C).
Acrylic Emulsion Polymer (A)
The acrylic emulsion polymer (A) in the pressure-sensitive adhesive composition for use in the present invention is a polymer (acrylic polymer) derived from constitutive monomers (constitutive monomer components) essentially including a (meth)acrylic alkyl ester and a carboxyl-containing unsaturated monomer. Specifically, the acrylic emulsion polymer (A) is a polymer obtained from a monomer mixture including a (meth)acrylic alkyl ester and a carboxyl-containing unsaturated monomer as essential components. Each of different acrylic emulsion polymers may be used alone or in combination as the acrylic emulsion polymer (A). As used herein the term “(meth)acrylic” refers to “acrylic” and/or “methacrylic” (either one or both of “acrylic” and “methacrylic.”
The (meth)acrylic alkyl ester is used as a principal monomer component to constitute the acrylic emulsion polymer (A) and mainly plays a role of developing adhesiveness, removability, and other basic properties as a pressure-sensitive adhesive (or as a pressure-sensitive adhesive layer). Of (meth)acrylic alkyl esters, acrylic alkyl esters may readily impart flexibility to the polymer constituting the pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) and help the pressure-sensitive adhesive layer to exhibit adhesion and tackiness; whereas methacrylic alkyl esters may readily impart hardness (rigidity) to the polymer constituting the pressure-sensitive adhesive layer and effectively control the removability of the pressure-sensitive adhesive layer. The (meth)acrylic alkyl ester is exemplified by, but not limited to, (meth)acrylic alkyl esters whose alkyl moiety being a linear, branched chain, or cyclic alkyl group having 1 to 16 more preferably 2 to 10, and furthermore preferably 4 to 8) carbon atoms.
Of the acrylic alkyl esters, preferred are acrylic alkyl esters whose alkyl moiety being an alkyl group having 2 to 14 (more preferably 4 to 8) carbon atoms, which are exemplified by acrylic alkyl esters whose alkyl moiety being a straight or branched chain alkyl group, such as n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, and isononyl acrylate; and alicyclic acrylic alkyl esters such as isobornyl acrylate. Among them, preferred are 2-ethylhexyl acrylate, n-butyl acrylate, and isobornyl acrylate.
Of the methacrylic alkyl esters, preferred are methacrylic alkyl esters whose alkyl moiety being an alkyl group having 1 to 16 (more preferably 1 to 8) carbon atoms, which are exemplified by methacrylic alkyl esters whose alkyl moiety being a straight or branched chain alkyl group, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, and t-butyl methacrylate; and alicyclic methacrylic alkyl esters such as cyclohexyl methacrylate, bornyl methacrylate, and isobornyl methacrylate. Among them, preferred are methyl methacrylate and n-butyl methacrylate.
The (meth)acrylic alkyl ester may be suitably selected according typically to the target tackiness, and each of different (meth)acrylic alkyl esters may be used alone or in combination.
The (meth)acrylic alkyl ester is present in a content of from 70 to 99.5 percent by weight, and more preferably from 85 to 99 percent by weight, based on the total weight (100 percent by weight) of constitutive monomers (entire constitutive monomers) constituting the acrylic emulsion polymer (A). The (meth)acrylic alkyl ester, if present in a content of more than 99.5 percent by weight, causes an excessively low content of the carboxyl-containing unsaturated monomer, thereby causes the pressure-sensitive adhesive composition to give a pressure-sensitive adhesive layer having anchoring capability and less-staining properties at insufficient levels or having insufficient emulsion stability. In contrast, the (meth)acrylic alkyl ester, if present in a content of less than 70 percent by weight, fails to contribute to satisfactory adhesiveness and removability of the acrylic pressure-sensitive adhesive layer. When two or more different (meth)acrylic alkyl esters are used, the total amount (total content) of the entire (meth)acrylic alkyl esters may fall within the above-specified range. Though not critical, the weight ratio of acrylic alkyl ester (s) to methacrylic alkyl ester(s) in content in the (math) acrylic alkyl ester(s) (content of acrylic alkyl ester(s): content of methacrylic alkyl ester(s)) is preferably from about 100:0 to about 30:70 and more preferably from 100:0 to 50:50.
The carboxyl-containing unsaturated monomer can form a protective layer on the surface of emulsion particles including the acrylic emulsion polymer (A) and exhibit the function of preventing the shear fracture of the emulsion particles. This function is further improved by neutralizing carboxyl group with a base. The stability of emulsion particles against shear fracture is more generally referred to as “mechanical stability”. The carboxyl containing unsaturated monomer, when used in combination with at least one multifunctional compound reactive with carboxyl group (e.g., a multifunctional epoxy compound), can also act as crosslinking points during the formation of the acrylic pressure-sensitive adhesive layer through water removal. In addition, the carboxyl-containing unsaturated monomer can increase the adhesion (anchoring capability) of the acrylic pressure-sensitive adhesive layer to the substrate through the multifunctional compound. The carboxyl-containing unsaturated monomer is exemplified by (meth)acrylic acid (acrylic acid and methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxyethyl acrylate, and carboxypentyl acrylate. As used herein the term “carboxyl-containing unsaturated monomer” also refers to and includes acid-anhydride-containing unsaturated monomers such as maleic anhydride and itaconic anhydride. Among them, acrylic acid is preferred for a high relative concentration on the emulsion particle surface to form a denser protective layer. Each of different carboxyl-containing unsaturated monomers may be used alone or in combination.
The carboxyl-containing unsaturated monomer is present in a content of from 0.5 to 10 percent by weight, preferably from 1 to 5 percent by weight, and more preferably from 2 to 4 percent by weight, based on the total weight (100 percent by weight) of constitutive monomers (entire constitutive monomers) constituting the acrylic emulsion polymer (A). The carboxyl-containing unsaturated monomer, if present in a content of more than 10 percent by weight, may be polymerized in water to cause thickening (viscosity increase) because such a carboxyl-containing unsaturated monomer (e.g., acrylic acid) is generally soluble in water. In addition, a pressure-sensitive adhesive layer, if formed, from a composition in this case, may suffer from increase in interaction with a functional group on the adherend polarizing plate surface and thereby suffer from adhesive strength increase with time, and this may impede the removal of the pressure-sensitive adhesive sheet from the adherend. In contrast, the carboxyl-containing unsaturated monomer, if present in a content of less than 0.5 percent by weight, fails to contribute to satisfactory mechanical stability of the emulsion particles. The carboxyl-containing unsaturated monomer in this case also invites insufficient adhesion (anchoring capability) of the acrylic pressure-sensitive adhesive layer to the transparent film substrate, thus causing adhesive residue.
For imparting a specific function to the polymer, one or more other monomer components than the (meth)acrylic alkyl esters and the carboxyl-containing unsaturated monomers may be used as monomer components (constitutive monomers) to constitute the acrylic emulsion polymer (A). Examples of the other monomer components are as follows. For example, for higher cohesive force, there may be added (used) any of amido-containing monomers such as (meth)acrylamide, N,N-diethyl(meth)acrylamide, and N-isopropyl(meth)acrylamide; and amino-containing monomers such as N,N-dimethylaminoethyl(meth)acrylate and N,N-dimethylaminopropyl(meth)acrylate. These may be used in an amount per each category of from about 0.1 to about 10 percent by weight. For refractive index control or for satisfactory reworkability, there may be added (used) any of (meth)acrylic aryl esters such as phenyl(meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; and styrenic monomers such as styrene. These may be used in an amount per each category of 15 percent by weight or less. For better crosslinking in the emulsion particles and higher cohesive force, there may be added (used) any of epoxy containing monomers such as glycidyl(meth)acrylate and allyl glycidyl ether; and multifunctional monomers such as trimethylolpropane tri(meth)acrylate and divinylbenzene. These may be used in an amount per each category of less than 5 percent by weight. For forming hydrazide crosslinks in a combination use with a hydrazide crosslinking agent and thereby particularly reducing staining, there may be added (used) any of keto-containing unsaturated monomers such as diacetoneacrylamide (DAN), allyl acetoacetate, and 2-(acetoacetoxy)ethyl(meth)acrylate in an amount of less than 10 percent by weight (and preferably from 0.5 to 5 percent by weight).
Examples of the other monomer components for use herein further include hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 10-hydroxydecyl(meth)acrylate, 12-hydroxylauryl(meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, N-methylol(meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. From the viewpoint of reduction in clouding as stain, such a hydroxyl-containing unsaturated monomer is desirably added (used) in a minimal amount. Specifically, the amount of the hydroxyl-containing unsaturated monomer is preferably less than 1 percent by weight, more preferably less than 0.1 percent by weight, and furthermore preferably substantially zero (e.g., less than 0.05 percent by weight). However, such a hydroxyl-containing monomer may be added (used) in an amount of from about 0.01 to about 10 percent by weight when used to introduce crosslinking points typically of crosslinking between hydroxyl group and isocyanate group, or metal crosslinking.
The amount of the other monomer components to be added (used) refers to a content based on the total weight (100 percent by weight) of constitutive monomers (entire constitutive monomers) constituting the acrylic emulsion polymer (A).
In a preferred embodiment particularly for better appearance of the pressure-sensitive adhesive sheet according to the present invention, monomer components (constitutive monomers) to constitute the acrylic emulsion polymer (A) include at least one monomer selected from the group consisting of methyl methacrylate, isobornyl acrylate, and vinyl acetate, of which methyl methacrylate is especially preferred. The monomer (the monomer selected from the group consisting of methyl methacrylate, isobornyl acrylate, and vinyl acetate) is present in a content of preferably from 1 to 15 percent by weight, more preferably from 2 to 10 percent by weight, and furthermore preferably from 2 to 5 percent by weight, based on the total weight (100 percent by weight) of constitutive monomers (entire constitutive monomers) constituting the acrylic emulsion polymer (A). The monomer, if present in a content of less than 1 percent by weight, may fail to effectively contribute to better appearance; whereas, if present in a content of more than 15 percent by weight, may cause the acrylic pressure-sensitive adhesive layer to be excessively rigid to thereby have insufficient adhesion. When the constitutive monomers constituting the acrylic emulsion polymer (A) include two or more monomers selected from the group consisting of methyl methacrylate, isobornyl acrylate, and vinyl acetate, the total sum of contents (total content) of methyl methacrylate, isobornyl acrylate, and vinyl acetate preferably falls within the above-specified range.
The acrylic emulsion polymer (A) for use herein can be obtained by subjecting the constitutive monomers (monomer mixture) to emulsion polymerization with an emulsifier and a polymerization initiator.
The emulsifier for use in the emulsion polymerization to form the acrylic emulsion polymer (A) is a reactive emulsifier containing a radically polymerizable functional group introduced into molecule (reactive emulsifier containing a radically polymerizable functional group). Specifically, the acrylic emulsion polymer (A) is an acrylic emulsion polymer polymerized with a reactive emulsifier containing a radically polymerizable functional group in molecule. Each of different reactive emulsifiers containing a radically polymerizable reactive group may be used alone or in combination.
The reactive emulsifier containing a radically polymerizable functional group is hereinafter also simply referred to as a “reactive emulsifier.” The reactive emulsifier is an emulsifier containing at least one radically polymerizable functional group in molecule (per molecule). The reactive emulsifier for use herein can be one or more of various reactive emulsifiers having at least one radically polymerizable functional group, which is exemplified by vinyl group, propenyl group, isopropenyl group, vinyl ether group (vinyloxy group), and allyl ether group (allyloxy group). The reactive emulsifier, when used, is integrated into the polymer, and this reduces stains derived from the emulsifier.
The reactive emulsifier is exemplified by reactive emulsifiers having a structure corresponding to a nonionic anionic emulsifier, except with a radically polymerizable functional group (radically reactive group), such as propenyl group or allyl ether group, being introduced. The nonionic-anionic emulsifier is an anionic emulsifier having a nonionic hydrophilic group and is exemplified by sodium polyoxyethylene alkyl ether sulfates, ammonium polyoxyethylene alkyl phenyl ether sulfates, sodium polyoxyethylene alkyl phenyl ether sulfates, and sodium polyoxyethylene alkyl sulfosuccinates. Hereinafter a reactive emulsifier having a structure corresponding to an anionic, emulsifier, except with a radically polymerizable functional, group being introduced, is also referred to as an “anionic reactive emulsifier”; whereas a reactive emulsifier having a structure corresponding to a nonionic-anionic emulsifier, except with a radically polymerizable functional group being introduced, is also referred to as a “nonionic-anionic reactive emulsifier.”
Among reactive emulsifiers, anionic reactive emulsifiers are preferred, of which nonionic-anionic reactive emulsifiers are more preferred. This is because such an anionic reactive emulsifier, when used, is integrated into the polymer and contributes to reduction in staining (causes further less stains). Particularly when the water-insoluble crosslinking agent (C) is a multifunctional epoxy crosslinking agent containing an epoxy group, the anionic reactive emulsifier, as having a catalytic activity, can improve the reactivity of the crosslinking agent. If no anionic reactive emulsifier is used, the crosslinking reaction may not complete even through aging, and this may cause the pressure-sensitive adhesive layer to have an adhesive strength that varies with time. Such incomplete crosslinking reaction may cause unreacted carboxyl groups to remain in the pressure-sensitive adhesive layer, which may in turn cause the pressure-sensitive adhesive layer to have an increasing adhesive strength to the adherend with time. The anionic reactive emulsifier is also preferred because it is integrated into the polymer, does not precipitate to the surface in contact with the adherend, and cannot cause clouding as stain, unlike quaternary ammonium compounds (see for example JP-A No. 2007-31585) that are generally used as catalysts for epoxy crosslinking agents.
The reactive emulsifiers as above are also available as commercial products typically under the trade name of “ADEKA REASOAP SE-10N” (from ADEKA CORPORATION), the trade name of “AQUALON HS-10” (from Dai-ichi Kogyo Seiyaku Co., Ltd.), and the trade name of “AQUALON HS-05” (from Dai-ichi Kogyo Seivaku Co., Ltd.).
The reactive emulsifier for use herein is preferably one having a ion concentration of 100 μg/g or less, from which impurity ions have been removed. This is because such impurity ions may become a problem. The anionic reactive emulsifier, when used, is preferably an ammonium salt reactive emulsifier. Impurities can be removed from the reactive emulsifier by a suitable process such as a process using an ion-exchange resin, a membrane-separation process, or an impurities precipitation-filtration process using an alcohol.
The reactive emulsifier may be blended (used) in an amount not critical, but preferably from 0.1 to 5 parts by weight and more preferably from 0.5 to 3 parts by weight per 100 parts by weight of the total amount of constitutive monomers (entire constitutive monomers) constituting the acrylic emulsion polymer (A). The reactive emulsifier, if blended in an amount of more than 5 parts by weight, may cause the pressure-sensitive adhesive (pressure-sensitive adhesive layer) to have insufficient cohesive force to thereby stain the adherend in a larger amount, or the emulsifier itself may stain the adherend. In contrast, the reactive emulsifier, if blended in an amount of less than 0.1 part by weight, may fail to maintain stable emulsification.
The polymerization initiator for use in the emulsion polymerization to form the acrylic emulsion polymer (A) is exemplified by, but not limited to, azo polymerization initiators such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2′-azobis(2-methylpropionamidine)disulfate, and 2,2′-azobis(N,N′-dimethyleneisobutyramidine); persulfates such as potassium peroxodisulfate and ammonium persulfate; peroxide polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide; and redox initiators using a peroxide in combination with a reducing agent, such as redox polymerization initiators using a peroxide and ascorbic acid (e.g., hydrogen peroxide water in combination with ascorbic acid), those using a peroxide in combination with an iron(II) salt (e.g., hydrogen peroxide water in combination with an iron (II) salt), and those using a persulfate in combination with sodium hydrogen-sulfite. Each of different polymerization initiators may be used alone or in combination.
The polymerization initiator may be blended (used) in an amount not critical, but preferably from 0.01 to 1 part by weight and more preferably from 0.02 to 0.5 part by weight per 100 parts by weight of the total amount of constitutive monomers (entire constitutive monomers) constituting the acrylic emulsion polymer (A), though the amount can be suitably determined according typically to the types of the initiator and the constitutive monomers.
The emulsion polymerization to form the acrylic emulsion polymer (A) can be performed by any arbitrary process such as regular batch polymerization, continuous dropping polymerization, or portion-wise dropping polymerization. In a preferred embodiment for less staining, the emulsion polymerization is performed by batch polymerization at a low temperature (typically 55° C. or lower and preferably 30° C. or lower). This is preferred probably because the polymerization, when performed under these conditions, can readily give a high-molecular-weight component, but less gives a low-molecular-weight component, and thus contributes to reduction in staining.
The acrylic emulsion polymer (A) is a polymer including constitutional units derived from the (meth)acrylic alkyl ester and constitutional units derived from the carboxyl-containing unsaturated monomer as essential constitutional units. The acrylic emulsion polymer (A) contains the constitutional units derived from the (math) acrylic alkyl ester in a content of preferably from 70 to 99.5 percent by weight and more preferably from 85 to 99 percent by weight. The acrylic emulsion polymer (A) contains the constitutional units derived from the carboxyl-containing unsaturated monomer in a content of preferably from 0.5 to 10 percent by weight, more preferably from 1 to 5 percent by weight, and furthermore preferably from 2 to 4 percent by weight.
The acrylic emulsion polymer (A) has a solvent-insoluble content of preferably 70% (percent by weight) or more, more preferably 75 percent by weight or more, and furthermore preferably 80 percent by weight or more. The solvent-insoluble content is a percentage of solvent-insoluble components and is also referred to as a “gel fraction.” The acrylic emulsion polymer (A), if having a solvent-insoluble content of less than 70 percent by weight, may contain larger amounts of low-molecular-weight components, and this may impede sufficient reduction of low-molecular-weight components in the pressure-sensitive adhesive layer merely through crosslinking. Such low-molecular-weight components may stain the adherend or bring an excessively high adhesive strength. The solvent-insoluble content can be controlled by the polymerization initiator, the reaction temperature, and the types of the emulsifier and the constitutive monomers. Though not critical, an upper limit of the solvent-insoluble content is typically preferably 99 percent by weight.
The “solvent-insoluble content” of the acrylic emulsion polymer (A) herein refers to a value calculated by a “solvent-insoluble content measurement method” as follows.
Solvent-Insoluble Content Measurement Method
About 0.1 g of the acrylic emulsion polymer (A) is sampled as a specimen, covered with a porous tetrafluoroethylene sheet (trade name “NTF1122”, supplied by Nitto Denko Corporation) having an average pore size of 0.2 μm, tied with a kite string, the weight of the resulting article is measured and defined as a “weight before immersion.” The weight before immersion is the total weight of the acrylic emulsion polymer (A) (the sampled specimen), the tetrafluoroethylene sheet, and the kite string. Independently, the total weight of the tetrafluoroethylene sheet and the kite string is measured and is defined as a “tare weight.”
Next, the article including the specimen acrylic emulsion polymer (A) covered with the tetrafluoroethylene sheet and tied with the kite string (this article is hereinafter also referred to as “sample”) is placed in ethyl acetate filled in a 50-ml vessel and left stand at 23° C. for 7 days. The sample (after ethyl acetate treatment) is retrieved from the vessel, transferred to an aluminum cup, dried in a drying oven at 130° C. for 2 hours to remove ethyl acetate, the weight of the dried sample is measured and is defined as a “weight after immersion.”
Based on these data, the solvent-insoluble content is calculated according to an equation as follows:
Solvent-insoluble content(percent by weight)=(X−Y)/(Z−Y)×100 (1)
wherein X is the weight after immersion; Y is the tare weight; and Z is the weight before immersion.
The acrylic emulsion polymer (A) may have a weight-average molecular weight (Mw) of a solvent-soluble fraction (hereinafter also referred to as “sol fraction”) not critical, but preferably from 4×104 to 20×104, more preferably from 5×104 to 15×104, and furthermore preferably from 6×104 to 10×104. The acrylic emulsion polymer (A), when having a weight-average molecular weight of the solvent-soluble fraction of 4×104 or more, may help the pressure-sensitive adhesive composition to have better wettability with the adherend and thereby contribute to better adhesiveness to the adherend. The acrylic emulsion polymer (A), when having a weight-average molecular weight of the solvent-soluble fraction of 20×104 or less, may help the pressure-sensitive adhesive composition to less remain on the adherend and contribute to further reduction in staining.
The weight-average molecular weight of the solvent-soluble fraction in the acrylic emulsion polymer (IQ can be determined by obtaining an extract (ethyl acetate solution) after the ethyl acetate treatment in the measurement of the solvent-insoluble content of the acrylic emulsion polymer (A), air-drying the extract at room temperature to give a sample (solvent-soluble fraction of the acrylic emulsion polymer (A)), and measuring the weight-average molecular weight of the sample by gel permeation chromatography (GPC). A specific measurement method is exemplified as follows:
Measurement Method
The GPC measurement is performed with a GPC analyzer “HLC-8220GPC” supplied by Tosoh Corporation to determine a molecular weight in terms of a polystyrene standard. The measurement is performed under conditions as follows:
Sample concentration: 0.2 percent by weight (THF solution)
Sample volume: 10 μl
Eluting solvent: THF
Flow rate: 0.6 ml/min
Measurement temperature: 40° C.
Columns: Sample columns; one TSKguardcolumn SuperHZ-H column and two TSKgel SuperHM-H columns
Detector: differential refractive index detector
The pressure-sensitive adhesive composition for use in the present invention may contain the acrylic emulsion polymer (A) in a content not critical, but preferably 80 percent by weight or more and more preferably from 90 to 99 percent by weight based on the total weight (100 percent by weight) of non-volatile components contained in the pressure-sensitive adhesive composition.
Compound (B)
The compound (B) in the pressure-sensitive adhesive composition for use in the Present invention (water-dispersible acrylic pressure-sensitive adhesive composition) is a compound represented by Formula (I) expressed as follows:
R1O—(PO)a-(EO)b—(PO)c—R2 (I)
In Formula (I), each of R1 and R2 independently represents a straight or branched chain alkyl group, or hydrogen atom, where R1 and R2 may be the same as or different from each other. The straight or branched chain alkyl group is preferably exemplified by, but not limited to, alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, propyl group, and butyl group. The substituents R1 and R2 are particularly preferably both hydrogen atoms.
In Formula (I), PO represents oxypropylene group [—CH2CH(CH3)O—]; and each “a” and “c” independently denotes a positive integer (an integer of 1 or more) and is preferably an integer of from 1 to 100, more preferably an integer of from 10 to 50, and furthermore preferably an integer of from 10 to 30. The numbers “a” and “c” may be the same as or different from each other,
In Formula (I), EO represents oxyethylene group [—CH2CH2O—]; and “b” denotes a positive integer (an integer of 1 or more) and is preferably an integer of from 1 to 50, more preferably an integer of from 1 to 30, and furthermore preferably an integer of from 1 to 15.
EO(s) and POs in Formula (I) are added (copolymerized) in a block manner. Specifically, the compound (B) is a triblock copolymer or a derivative thereof, which triblock copolymer has an EO block [polyoxyethylene block, polyethylene glycol (PEG) block] and, present on both sides thereof, PO blocks [polyoxypropylene block, polypropylene glycol (PPG) block].
The compound (B), as blended in the pressure-sensitive adhesive composition, can exhibit a defoaming activity to reduce or eliminate bubble-derived defects.
The compound has a block structure including a polyoxyethylene block located at the center part of the molecule; and PO blocks serving as hydrophobic groups at both ends of the molecule. The compound (B) is therefore hardly uniformly aligned at the vapor-liquid interface and can exhibit a defoaming activity. By contrast, PEG-PPG-PEG triblock copolymers having polyoxyethylene blocks at both ends of the molecule, and diblock copolymers of a polyoxyethylene and a polyoxypropylene are more readily aligned at the vapor-liquid interface than such a PPG-PEG-PPG triblock copolymer does, and they have an activity of stabilizing bubbles (foams).
In addition, the compound (B) is highly hydrophobic, hardly causes clouding as stain on the adherend even in a high-humidity environment, and further lasses stain the adherend. A highly hydrophilic compound (particularly a water-soluble compound), if used and placed in a high-humidity environment, may often cause clouding as stain, because the hydrophilic compound is dissolved in water and readily transfers or migrates to the adherend, or bleeds out to the adherend, swells, and thereby causes clouding of the adherend.
The pressure-sensitive adhesive composition for use in the present invention, as employing the compound (B), can give a pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) that is resistant to clouding (hygroscopic clouding) even during storage under humid conditions. When a pressure-sensitive adhesive sheet is used as a surface-protecting film for an optical member, clouding, if occurring in the pressure-sensitive adhesive layer (namely, clouding occurring in the pressure-sensitive adhesive sheet), may impede or adversely affect the inspection process of the optical member.
The compound (B) may have a percentage (in weight percent (%)) of the “total weight of EO(s)” based on the “total weight of compound(s) (B)” [(total weight of EO(s))/(total weight of compound(s) (B))×100] not critical, but preferably 50 percent by weight or less, more preferably from 5 to 50 percent by weight, and furthermore preferably from 10 to 30 percent by weight. The compound (B), if having the percentage (EO content) of more than 50 percent by weight, may have high hydrophilicity and lose its defoaming activity. The compound (B), if having the percentage of less than 5 percent by weight, may have excessively high hydrophobicity to cause crawling. The term “total weight of compound(s) (B)” refers to the “total sum of weights of entire compounds (B) contained in the pressure-sensitive adhesive composition for use in the present invention”; whereas the term “total weight of EO(s)” refers to the “total sum of weights of EOs contained in entire compounds (B) in the pressure-sensitive adhesive composition for use in the present invention.” The percentage of the “total weight of EO(s)” based on the “total weight of compound(s) (B)” is also referred to as an “ED content.” The EO content may be measured by a technique such as NMR, chromatography, or time-of-flight secondary ion mass spectrometry (TOE-SIMS).
The compound (B) in the pressure-sensitive adhesive composition for use in the present invention preferably has a number-average molecular weight of from 1500 to 4000. The compound (B), if having a number-average molecular weight of less than 1500, may have excessively high compatibility with the system (system of the pressure-sensitive adhesive composition) and fail to effectively exhibit a defoaming activity. In contrast, the compound (B), if having a number-average molecular weight of more than 4000, may have excessively high incompatibility with the system and cause the pressure-sensitive adhesive composition to suffer from crawling upon the application typically to the substrate, although the compound (B) exhibits a high defoaming activity.
The compound (B) is also available as any of commercial products, which are exemplified by trade names “ADEKA Pluronic 25R-1”, “ADEKA Pluronic 25R-2”, “ADEKA Pluronic 17R-2”, and “ADEKA Pluronic 17R-3” each from ADEKA CORPORATION; and trade names “Pluronic RPE Series” from BASF Japan Ltd.
Each of different compounds may be used alone or in combination as the compound (B).
The compound (B) is preferably blended alone without using a solvent to prepare the pressure-sensitive adhesive composition for use in the present invention. However, typically for better blending workability, the compound (B) may be used in the form of a dispersion or solution in a solvent. The solvent is exemplified by 2-ethylhexanol, Butyl CELLOSOLVE, dipropylene glycol, ethylene glycol, propylene glycol, n-propyl alcohol, and isopropyl alcohol.
The compound (B) may be blended in an amount (content in the pressure-sensitive adhesive composition for use in the present invention) not critical, but preferably from 0.01 to 1 part by weight, more preferably from 0.02 to 0.8 part by weight, furthermore preferably from 0.02 to 0.5 part by weight, and most preferably from 0.02 to 0.3 part by weight, per 100 parts by weight of the acrylic emulsion polymer (A). The compound (B), if blended in an amount of less than 0.01 part by weight, may fail to impart sufficient defoaming activity to the composition; whereas, if blended in an amount of more than 1 part by weight, may readily cause stains.
Water-Insoluble Crosslinking Agent (C)
The crosslinking agent to be used in the pressure-sensitive adhesive composition for use in the present invention is preferably, but not limited to, any of water-insoluble crosslinking agents, because they can less cause stains and prevent adhesive strength increase. Among them, more preferred is a water-insoluble crosslinking agent (C) having two or more carboxyl-reactive functional groups in molecule (per molecule), which carboxyl-reactive functional groups are reactive with carboxyl group. As used herein the term “water-insoluble crosslinking agent (C) having two or more carboxyl-reactive functional groups per molecule” is also simply referred to as a “water-insoluble crosslinking agent (C).” Specifically, the pressure-sensitive adhesive composition for use in the present invention preferably further contains a water-insoluble crosslinking agent (C).
The water-insoluble crosslinking agent (C) is a water-insoluble compound that has two or more (e.g., two to six) carboxyl-reactive functional groups in molecule (per molecule). Though not critical, the water-insoluble crosslinking agent (C) preferably has three to five carboxyl-reactive functional groups per molecule. With an increasing number of carboxyl-reactive functional groups per molecule, the pressure-sensitive adhesive composition undergoes denser crosslinking, namely, the polymer constituting the acrylic pressure-sensitive adhesive layer has a denser crosslinked structure. This can prevent the spread by wetting of the pressure-sensitive adhesive layer after its formation. In addition, such dense crosslinked structure constrains the polymer constituting the acrylic pressure-sensitive adhesive layer and thereby prevents increase in adhesive strength of the pressure-sensitive adhesive layer to the adherend, with time. The adhesive strength increase with time is caused by segregation of functional groups (carboxyl groups) contained in the pressure-sensitive adhesive layer to the surface in contact with the adherend. In contrast, the water-insoluble crosslinking agent (C), if having carboxyl-reactive functional groups in an excessively large number of more than 6 per molecule, may cause the formation of a gelled substance.
The carboxyl-reactive functional groups in the water-insoluble crosslinking agent (C) are exemplified by, but not limited to, epoxy groups, isocyanate groups, and carbodiimide groups. Among them, epoxy groups are preferred from the viewpoint of reactivity. Of epoxy groups, glycidylamino groups are more preferred, because they are highly reactive, less cause unreacted components to remain even after the crosslinking reaction, advantageously contribute to reduction in staining, and can prevent increase in adhesive strength to the adherend, which increase is caused by unreacted carboxyl groups remained in the acrylic pressure-sensitive adhesive layer. Specifically, water-insoluble crosslinking agent (C) is preferably any of epoxy crosslinking agents having epoxy groups, of which a crosslinking agent having glycidylamino groups (glycidylamino crosslinking agent) is more preferred. An epoxy crosslinking agent (particularly glycidylamino crosslinking agent), when employed as the water-insoluble crosslinking agent (C), has preferably two or more (e.g., two to six) and more preferably three to five epoxy groups (particularly glycidylamino groups) per molecule.
The water-insoluble crosslinking agent (C) is a water-insoluble compound. The term “water-insoluble” refers to that the compound in question has a solubility of 5 parts by weight or less, preferably 3 parts by weight or less, and furthermore preferably 2 parts by weight or less, in 100 parts by weight of water at 25° C. The solubility is the weight of the compound (crosslinking agent) that can be dissolved in 100 parts by weight of water. A water-insoluble crosslinking agent, when used, may less cause clouding as stain on the adherend and contribute to reduction in staining, which clouding as stain is caused in a high-humidity environment (under humid conditions) by a residual crosslinking agent not involved in crosslinking. By contrast, a water-soluble crosslinking agent, if used, remained, and placed in a high-humidity environment (under humid conditions), is readily dissolved in water, transfers to the adherend, and often causes clouding as stain. The water-insoluble crosslinking agent more contributes to the crosslinking reaction (reaction with carboxyl group) and more effectively prevents adhesive strength increase with time than the water-soluble crosslinking agent does. In addition, the water-insoluble crosslinking agent has high reactivity for the crosslinking reaction, thereby facilitates the crosslinking reaction through aging, and can prevent increase in adhesive strength to the adherend due to unreacted carboxyl groups remained in the pressure-sensitive adhesive layer.
The solubility of a crosslinking agent in water can be measured typically by a method as follows.
Water Solubility Measurement Method
Water (25° C.) and the sample crosslinking agent in equal weights are mixed using a stirrer at a number of revolutions of 300 rpm for 10 minutes, and the mixture is separated by centrifugal separation into an aqueous phase and an oily phase. Next, the aqueous phase is collected, dried at 120° C. for one hour, a weight loss on drying is determined, from which the content of non-volatile components in the aqueous phase (part by weight of non-volatile components per 100 Parts by weight of water) is determined.
Specific examples of the water-insoluble crosslinking agent (C) include glycidylamino crosslinking agents such as 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (e.g., trade name “TETRAD-C” supplied by MITSUBISHI GAS CHEMICAL COMPANY, INC.) [solubility in 100 parts by weight of water at 25° C.: 2 parts by weight or less] and 1,3-bis(N,N-diglycidylaminomethyl)benzene (e.g., trade name “TETRAD-X” supplied by MITSUBISHI GAS CHEMICAL COMPANY, INC.) [solubility in 100 parts by weight of water at 25° C.: 2 parts by weight or less]; and other epoxy crosslinking agents such as tris(2,3-epoxypropyl)isocyanurate (e.g., trade name “TEPIC-G” supplied by Nissan Chemical Industries, Ltd.) [solubility in 100 parts by weight of water at 25° C.: 2 parts by weight or less]. Each of different water-insoluble crosslinking agents may be used alone or in combination as the water-insoluble crosslinking agent (C).
To prepare the pressure-sensitive adhesive composition for use in the present invention, the water-insoluble crosslinking agent (C), when being a liquid one, may be added (blended) as intact, or may be dissolved in and/or diluted with, an organic solvent before blending. The amount of the organic solvent to be used is, however, preferably minimized. It is not desirable to blend (add) the water-insoluble crosslinking agent (C) in the form of an emulsion emulsified with an emulsifier. This is because the emulsifier bleeds out and readily causes stains (particularly clouding as stain).
The water-insoluble crosslinking agent (C) is blended preferably in such an amount (content in the pressure-sensitive adhesive composition for use in the present invention) that the carboxyl-reactive functional groups of the water-insoluble crosslinking agent (C) are present in an amount of from 0.3 to 1.3 moles per 1 mole of carboxyl groups of the carboxyl-containing unsaturated monomer used as a constitutive monomer constituting the acrylic emulsion polymer (A). Specifically, the molar ratio [(carboxyl-reactive functional group)/(carboxyl group)] is preferably from 0.3 to 1.3, more preferably from 0.4 to 1.1, and furthermore preferably from 0.5 to 1.0. The molar ratio is the ratio (molar ratio) of the “total number of moles of carboxyl-reactive functional groups in entire water-insoluble crosslinking agents (C)” to the “total number of moles of carboxyl groups in entire carboxyl-containing unsaturated monomers to be used as constitutive monomers constituting the acrylic emulsion polymer (A).” If the ratio [(carboxyl-reactive functional group)/(carboxyl group)] is less than 0.3, the acrylic pressure-sensitive adhesive layer may contain a large amount of unreacted carboxyl groups and may suffer from adhesive strength increase with time, because such unreacted carboxyl groups interact with the adherend. If the ratio exceeds 1.3, the acrylic pressure-sensitive adhesive layer may contain a large amount of an unreacted water-insoluble crosslinking agent (C) and may thereby suffer from visual defects.
Particularly when the water-insoluble crosslinking agent (C) is an epoxy crosslinking agent, the molar ratio [(epoxy group)/(carboxyl group)] is preferably from 0.3 to 1.3, more preferably from 0.4 to 1.1, and furthermore preferably from 0.5 to 1.0. When the water-insoluble crosslinking agent (C) is a glycidylamino crosslinking agent, the molar ratio [(glycidylamino group)/(carboxyl group)] preferably falls within the above-specified range.
For example, when 4 g of a water-insoluble crosslinking agent (C) having a carboxyl-reactive functional group equivalent of 110 (g/eq) is added (blended) to the pressure-sensitive adhesive composition, the number of moles of the carboxyl-reactive functional groups in the water-insoluble crosslinking agent can be calculated typically according to an equation as follows:
Number of moles of carboxyl-reactive functional groups in the water-insoluble crosslinking agent (C)=[Amount of water-insoluble crosslinking agent (C) to be blended (added)]/[Functional group equivalent]=4/110
When 4 q of an epoxy crosslinking agent having an epoxy equivalent of 110 (g/eq) is added (blended) as the water-insoluble crosslinking agent (C), the number of moles of epoxy groups in the epoxy crosslinking agent can be calculated according to an equation as follows:
Number of moles of epoxy groups in the epoxy crosslinking agent-[Amount of the epoxy crosslinking agent to be blended (added)]/[Epoxy equivalent]=4/110
The pressure-sensitive adhesive composition for use in the present invention is a water-dispersible pressure-sensitive adhesive composition. The term “water-dispersible” refers to that the substance in question is dispersible in an aqueous medium. Specifically, the pressure-sensitive adhesive composition for use in the present invention is a pressure-sensitive adhesive composition that is dispersible in an aqueous medium. The aqueous medium is a medium (dispersion medium) including water as an essential component and may be water alone or a mixture of water with a water-soluble organic solvent. The pressure-sensitive adhesive composition for use in the present invention may also be a dispersion typically with the aqueous medium.
The pressure-sensitive adhesive composition for use in the present invention may contain a multifunctional hydrazide crosslinking agent as a crosslinking agent other than the water-insoluble crosslinking agent (C). The multifunctional hydrazide crosslinking agent, when used, may help the pressure-sensitive adhesive composition to form an acrylic pressure-sensitive adhesive layer that is improved in removability, adhesiveness, and anchoring capability with respect to the substrate. The multifunctional hydrazide crosslinking agent (hereinafter also simply referred to as “hydrazide crosslinking agent”) is a compound having at least two hydrazide groups in molecule (per molecule). The multifunctional hydrazide crosslinking agent preferably has two or three, and more preferably two, hydrazide groups per molecule. Compounds to be used as the hydrazide crosslinking agent are preferably exemplified by, but not limited to, dihydrazide compounds such as oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, pimelic dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, phthalic dihydrazide, isophthalic dihydrazide, terephthalic dihydrazide, 2,6-naphthalenedicarboxylic dihydrazide, naphthalic dihydrazide, acetonedicarboxylic dihydrazide, fumaric dihydrazide, maleic dihydrazide, itaconic dihydrazide, trimellitic dihydrazide, 1,3,5-benzenetricarboxylic dihydrazide, pyromellitic dihydrazide, and aconitic dihydrazide. Among them, adipic dihydrazide and sebacic dihydrazide are particularly preferred. Each of different hydrazide crosslinking agents may be used alone or in combination.
The hydrazide crosslinking agent for use herein is also available as any of commercial products such as “Adipic Dihydrazide (Reagent)” from Tokyo Chemical Industry Co., Ltd.; and “Adipoyl Dihydrazide (Reagent)” from Wako Pure Chemical Industries, Ltd.
The hydrazide crosslinking agent may be blended in an amount (content in the pressure-sensitive adhesive composition for use in the present invention) not critical, but preferably from 0.025 to 2.5 moles, more preferably from 0.1 to 2 moles, and furthermore preferably from 0.2 to 1.5 moles, per 1 mole of keto groups in a keto-containing unsaturated monomer for use as a constitutive monomer constituting the acrylic emulsion polymer (A). The hydrazide crosslinking agent, if blended in an amount of less than 0.025 mole, may fail to exhibit sufficient effects as a crosslinking agent. This may cause the acrylic pressure-sensitive adhesive layer or pressure-sensitive adhesive sheet to be removed heavily and may often cause clouding as stain on the adherend due to residual low-molecular-weight components in the polymer constituting the acrylic pressure-sensitive adhesive layer. In contrast, the hydrazide crosslinking agent, if blended in an amount of more than 2.5 moles, may remain as an unreacted crosslinking agent component, which may cause stains.
In a preferred embodiment for less staining, the pressure-sensitive adhesive composition for use in the present invention is combined with no quaternary ammonium salt. In a more preferred embodiment, the composition is combined with no quaternary ammonium compound. Accordingly, the pressure-sensitive adhesive composition for use in the present invention preferably contains substantially no quaternary ammonium salt and more preferably contains substantially no quaternary ammonium compound. These compounds are generally used typically as catalysts for better reactivity of epoxy crosslinking agents. These compounds, however, are not integrated into the polymer constituting the pressure-sensitive adhesive layer, can freely move or migrate in the pressure-sensitive adhesive layer, and readily precipitate to the surface in contact with the adherend. Accordingly, these compounds, if contained in the pressure-sensitive adhesive composition, may often cause clouding as stain and impede satisfactory reduction in staining. Specifically, the pressure-sensitive adhesive composition for use in the present invention has a quaternary ammonium salt content of preferably less than 0.1 percent by weight, more preferably less than 0.01 percent by weight, and furthermore preferably less than 0.005 percent by weight, based on the total weight (100 percent by weight) of non-volatile components in the pressure-sensitive adhesive composition. The composition preferably has a quaternary ammonium compound content falling within the above-specified range.
The quaternary ammonium salt is exemplified by, but not limited to, a compound represented by a formula as follows:
In the formula, each of R3, R4, R5, and R6 is not hydrogen atom, but an alkyl group, an aryl group, or a group derived from them (e.g., a substituted alkyl group or aryl group); and X− represents a counter ion.
The quaternary ammonium salt and the quaternary ammonium compound are exemplified by, but not limited to, alkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, as well as salts of them; arylammonium hydroxides such as tetraphenylammonium hydroxide, as well as salts of them; and bases and salts of them, which bases include, as a cation, any of trilaurylmethylammonium ion, didecyldimethylammonium ion, dicocoyldimethylammonium ion, distearyldimethylammonium ion, dioleyldimethylammonium ion, cetyltrimethylammonium ion, stearyltrimethylammonium ion, behenyltrimethylammonium ion, cocoylbis(2-hydroxyethyl)methylammonium ion, polyoxyethylene (15) coco-stearylmethylammonium ion, oleylbis(2-hydroxyethyl)methylammonium ion, cocobenzyldimethylammonium ion, laurylbis(2-hydroxyethyl)methylammonium ion, and decylbis(2-hydroxyethyl)methylammonium ion.
In a preferred embodiment for less staining, the pressure-sensitive adhesive composition for use in the present invention is combined with none of tertiary amines and imidazole compounds. Such tertiary amines and imidazole compounds are generally used typically as catalysts for better reactivity of epoxy crosslinking agents, as with the quaternary ammonium salt (or quaternary ammonium compound). Accordingly, the pressure-sensitive adhesive composition for use in the present invention preferably contains substantially none of tertiary amines and imidazole compounds. Specifically, the pressure-sensitive adhesive composition for use in the present invention may have a content of tertiary amines and imidazole compounds (total content of tertiary amines and imidazole compounds) not critical, but preferably less than 0.1 percent by weight, more preferably less than 0.01 percent by weight, and furthermore preferably less than 0.005 percent by weight, based on the total weight (100 percent by weight) of non-volatile components in the pressure-sensitive adhesive composition.
The tertiary amines are exemplified by tertiary amine compounds such as triethylamine, benzyldimethylamine, and α-methylbenzyl-dimethylamine. The imidazole compounds are exemplified by 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 4-ethylimidazole, 4-dodecylimidazole, 2-phenyl-4-hydroxymethylimidazole, 2-ethyl-4-hydroxymethylimidazole, 1-cyanoethyl-4-methylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole.
The pressure-sensitive adhesive composition for use in the present invention may further contain any of other additives than those mentioned above, within ranges not adversely affecting reduction in staining. The additives are exemplified by pigments, fillers, leveling agents, dispersing agents, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, ultraviolet stabilizers, age inhibitors, and antiseptic agents.
The leveling agents are exemplified by, but not limited to, acetylenic diol compounds (diol compounds having at least one acetylenic bond per molecule) and fluorocarbon modified polyacrylates. The leveling agent or agents may be used in an amount (content in the pressure-sensitive adhesive composition for use in the present invention) not critical, but preferably from 0.01 to 10 parts by weight and more preferably from 0.1 to 5 parts by weight, per 100 parts by weight of the acrylic emulsion polymer (A). Each of different leveling agents may be used alone or in combination.
The pressure-sensitive adhesive composition for use in the present invention can be prepared by mixing the acrylic emulsion polymer (A) and the compound (B) with each other. Where necessary, any of other optional components such as the water-insoluble crosslinking agent (C), other crosslinking agents, and additives may be mixed therewith. The mixing may be performed by any known or customary emulsion mixing process, but is preferably performed by stirring with a stirrer. The stirring may be performed under any conditions, but is performed at a temperature of preferably from 10° C. to 50° C. and more preferably from 20° C. to 35° C. for a duration of preferably from 5 to 30 minutes and more preferably from 10 to 20 minutes at a number of revolutions of preferably from 10 to 2000 rpm and more preferably from 30 to 1000 rpm.
The timing for adding the compound (B) in the mixing is not critical. The compound (B) may be added during polymerization to form an acrylic emulsion polymer (A), or may be mixed with the resulting acrylic emulsion polymer (A) after the polymerization. The timing for adding the water-insoluble crosslinking agent (C) is also not critical, but is preferably immediately before application of the pressure-sensitive adhesive composition from the viewpoint of pot life.
The pressure-sensitive adhesive composition obtained in the above manner is applied to at least one side of the transparent film substrate, dried according to necessity to form an acrylic pressure-sensitive adhesive layer, and thereby yields a pressure-sensitive adhesive sheet according to the present invention. This is a pressure-sensitive adhesive, sheet including the transparent film substrate and, on at least one side thereof, an acrylic pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for use in the present invention. Crosslinking may be performed typically by heating the pressure-sensitive adhesive sheet after dehydration and drying in the drying step. The acrylic pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to the present invention is preferably formed by a so-called direct process, in which the pressure-sensitive adhesive composition is directly applied to the transparent film substrate surface. The acrylic pressure-sensitive adhesive layer may also be formed by a so-called transfer process, in which an acrylic pressure-sensitive adhesive layer is once provided on a release film and is then transferred (laminated) onto the transparent film substrate. However, the acrylic pressure-sensitive adhesive layer, if formed by the transfer process, may fail to have sufficient anchoring capability (adhesion) to the transparent film substrate. This is because the acrylic pressure-sensitive adhesive layer has a high solvent-insoluble content. For this reason, the direct process is more preferably employed. The pressure-sensitive adhesive sheet according to the present invention, however, is not limited in production method, as long as being a pressure-sensitive adhesive sheet having the substrate and, on at least one side thereof, an acrylic pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for use in the present invention.
The acrylic pressure-sensitive adhesive layer (after crosslinking) in the pressure-sensitive adhesive sheet according to the present invention may have a thickness not critical, but preferably from 1 to 50 μm, more preferably from 1 to 35 μm, and furthermore preferably from 3 to 25 μm.
The acrylic pressure-sensitive adhesive layer (after crosslinking) may have a solvent-insoluble content not critical, but preferably 90 percent by weight or more and more preferably 95 percent by weight or more. The acrylic pressure-sensitive adhesive layer, if having a solvent insoluble content of less than 90 percent by weight, may cause larger transfer of contaminants (staining components) to the adherend, thereby cause clouding as stain, or may have insufficient removability (may be removable heavily or hardly). An upper limit of the solvent-insoluble content of the acrylic pressure-sensitive adhesive layer (after crosslinking) is not critical, but is typically preferably 99 percent by weight.
The solvent-insoluble content of the acrylic pressure-sensitive adhesive layer (after crosslinking) can be measured by the procedure as with the solvent-insoluble content measurement method for the acrylic emulsion polymer. Specifically, the solvent-insoluble content can be measured by a procedure corresponding to the “solvent-insoluble content measurement method”, except that the term “acrylic emulsion polymer (A)” is read as “acrylic pressure-sensitive adhesive layer (after crosslinking).”
The acrylic polymer (after crosslinking) constituting the acrylic pressure-sensitive adhesive layer may have a glass transition temperature not critical, but preferably from −70° C. to −10° C., more preferably from −70° C. to −20° C., furthermore preferably from −70° C. to −40° C., and most preferably from −70° C. to −60° C. The acrylic polymer, if having a glass transition temperature of higher than −10° C., may have an insufficient adhesive strength and cause to suffer from gaps or separation typically upon working. The acrylic polymer, if having a glass transition temperature of lower than −70° C., may cause to be removed heavily at higher peel, rates (tensile speeds), thus lowering the working efficiency. The glass transition temperature of the acrylic polymer (after crosslinking) constituting the acrylic pressure-sensitive adhesive layer can also be controlled typically by the monomer formulation to prepare the acrylic emulsion polymer (A).
The pressure-sensitive adhesive sheet according to the present invention has an adhesive strength to a polarizing plate of preferably from 0.01 to 5 N/25 mm, more preferably from 0.02 to 3 N/25 mm, furthermore preferably from 0.03 to 2 N/25 mm, and most preferably from 0.04 to 1 N/25 mm at a tensile speed of 0.3 m/min. The polarizing plate is a triacetyl cellulose (TAC) plate and is one having an arithmetic mean surface roughness Ra of 50 nm or less. The adhesive strength is determined by a 180-degree peel test and is a release force when the pressure-sensitive adhesive sheet, once applied to the polarizing plate, is peeled off therefrom. The pressure-sensitive adhesive sheet, if having the adhesive strength of more than 5 N/25 mm, may become heavily removable and exhibit inferior productivity and handleability in production processes for such polarizing plates and liquid crystal display devices. The pressure-sensitive adhesive sheet, if having the adhesive strength of less than 0.01 N/25 mm, may undergo gaps or separation during the production processes and exhibit an inferior protection function as a surface-protecting pressure-sensitive adhesive sheet. The arithmetic mean surface roughness Ra can be measured typically with the KLA-Tencor P-15 (stylus surface profilometer). The surface roughness (arithmetic mean surface roughness Pa) can be measured typically at a measurement length of 1000 μm, a scanning speed of 50 μm/sec, and a scanning pass count of one pass, under a load of 2 mg, though the conditions are not critical.
The pressure-sensitive adhesive sheet according to the present invention may have a total luminous transmittance in the visible light region not critical, but preferably from 80% to 97% and more preferably from 85% to 95%, as determined according to JIS K7361-1. The pressure-sensitive adhesive sheet according to the present invention may have a haze not critical, but preferably from 1.0% to 3.5% and more preferably from 2.0% to 3.2%, as determined according to JIS K7136. The pressure-sensitive adhesive sheet, if having a total luminous transmittance and/or a haze out of the above-specified range, may readily impede the visual inspection of the adherend.
The top coat layer surface of the transparent film substrate, namely, the top coat layer surface of the pressure-sensitive adhesive sheet according to the present invention, may have a surface resistivity not critical, but preferably 100×108 Ω/square or less (e.g., from 0.1×108 to 100×108 Ω/square), more preferably 50×108 Ω/square or less from 0.1×108 to 50×108 Ω/square), and furthermore preferably from 1×108 to 50×108 Ω/square. The pressure-sensitive adhesive sheet, when having a surface resistivity of 100×108 Ω/square or less on the top coat layer surface, is preferably usable particularly as a surface-protecting film for use typically in a working or transportation process of static-sensitive articles such as liquid crystal cells and semiconductor devices. The surface resistivity can be calculated from a surface resistance, which is measured at an ambient temperature of 23° C. and relative humidity of 55% using a commercially available insulation resistance measurement instrument. Specifically, a surface resistivity value obtained by the surface resistivity measurement method outlined in Examples mentioned later is preferably employed.
The top coat layer surface of the transparent film substrate, namely, the top coat layer surface of the pressure-sensitive adhesive sheet according to the present invention, may have a frictional coefficient not critical, but preferably 0.4 or less. The pressure-sensitive adhesive sheet, when controlled to have a small frictional coefficient of 0.4 or less and when receives a load (such a load as to cause scratches) on the top coat layer surface, can turn the load aside along the top coat layer surface and thus contribute to a lower frictional force. This further satisfactorily prevents an event where the top coat layer undergoes cohesive failure or is separated from the base layer (suffers from interfacial failure) to cause scratches. A lower limit of the frictional coefficient is not critical, but is typically preferably 0.1 and more preferably 0.15 in consideration of the balance with other properties such as visual quality and printability. Specifically, the frictional coefficient is not critical, but is preferably from 0.1 to 0.4 and more preferably from 0.15 to 0.4.
The frictional coefficient can for example be a value determined by rubbing the top coat layer surface of the transparent film substrate (or of the pressure-sensitive adhesive sheet according to the present invention) with a vertical load of 40 mN and measuring a frictional coefficient at an ambient temperature of 23° C. and relative humidity of 50%. The frictional coefficient can be reduced (controlled) by a suitable technique such as a technique of incorporating a lubricant (e.g., a leveling agent) to the top coat layer, or a technique of increasing the crosslinking density of the top coat layer by adding a crosslinking agent and/or by controlling film-forming conditions.
In a preferred embodiment, the top coat layer surface of the transparent film substrate, namely, the top coat layer surface of the pressure-sensitive adhesive sheet according to the present invention, has such a property as to be easily printable with an oil-based ink or a water-based ink (e.g., with an oil-based marker). This property is hereinafter also referred to as “printability.” When the surface-protecting film (pressure-sensitive adhesive sheet) according to this embodiment is applied onto an adherend (e.g., an optical component) and when the adherend with the surface-protecting film is in a working or transportation process, the surface-protecting film is suitable for printing and indicating, for example, an identification number of the adherend to be protected. The pressure-sensitive adhesive sheet according to the preferred embodiment of the present invention therefore serves as a surface-protecting film having not, only superior visual quality but also excellent printability. In a more preferred embodiment, the pressure-sensitive adhesive sheet serves as a surface-protecting film having satisfactory printability with an oil-based ink containing a pigment in an alcoholic solvent. In another preferred embodiment, the pressure-sensitive adhesive sheet has such a property as to be resistant to rub-off of printed ink by friction or transferring. This property is hereinafter also referred to as “ink adhesion.” The level of printability can be grasped typically by a printability evaluation as follows.
Printability (Ink Adhesion) Evaluation
The top coat layer surface is printed with Xstamper supplied by Shachihata Inc.; on top of the print, is affixed a cellophane pressure-sensitive adhesive tape (product No. 405, 19 mm wide) supplied by Nichiban Co., Ltd.; and the tape is peeled off at a peel speed of 30 m/min and a peel angle of 180 degrees. The post-peeling surface is visually observed. This measurement is performed at an ambient temperature of 23° C. and relative humidity of 50%. A sample having a peeled area of the print of 50% or larger is evaluated as poor (P) (poor printability); whereas a sample having an unpeeled area of the print of 50% or larger is evaluated as good (G) (good printability).
In another preferred embodiment, the top coat layer surface of the transparent film substrate, namely, the top coat layer surface of the pressure-sensitive adhesive sheet according to the present invention, has solvent resistance at such a level where rubbing off the ink with an alcohol (e.g., ethanol) for modification or deletion would not cause significant changes (cloudiness) to the appearance. The solvent resistance level can be assessed typically by a solvent resistance evaluation as follows.
Solvent Resistance Evaluation
In a dark room blocked from outside light, the top coat layer surface is wiped 15 times with a cleaning cloth (fabric) wetted with ethanol, and the appearance of the wiped surface is visually observed. A sample indicating no visual change between regions wiped with ethanol and the other regions (indicating no visual change due to wiping with ethanol) is evaluated as good (G) (good solvent resistance); whereas a sample indicating wiping streaks is evaluated as poor (P) (poor solvent resistance).
The pressure-sensitive adhesive sheet according to the present invention satisfactorily less causes clouding as stain on the adherend. This can be evaluated typically in a manner as follows. The pressure-sensitive adhesive sheet is laminated onto a polarizing plate (trade name “SEG1425DUHC”, supplied by Nitto Denko Corporation) at 0.25 MPa and 0.3 m/min, left stand at 80° C. for 4 hours, and the pressure sensitive adhesive sheet is removed from the polarizing plate. The polarizing plate, from which the pressure sensitive adhesive sheet has been removed, is further left stand at an ambient temperature of 23° C. and relative humidity of 90% for 12 hours, and the surface of which is observed. It is preferred that no clouding is observed in the polarizing plate surface. A pressure-sensitive adhesive sheet, if causing clouding on the adherend polarizing plate under humid conditions (high-humidity conditions) after its application and removal, may be insufficiently reduced in staining for use as a surface-protecting film for an optical member.
The pressure-sensitive adhesive sheet according to the present invention can be formed into a roll and can be wound as a roll with a release film (separator) protecting the acrylic pressure-sensitive adhesive layer. The backside of the pressure-sensitive adhesive sheet may bear a back treatment layer (a surface release treatment layer or a soil-resistant layer) as formed by a surface release treatment and/or a soil resistant finishing. These treatments are performed typically with any of releasing agents such as silicone, fluorochemical, long-chain alkyl, or fatty amide releasing agents; and silica powders. The “backside” refers to a surface of the pressure-sensitive adhesive sheet opposite to the surface bearing the acrylic pressure-sensitive adhesive layer and is generally the top coat layer surface. In a preferred embodiment, the pressure-sensitive adhesive sheet according to the present invention has a structure of [(acrylic pressure-sensitive adhesive layer)/(transparent film substrate)/(back treatment layer)].
The pressure-sensitive adhesive sheet according to the present invention has adhesiveness and removability (easiness to remove) at satisfactorily levels, is removable, and is used in applications where the sheet will be removed (for removable use). Specifically, in a preferred embodiment, the pressure-sensitive adhesive sheet according to the present invention is used in applications where the sheet will be removed. Such applications are exemplified by masking tapes such as those for protection or curing in construction, those for automobile painting, those for electronic components (e.g., lead frames and printed circuit boards), and those for sand blasting; surface-protecting films such as those for aluminum sash, those for optical plastics, those for optical glass, those for automobiles, and those for metal plates; pressure-sensitive adhesive tapes for use in production processes of semiconductor/electronic components, such as backgrinding tapes, pellicle-fixing tapes, dicing tapes, lead-frame-fixing tapes, cleaning tapes, dedusting tapes, carrier tapes, and cover tapes; packaging tapes for electronic appliances and electronic components; temporal tacking tapes upon transportation; binding tapes; and labels.
In addition, the pressure-sensitive adhesive sheet according to the present invention less suffers from dimples, bubble defects, and other visual defects in the pressure-sensitive adhesive layer, less appears cloudy even though having a top coat layer, and has superior visual quality. The pressure-sensitive adhesive sheet according to the present invention, as having the top coat layer, can exhibit scratch resistance and antistatic properties at satisfactory levels. For these reasons, the pressure-sensitive adhesive sheet according to the present invention is advantageously usable in the surface protection of optical members (e.g., optical plastics, optical glass, and optical films) typically as a surface-protecting film for an optical member. The optical members are exemplified by polarizing plates, retardation films, anti-reflective films, wave plates, compensation films, and brightness enhancing films constituting panels such as liquid crystal displays, organic electroluminescence (organic EL) displays, and field emission displays. This is because these applications require especially excellent properties such as visual quality, scratch resistance, and antistatic properties. However, the pressure-sensitive adhesive sheet can also be used for other applications not limited to the above ones and can be used typically in surface-protection, failure-prevention, removal of foreign matter, or masking upon production of microfabricated components such as semiconductors (semiconductor devices), circuits, printed circuit boards, masks, and lead frames.
The present invention will be illustrated in further detail with reference to several examples below, which are by no means intended to limit the scope of the invention.
In a reactor was placed 25 g of toluene, the reactor inside temperature was raised to 105° C., and a solution was continuously added dropwise to toluene in the reactor over 2 hours. The solution was a mixture of 30 g of methyl methacrylate (MMA), 10 g of n-butyl acrylate (BA), 5 g of cyclohexyl methacrylate (CHMA), and 0.2 g of azobisisobutyronitrile. After the completion of dropwise addition, the reactor inside temperature was adjusted to a temperature range of from 110° C. to 115° C., and a copolymerization reaction was performed by holding the resulting mixture within the temperature range for 3 hours. After a lapse of 3 hours, the mixture in the reactor was combined with a mixture of 4 g of toluene and 0.1 g of azobisisobutyronitrile added dropwise and then held within the temperature range for one hour. The reactor inside temperature was allowed to fall down to 90° C., and the mixture was diluted with toluene so as to have a NV of 5 percent by weight, and yielded a solution (Binder Solution 1) containing 5 percent by weight of an acrylic polymer as a binder (Binder Polymer 1; Tg: 48° C.) in toluene.
Next, 2 g of Binder Solution 1 (containing 0.1 g of Binder Polymer 1) and 40 g of ethylene glycol monoethyl ether were placed in a 150-mL beaker, followed by stirring. The mixture in the beaker was further combined with 1.2 g of Electroconductive Polymer Solution 1 (aqueous solution) containing a polyethylenedioxythiophene (PEDT) and a polystyrenesulfonate (PSS) and having a NV of 4.0 percent by weight, 55 g of ethylene glycol monomethyl ether, 0.05 g of a polyether-modified polydimethylsiloxane leveling agent (lubricant solution) (trade name “BYK-300” supplied by BYK Chemie GmbH, NV: 52 percent by weight), and 0.02 g of a melamine crosslinking agent (trade name “NIKALAC MW-30M” supplied by Sanwa Chemical Co., Ltd., non-volatile content: 100%), followed by vigorous stirring for about 20 minutes. In this manner, was prepared a top coat layer coating composition (NV: 0.2 percent by weight). The composition contained 48 parts by weight of the electroconductive polymer, 26 parts by weight of the lubricant, and 20 parts by weight of the melamine crosslinking agent per 100 parts by weight of Binder Polymer 1 (acrylic polymer) each in solids content.
Top Coat Layer Formation
To a 38 μm thick by 30 cm wide by 40 cm long transparent poly(ethylene terephthalate) film (PET film) having one surface treated with corona discharge, the top coat layer coating composition was applied on the corona-discharged surface using a bar coater to a dry thickness of about 10 nm. The applied composition was dried by heating at 130° C. for 2 minutes to form a top coat layer on one side of the PET film. In this manner, was prepared a transparent film substrate (hereinafter also referred to as “SUB 1” (Substrate 1)) having a PET film and, on one side thereof, a transparent top coat layer.
A transparent film substrate (hereinafter also referred to as “SUB 2”) having a PET film and, on one side thereof, a transparent top coat layer was prepared by the procedure of Production Example 1, except for using Electroconductive Polymer Solution 1 in an amount of 2.5 g instead of 1.2 g; using ethylene glycol monomethyl ether in an amount of 17 g instead of 55 g; and applying the resulting top coat layer coating solution to a dry thickness of about 20 nm.
A transparent film substrate (hereinafter also referred to as “SUB 3”) having a PET film and, on one side thereof, a transparent top coat layer was prepared by the procedure of Production Example 1, except for using ethylene glycol monoethyl ether in an amount of 19 g instead of 40 g; using Electroconductive Polymer Solution 1 in an amount of 0.7 g instead of 1.2 g; using no ethylene glycol monomethyl ether; and applying the resulting top coat layer coating solution to a dry thickness of about 40 nm.
A transparent film substrate (hereinafter also referred to as “SUB 4”) having a PET film and, on one side thereof, a transparent top coat layer was prepared by the procedure of Production Example 3, except for using ethylene glycol monoethyl ether in an amount of 15 g instead of 19 g; and applying the resulting top coat layer coating solution to a dry thickness of about 50 nm.
In a reactor was placed 25 g of toluene, the reactor inside temperature was raised to 105° C., and a solution was continuously added dropwise to toluene in the reactor over 2 hours. The solution was a mixture of 32 g of methyl methacrylate (MMA), 5 g of n-butyl acrylate (BA), 0.7 g of methacrylic acid (MAA), 5 g of cyclohexyl methacrylate (CHMA), and 0.2 g of azobisisobutyronitrile. After the completion of dropwise addition, the reactor inside temperature was adjusted to a temperature range of from 110° C. to 115° C., and a copolymerization reaction was performed by holding the resulting mixture within the temperature range for 3 hours. After a lapse of 3 hours, the mixture in the reactor was combined with a mixture of 4 g of toluene and 0.1 g of azobisisobutyronitrile added dropwise and then held within the temperature range for one hour. The reactor inside temperature was allowed to fall down to 90° C., and the mixture was diluted with 31 g of toluene. In this manner, was prepared a solution (Binder Solution 2) containing about 42 percent by weight of an acrylic polymer as a binder (Binder Polymer 2; Tg: 72° C.) in toluene.
Next, 5.5 g of Binder Solution 2 (containing 2.3 g of Binder Polymer 2) and 30 g of ethylene glycol monoethyl ether were placed in a 150-mL beaker, followed by stirring. The mixture in the beaker was combined with 14 g of Electroconductive Polymer Solution 2 (aqueous solution) containing PEDT and PSS and having a NV of 1.3 percent by weight, 6 g of ethylene glycol monomethyl ether, and 0.5 g of a lubricant solution (BYK-300), followed by vigorous stirring for about 30 minutes. In this manner, was prepared a top coat layer coating composition. This contained 8 parts by weight of the electroconductive polymer and 11 part by weight of the lubricant per 100 parts by weight of Binder Polymer 2 (acrylic polymer) each in solids content. The top coat layer coating composition contained no crosslinking agent.
Top Coat Layer Formation
To a 38 μm thick by 30 cm wide by 40 cm long transparent poly(ethylene terephthalate) film (PET film) having one surface treated with corona discharge, the top coat layer coating composition was applied on the corona-discharged surface using a bar coater to a dry thickness of about 610 nm. The applied composition was dried by heating at 80° C. for 2 minutes to form a top coat layer. In this manner, was prepared a transparent film substrate (hereinafter also referred to as “SUB 5”) having a PET film and, on one side thereof, a transparent top coat layer.
In a reactor was placed 25 g of toluene, the reactor inside temperature was raised to 105° C., and a solution was continuously added dropwise to toluene in the reactor over 2 hours. The solution was a mixture of 30 g of methyl methacrylate (MMA), 10 g of n-butyl acrylate (BA), 5 q of cyclohexyl methacrylate (CHMA), 5 g of hydroxyethyl methacrylate (HEMA), and 0.2 q of azobisisobutyronitrile. After the completion of dropwise addition, the reactor Inside temperature was adjusted to a temperature range of from 110° C. to 115° C., and a copolymerization reaction was performed by holding the resulting mixture within the temperature range for 3 hours. After a lapse of 3 hours, the mixture in the reactor was combined with a mixture of 4 of toluene and 0.1 g of azobisisobutyronitrile added dropwise and then held within the temperature range for one hour. The reactor inside temperature was allowed to fall down to 90° C., and the mixture was diluted with toluene. In this manner, was prepared a solution (Binder Solution 3) containing about 5 percent by weight of an acrylic polymer as a binder (Binder Polymer 3; Tg: 49° C.) in toluene.
Next, 2 q of Binder Solution 3 (containing 0.1 g of Binder Polymer 3) and 40 g of ethylene glycol monoethyl ether were placed in a 150-mL beaker, followed by stirring. The mixture in the beaker was further combined with 1.2 g of Electroconductive Polymer Solution 1 (aqueous solution) containing a polyethylenedioxythiophene (PEDT) and a polystyrenesulfonate (PSS) and having a NV of 4.0 percent by weight, 55 g of ethylene glycol monomethyl ether, 0.05 g of a polyether-modified polydimethylsiloxane leveling agent (lubricant solution) (trade name “BYK-300” supplied by BYK Chemie GmbH, NV: 52 percent by weight), and 0.02 g of a melamine crosslinking agent (trade name “NIKALAC MW-30M” supplied by Sanwa Chemical Co., Ltd.), followed by vigorous stirring for about 20 minutes. In this manner, was prepared a top coat layer coating composition (NV: 0.2 percent by weight). This contained 48 parts by weight of the electroconductive polymer, 26 parts by weight of the lubricant, and 20 parts by weight of the melamine crosslinking agent per 100 parts by weight of Binder Polymer 3 (acrylic polymer) each in solids content.
Top Coat Layer Formation
To a 38 μm thick by 30 cm wide by 40 cm long transparent poly(ethylene terephthalate) film (PET film) having one surface treated with corona discharge, the top coat layer coating composition was applied on the corona-discharged surface using a bar coater to a dry thickness of about 8 nm. The applied composition was dried by heating at 130° C. for 2 minutes to form a top coat layer on one side of the PET film. In this manner, was prepared a transparent film substrate (hereinafter also referred to as “SUB 6”) having a PET film and, on one side thereof, a transparent top coat layer.
Table 1 indicates formulations (compositions) of the top coat layers in the above-prepared transparent film substrates (SUBS 1 to 6); and evaluation data of the transparent film substrates according to evaluation procedures mentioned later.
In a vessel, were placed 90 parts by weight of water and, as indicated in Table 2, 96 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of acrylic acid (AA), and 3 parts by weight of a nonionic-anionic reactive emulsifier (trade name “AQUALON HS-10” supplied by Dai-ichi Kogyo Seiyaku Co., Ltd.), followed by stirring by a homomixer, to give a monomer emulsion.
Next, 50 parts by weight of water, 0.01 part by weight of a polymerization initiator (ammonium persulfate), and the above-prepared monomer emulsion in an amount corresponding to 10 percent by weight of the prepared amount were placed in a reactor equipped with a condenser, a nitrogen inlet tube, a thermometer, and a stirrer, followed by emulsion polymerization at 75° C. for one hour with stirring. The mixture was combined with 0.05 part by weight of the polymerization initiator (ammonium persulfate), subsequently further combined with the whole quantity of the residual monomer emulsion (in an amount corresponding to 90 percent by weight) added over 3 hours with stirring, and was allowed to react at 75° C. for 3 hours. Next, this was cooled to 30° C., combined with an aqueous ammonia having a concentration of 10 percent by weight so as to have a pH of 8, and yielded an acrylic emulsion polymer water dispersion.
The above-prepared acrylic emulsion polymer water dispersion was combined with 1.0 part by weight of “ADEKA Pluronic 25R-1” as a compound (B), 0.2 part by weight of “EFKA-3570” as a leveling agent, and 3 parts by weight of an epoxy crosslinking agent [trade name “TETRAD-Cu” supplied by MITSUBISHI GAS CHEMICAL COMPANY, INC., 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, epoxy equivalent: 110, number of functional groups: 4] as a water-insoluble crosslinking agent, per 100 parts by weight of solid components in the acrylic emulsion polymer. The resulting mixture was stirred using a stirrer at 23° C. and 300 rpm for 10 minutes, and thereby yielded a water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 1” (Pressure-sensitive Adhesive 1)).
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 2”) was prepared by the procedure of Production Example 7, except for using 3 parts by weight of “ADEKA REASOAP SE-10N” as a reactive emulsifier instead of “AQUALON HS-10”, as indicated in Table 2.
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PEA 3”) was prepared by the procedure of Production Example 7, except for using 92 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of methyl methacrylate (MMA), and 4 parts by weight of acrylic acid (AA) as constitutive monomers to form an acrylic emulsion polymer, as indicated in Table 2.
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 4”) was prepared by the procedure of Production Example 8, except for using 0.5 part by weight of “ADEKA Pluronic 17R-3” as a compound (B) instead of “ADEKA Pluronic 25R-1”, as indicated in Table 2.
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 5”) was prepared by the procedure of Production Example 7, except for using 0.5 part by weight of “PPO-PEO-PPO” as a compound (B) instead of “ADEKA Pluronic 25R-1”; and using 3 parts by weight of “TETRAD-X” as a water-insoluble crosslinking agent (C) instead of “TETRAD-C”, as indicated in Table 2.
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 6”) was prepared by the procedure of Production Example 7, except for using no copolymer as the compound (B), as indicated in Table 2.
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 7”) was prepared by the procedure of Production Example 7, except for using, instead of the copolymer serving as the compound (B), 0.5 part by weight of “POLYRan (EO-PO)” as another compound than compound (B), as indicated in Table 2
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 8”) was prepared by the procedure of Production Example 7, except for using, instead of the copolymer serving as the compound (B), 3.0 parts by weight of “PEO-PPO-PEO” as another compound than compound (B), as indicated in Table 2.
A water-dispersible acrylic pressure-sensitive adhesive composition (hereinafter also referred to as “PSA 9”) was prepared by the procedure of Production Example 7, except for using “ADEKA Pluronic 25R-1” as the compound (B) in an amount of 0.1 part by weight per 100 parts by weight of solid components in the acrylic emulsion polymer, as indicated in Table 2.
Table 2 indicates the formulations of the above-prepared water-dispersible acrylic pressure-sensitive adhesive compositions (PSAs 1 to 9).
With reference to Table 3, a pressure-sensitive adhesive sheet was prepared in the following manner. Specifically, the above-prepared water-dispersible acrylic pressure-sensitive adhesive composition (PSA 1) was applied to a surface of the above-prepared transparent film substrate (SUB 1) opposite to the top coat layer using an applicator (TESTER SANGYO CO., LTD) to a dry thickness of 15 μm. The applied composition was dried in an oven with internal air circulation at 120° C. for 2 minutes to give a pressure-sensitive adhesive layer. To a PET film having a surface treated with a silicone (“MRF38” supplied by Mitsubishi Plastics, Inc.), the dried pressure-sensitive adhesive layer was laminated on the silicone-treated surface, aged at 50° C. for 3 days, and yielded the pressure-sensitive adhesive sheet.
Pressure-sensitive adhesive sheets were prepared by the procedure of Example 1, except for using a water-dispersible acrylic pressure-sensitive adhesive composition of different type and/or a transparent film substrate of different type, as indicated in Table 3
The product under the trade name of “Diafoil T100G” (supplied by Mitsubishi Chemical Corporation) used as a substrate in Comparative Example 6 was a PET film having an antistatic layer on one side thereof (antistatically treated PET film). The antistatic layer contained a compound having an ammonium base as an antistatic agent.
Evaluations
The above-prepared transparent film substrates, and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were evaluated according to measurement methods or evaluation methods mentioned below. The solvent-insoluble content and the weight-average molecular weight of a solvent-soluble fraction of the acrylic emulsion polymer; and the solvent-insoluble content of the acrylic pressure-sensitive adhesive layer (after crosslinking) were measured by the aforementioned measurement methods.
Evaluation data are indicated in Tables 1 to 3.
(1) Top Coat Layer Thickness (Average Thickness and Thickness Variation)
The top coat layer thickness was measured by observing a cross section of each of the transparent film substrates prepared in Production Examples with a transmission electron microscope (TEM).
Independently, the peak intensities of sulfur atom (derived from PEDT and PSS contained in the top coat layer) were measured in the top coat layer surface of each transparent film substrate with an X-ray fluorescence analyzer (XRF analyzer, Model “ZSX-100e” supplied by Rigaku Corporation). The X-ray fluorescence analysis was performed under conditions as follows:
X-ray Fluorescence Analysis
Instrument: XRF analyzer, Model “ZSX-100e” supplied by Rigaku Corporation
X-ray source: vertical Rh tube
Analysis range: within a circle of 30 mm diameter
Detected X-ray: S-Kα
Dispersive crystal: Ge crystal
Output: 50 kV, 70 mA
Based on the top coat layer thickness (the measured value) obtained by TEM observation and the data of the X-ray fluorescence analysis, a calibration curve was plotted to derive the top coat layer thickness from peak intensities observed in the X-ray fluorescence analysis.
The top coat layer thickness of each transparent film substrate was measured using the calibration curve. Specifically, X-ray fluorescence analysis was performed starting from one end of the width through the other end at 1/6, 2/6, 3/6, 4/6, and 5/6 the width along a straight line across the width (in a direction perpendicular to the bar coater's moving direction) of the area bearing the top coat layer. Based on the obtained data (sulfur atom X-ray intensities (kcps)) together with the top coat layer formulation (the content of PEDT and PSS) and the calibration curve, were determined the thicknesses of the top coat layer at the respective five measurement points. The average thickness Dave was determined by averaging the top coat layer thickness values at the five measurement points. The thickness variation ΔD was calculated by substituting the average thickness Dave, the maximum value Dmax and the minimum value Dmin of the top coat layer thickness values at the five measurement points into an equation as follows: ΔD=(Dmax−Dmin)/Dave×100(%).
(2) X-Ray Intensity Variation in Top Coat Layer Surface
The average X-ray intensity Iave was determined by averaging the sulfur atom X-ray intensities (kcps) obtained at the respective locations (five measurement locations) by X-ray fluorescence analysis. The X-ray intensity variation ΔI was calculated by substituting the average X-ray intensity Iave, the maximum value Imax and the minimum value Imin of the X-ray intensities at the respective locations (five measurement locations) into an equation as follows: ΔI=(Imax−Imin)/Iave×100(%).
(3) Transparent Film Substrate Appearance
The backside (top coat layer side surface) of each of the transparent film substrates (SUBs 1 to 6) was visually observed in a bright room having a window admitting outside light. The observation was performed beside the window where no direct sunlight was got during the daytime on a sunny day. The transparent film substrate appearance was evaluated based on the observation data according to criteria as follows:
Good (G; good appearance): neither unevenness nor streak was observed;
Poor (P; poor appearance): unevenness and/or streaks were observed.
(4) Top Coat Layer Surface Resistivity
The surface resistance Rs on the top coat layer side surface of each of the above-prepared transparent film substrates (SUBs 1 to 6) was measured according to JIS K6911 at an ambient temperature of 23° C. and relative humidity of 55% using an insulation resistance tester (trade name “Hiresta-up MCP-HT450” supplied by Mitsubishi Chemical Analytech Co., Ltd.). A voltage of 100 V was applied, and the surface resistance Rs was read 60 seconds into the measurement. Based on the data, the surface resistivity was calculated according to an equation as follows:
ρs=Rs×E/V×π(D+d)/(D−d)
wherein ρs represents the surface resistivity (Ω/square); Rs represents the surface resistance (Ω); B represents the applied voltage (V); V represents the measured voltage (V); D represents the inner diameter (cm) of the ring portion of the surface electrode; and d represents the outer diameter (cm) of the inner circular portion of the surface electrode.
(5) Top Coat Layer Surface Scratch Resistance
A sample of 10 cm2 (10 cm wide by 10 cm long) was cut out from each of the above-prepared transparent film substrates (SUBs 1 to 6). An examiner scratched the backside (the top coat layer side surface) of the sample by fingernails in a bright room having a window admitting outside light, and the scratch resistance was evaluated by whether or not the sample was scratched by the fingernails. Specifically, the backside of the sample after being scratched by the fingernails was observed with an optical microscope. A sample where debris scraped off from the top coat layer was observed was evaluated as poor (P) (poor scratch resistance); whereas a sample where no debris was observed was evaluated as good (G) (good scratch resistance).
(6) Resistance to Adhesive Strength Increase
Initial Adhesive Strength
Each of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples (sample size: 25 mm wide by 100 mm long) was laminated onto a polarizing plate using a laminator (compact laminator supplied by TESTER SANGYO CO., LTD.) at 0.25 MPa and 0.3 m/min. The polarizing plate was made from a triacetyl cellulose (TAC) and had an arithmetic mean surface roughness Ra of about 21 nm in the machine direction (MD), about 31 nm in the transverse direction (TD), and about 26 nm on an average of the machine direction (MD) and the transverse direction (TD).
The laminated sample including the pressure-sensitive adhesive sheet and the polarizing plate was left stand at at an ambient temperature of 23° C. and relative humidity of 50% for 20 minutes, subjected to a 180-degree peel test under conditions mentioned below, the adhesive strength (N/25 mm) of the pressure-sensitive adhesive sheet to the polarizing plate was measured and defined as an “initial adhesive strength.”
Adhesive Strength after One-Week Application/Storage at 40° C.
Each of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples (sample size: 25 mm wide by 100 mm long) was laminated onto a polarizing plate using a laminator (compact laminator supplied by TESTER SANGYO CO., LTD.) at 0.25 MPa and 0.3 m/min. The polarizing plate was made from a triacetyl cellulose (TAO) and had an arithmetic mean surface roughness Ra of about 21 nm in the machine direction (MD), about 31 nm in the transverse direction (TD), and about 26 nm on an average of the machine direction (MD) and the transverse direction (TD).
The laminated sample including the pressure-sensitive adhesive sheet and the polarizing plate was stored at an ambient temperature of 40° C. for one week, left stand at an ambient temperature of 23° C. and relative humidity of 50% for hours, subjected to a 180-degree peel test under the conditions mentioned later, the adhesive strength (N/25 mm) of the pressure-sensitive adhesive sheet to the polarizing plate was measured and defined, as an “adhesive strength after one-week application/storage at 40° C.”
The 180-degree peel test was performed using a tensile tester at an ambient temperature of 23° C. and relative humidity of 50% and at a tensile speed of 0.3 m/min.
A sample having a difference between the initial adhesive strength and the adhesive strength after one-week application/storage at 40° C. [(adhesive strength after one-week application/storage at 40° C.)−(initial adhesive strength)] of 0.10 N/25 mm or less could be determined as having satisfactory resistance to adhesive strength increase.
(7) Cloudiness (Clouding Resistance) of Pressure Sensitive Adhesive Sheet Upon Storage Under Humid Conditions
Each of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples was left stand at an ambient temperature of 50° C. and relative humidity of 95% for 24 hours (stored under humid conditions), the haze of the resulting sample was measured using “DIGITAL HAZEMETER NDH 20D” supplied by Nippon Denshoku Industries Co., Ltd. and defined as a “haze after storage under humid conditions.” The measurement was performed within 3 minutes after the retrieval of the sample from the environment at a temperature of 50° C. and relative humidity of 95%. As a comparison, the haze of the sample before the storage under humid conditions was also measured and defined as a “haze before storage under humid conditions.”
(8) Pressure-Sensitive Adhesive Sheet Appearance (Visual Quality)
The acrylic pressure-sensitive adhesive layer surface of each of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and defects (dimples and bubbles) in the observation area of 10 cm long by 10 cm wide were counted. The appearance (visual quality) of the pressure-sensitive adhesive sheet was evaluated based on the above-obtained data and the evaluation data of the transparent film substrate appearance according to criteria as follows:
Poor appearance (P) of the pressure-sensitive adhesive sheet: the transparent film substrate had a poor appearance, or the number of defects was 101 or more although the transparent film substrate had a good appearance;
Good appearance (G) of the pressure-sensitive adhesive sheet: the transparent film substrate had a good appearance, and the number of defects was from 0 to 100.
Abbreviations used in Tables 2 and 3 are as follows:
Hereinafter the percentage of the “total weight of EO(s)” based on the “total weight of compound(s) (B)” is indicated as an “EO content.”
Constitutive Monomers
2EHA: 2-ethylhexyl acrylate
MMA: methyl methacrylate
AA: acrylic acid
Emulsifier
HS-10: trade name “AQUALON HS-10” (nonionic-anionic reactive emulsifier) supplied by Dai-ichi Kogyo Seiyaku Co., Ltd.
SE-10N: trade name “ADEKA REASOAP SE-10N” (nonionic-anionic reactive emulsifier) supplied by ADEKA CORPORATION
Crosslinking Agent
TETRAD C: trade name “TETRAD-C” (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, epoxy equivalent: 110, number of functional groups: 4) supplied by MITSUBISHI GAS CHEMICAL COMPANY, INC.
TETRAD X: trade name “TETRAD-X” (1,3-bis(N,N-diglycidylaminomethyl)benzene, epoxy equivalent: 100, number of functional groups: 4) supplied by MITSUBISHI GAS CHEMICAL COMPANY, INC.
Compound (B)
ADEKA Pluronic 25R-1: trade name “ADEKA Pluronic 25R-1” (number-average molecular weight: 2800, EO content: 10 percent by weight, active ingredient: 100 percent by weight) supplied by ADEKA CORPORATION
ADEKA Pluronic 17R-3: trade name “ADEKA Pluronic 17R-3” (number-average molecular weight: 2000, EO content: 30 percent by weight, active ingredient: 100 percent by weight) supplied by ADEKA CORPORATION
PPO-PEO-PPO: Poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) (number-average molecular weight: 2000, EO content: 50 percent by weight, active ingredient: 100 percent by weight) supplied by SIGMA-ALDRICH Co., LLC.
Compound Other than Compound (B)
POLYRan (EO-PO): Poly(ethylene glycol-ran-propylene glycol) (number-average molecular weight: 2500, BO content: 75 percent by weight, active ingredient: 100 percent by weight) supplied by SIGMA-ALDRICH Co., LLC.
PEO-PPO-PEO: Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (number-average molecular weight: 1900, EO content: 50 percent by weight, active ingredient: 100 percent by weight) supplied by SIGMA-ALDRICH Co., LLC.
Leveling Agent
EFKA-3570: neutralized fluorocarbon-modified polymer supplied by BASF SE
Substrate (Transparent Film Substrate)
T100G: trade name “Diafoil T100G” (antistatically treated PET film) supplied by Mitsubishi Chemical Corporation
The data in Table 3 demonstrate as follows. The pressure-sensitive adhesive sheets according to Examples satisfied conditions specified in the present invention, had a good appearance, and suffered from small increase in adhesive strength with time after application. They had antistatic properties and scratch resistance at satisfactory levels and did not become cloudy even when stored under humid conditions.
In contrast, Comparative Examples 1 to 3 did not employ a compound (B); and Comparative Examples 4 and 5 had a substrate top coat layer having an average thickness and/or a thickness variation not satisfying conditions specified in the present invention. The pressure-sensitive adhesive sheets according to these comparative examples had a poor appearance. Among them, Comparative Example 5 containing no melamine crosslinking agent as a component to constitute the top coat layer also had poor scratch resistance. Comparative Example 2 employed, instead of a compound (B), a compound other than the compound (B). The pressure-sensitive adhesive sheet according to this comparative example had a haze largely increased after storage under humid conditions and thus appeared cloudy through storage under humid conditions. Comparative Example 6 employed a substrate antistatic layer being not a top coat layer including a polythiophene, an acrylic resin, and a melamine crosslinking agent. The pressure-sensitive adhesive sheet according to this comparative example had a haze increased after storage under humid conditions and had poor scratch resistance.
The pressure-sensitive adhesive sheets according to embodiments of the present invention are used in applications where they will be removed. They are preferably usable particularly in surface protection of optical members (e.g., optical plastics, optical glass, and optical films) typically as a surface-protecting film for an optical member. The optical members are exemplified by polarizing plates, retardation films, anti-reflective films, wave plates, compensation films, and brightness enhancing films constituting panels such as liquid crystal displays, organic electroluminescence (organic EL) displays, and field emission displays. The pressure-sensitive adhesive sheets according to the present invention are also usable in surface-protection, failure-prevention, removal of foreign matter, or masking upon production of microfabricated components such as semiconductors (semiconductor devices), circuits, printed circuit boards, masks, and lead frames.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-091485 | Apr 2011 | JP | national |
| 2011-091503 | Apr 2011 | JP | national |
| 2011-091509 | Apr 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/059522 | 4/6/2012 | WO | 00 | 10/11/2013 |
