Patent Application
20190161650
The present application claims priority to Japanese Patent Application No. 2017-229864 filed on Nov. 30, 2017; the entire content thereof is incorporated herein by reference.
The present invention relates to a pressure-sensitive adhesive sheet.
In general, pressure-sensitive adhesive (PSA) exists as a soft solid (a viscoelastic material) in a room temperature range and has a property to adhere easily to adherend with some pressure applied. Because of such properties, PSA has been widely used as, for instance, an on-substrate PSA sheet having a PSA layer on a support substrate or a substrate-free PSA sheet with no support substrate, for purposes such as bonding, fixing and protecting parts in smartphones and other mobile electronics. Technical documents related to double-faced PSA tape used in fixing parts of mobile electronics include Japanese Patent Application Publication No. 2017-132911, Japanese Patent Application Publication No. 2013-100485, Japanese Patent Application Publication No. 2017-002292 and Japanese Patent Application Publication No. 2015-147873.
When fixing parts with PSA sheets in mobile electronics, bonding areas are usually small due to limiting factors such as size and weight. PSA sheets used for this purpose need to have adhesive strength capable of achieving good fastening even onto small areas, calling for higher levels of properties that are necessary to meet demand for weight reduction and downsizing. In particular, with respect to mobile electronics with touch displays typified by smartphones, while products themselves are becoming smaller and thinner, their displays are becoming larger for their visibility and ease of navigation; because of these unique circumstances, the PSA is required to provide adhesive bonding performance under more demanding conditions. For instance, in this application, besides limited bonding areas, for instance, flexible parts such as flexible printed circuits (FPC) are folded, placed in limited internal spaces in mobile electronics, precisely positioned and stably fixed with PSA sheets.
In these applications, from the standpoint of the adhesive strength, conformability, weight, etc., it is preferable to use substrate-free, adhesively double-faced PSA sheets. However, because a substrate-free PSA sheet is essentially formed of a viscoelastic body, it has disadvantages to a substrate-supported PSA sheet in view of processability (suitability to processing). In particular, for fixing a part of a mobile electronic device, when subjected to a cutting process such as punching and formed in a shape (a ribbon shape, a frame shape, etc.) corresponding to a shape of a part to be fixed and applied to the adherend, it tends to be harder to precisely process a substrate-free PSA sheet formed solely of a viscoelastic body. Until applied to an adherend or for a certain period of time after applied, unwanted part (part to be removed) of the PSA sheet and the cut-out piece to be used may remain adjacent to each other. In such a case, the PSA may undergo self-fusion (or blocking) at their interface and removal of the unwanted part of the PSA sheet may become time-consuming.
The present invention has been made in view of such circumstances with an objective to provide a PSA sheet highly suited for processing (that can be easily processed).
The present description provides a PSA sheet comprising a substrate layer and a PSA layer provided on at least one face of the substrate layer. The PSA layer has a total thickness TPSA and the substrate layer has a thickness TS at a TS/TPSA ratio value greater than 0.3. The PSA layer has a storage modulus at 25° C., G′(25° C.) of 0.15 MPa or greater and a loss modulus at 25° C., G″(25° C.) of 2.0 MPa or less.
The PSA sheet disclosed herein is characterized primarily by having a substrate layer that has a thickness satisfying the TS/TPSA ratio value greater than 0.3 relative to the PSA layer. With the use of a substrate layer having a thickness that satisfies the TS/TPSA ratio value, the PSA sheet can be made easier to cut and handle. The TS/TPSA ratio value being greater than 0.3 means that the thickness of the PSA layer is limited. This limits the cross-sectional area susceptible to blocking by the PSA layer that has been put through a cutting process, thereby making it possible to prevent lowering of efficiency caused by the blocking when removing the unwanted part of the PSA sheet.
The PSA sheet disclosed herein is characterized secondarily by the PSA layer having a storage modulus at 25° C., G′(25° C.), of 0.15 MPa or greater as well as a loss modulus at 25° C., G″(25° C.), of 2.0 MPa or less. With a PSA having such G′(25° C.) and G″(25° C.), the PSA sheet can combine good suitability to cutting based on the G′(25° C.) at or above a certain value with blocking resistance based on the G″(25° C.) at or below a prescribed value. The PSA sheet in this embodiment shows excellent processability.
As used herein, when the simple term “processability” is used, it should be understood in a broad sense, including aforementioned suitability to cutting as well as ease of handling during application, etc., and efficiency of removal.
In a preferable embodiment of the PSA sheet disclosed herein, the substrate layer has a thickness of 20 μm or greater. With the use of a substrate layer having such a thickness, a preferable TS/TPSA ratio value can be obtained and excellent processability can be further obtained. The substrate layer according to a preferable embodiment is formed of resin film. In particular, a substrate layer formed of polyester-based resin is preferable. A substrate layer formed of polyester-based resin such as polyethylene terephthalate (PET) with a certain thickness has rigidity suited for cutting, removal, etc.
In another preferable embodiment, the substrate layer is formed of a foam sheet. For instance, because the PSA sheet comprising a foam sheet usually has a certain thickness, when fixing a folded resin plate with the PSA sheet, damage (breaking and cracking) to the resin plate can be preferably prevented based on the thickness suited for the R-curve of a fold in the resin plate and the cushioning properties.
In a preferable embodiment of the PSA sheet disclosed herein, the PSA layer has a storage modulus at 85° C., G′(85° C.), of 0.02 MPa or greater. The PSA sheet having such a PSA layer is less likely to deform under a continuously-applied load.
In a preferable embodiment of the PSA sheet disclosed herein, the PSA layer is an acrylic PSA layer comprising an acrylic polymer. With the use of an acrylic polymer, a PSA layer having specific viscoelastic properties can be preferably fabricated.
In a preferable embodiment, as the PSA layer, the PSA sheet disclosed herein comprises a first PSA layer provided on a first face of the substrate layer as well as a second PSA layer provided on a second face of the substrate layer. The art disclosed herein can be preferably implemented in an embodiment of an on-substrate (substrate-supported) double-faced PSA sheet.
The PSA sheet disclosed herein is suited for cutting including punching and thus can be used in various applications after processed into a prescribed shape such as a ribbon shape and a frame shape. In a preferable embodiment, it can be used for fixing parts of mobile electronic devices. The PSA sheet (typically a double-faced PSA sheet) has a substrate layer in at least a prescribed thickness; and therefore, with respect to an adherend having a plate form (e.g. a resin plate) that can be damaged when folded, when fixing the adherend in a folded position, the fold in the adherend can be provided with an R-curve corresponding to the thickness of the PSA sheet. This can reduce the risk of causing damage to the adherend upon folding. When the adherend is FPC, the risk of disconnection can be reduced. In other words, the PSA sheet (preferably a double-faced PSA sheet) disclosed herein is preferably used for fixing an adherend plate (e.g. a resin plate) in a folded position. Applications of the PSA sheet disclosed herein include fixing of FPC.
Preferred embodiments of the present invention are described below. Matters necessary to practice this invention other than those specifically referred to in this description can be understood by a person skilled in the art based on the disclosure about implementing the invention in this description and common general knowledge at the time of application. The present invention can be practiced based on the contents disclosed in this description and common technical knowledge in the subject field. In the drawings referenced below, a common reference numeral may be assigned to members or sites producing the same effects, and duplicated descriptions are sometimes omitted or simplified. The embodiments described in the drawings are schematized for clear illustration of the present invention, and do not necessarily represent accurate sizes or reduction scales of the PSA sheet of this invention that is actually provided as a product.
As used herein, the term “PSA” refers to, as described earlier, a material that exists as a soft solid (a viscoelastic material) in a room temperature range and has a property to adhere easily to adherend with some pressure applied. As defined in “Adhesion: Fundamental and Practice” by C. A. Dahlquist (McLaren & Sons (1966), P. 143), PSA referred to herein can be a material that has a property satisfying complex tensile modulus E* (1Hz)<107 dyne/cm2 (typically, a material that exhibits the described characteristics at 25° C.).
As used herein, the term “(meth)acryloyl” comprehensively refers to acryloyl and methacryloyl. Similarly, the term “(meth)acrylate” comprehensively refers to acrylate and methacrylate, and the term “(meth)acryl” comprehensively refers to acryl and methacryl.
As used herein, the term “acrylic polymer” refers to a polymer comprising, as a monomeric unit constituting the polymer, a monomeric unit derived from a monomer having at least one (meth)acryloyl group per molecule. Hereinafter, a monomer having at least one (meth)acryloyl group per molecule is referred to as “acrylic monomer” as well. As used herein, the acrylic polymer is defined as a polymer comprising a monomeric unit derived from an acrylic monomer.
The PSA sheet disclosed herein is an on-substrate PSA sheet formed to have the PSA layer on one or each face of a substrate layer (support substrate). The concept of PSA sheet herein may encompass so-called PSA tape, PSA labels, PSA film, etc. The PSA sheet disclosed herein can be in a roll or in a flat sheet. Alternatively, the PSA sheet may be processed into various shapes.
The PSA disclosed herein may have, for example, cross-sectional constitutions schematically illustrated in
The PSA sheet disclosed herein is characterized by having a ratio of the substrate layer's thickness TS to the PSA layer's total thickness TPSA, TS/TPSA, greater than 0.3 (when two (first and second) PSA layers are included, their combined thickness; the same applies, hereinafter). This increase the ease of cutting and handling the PSA sheet. The thickness of the PSA layer is decreased in relative, to limit the cross-sectional area subject to blocking by the PSA layer that has been put through a cutting process, thereby making it possible to prevent lowering of efficiency of removing unwanted part of the PSA sheet caused by the blocking. The TS/TPSA value is preferably 0.4 or greater, more preferably 0.6 or greater, or yet more preferably 0.8 or greater. The minimum TS/TPSA value is not particularly limited. It is usually 50 or less, or suitably about 30 or less (e.g. 10 or less). The TS/TPSA value can be 1 or less.
The PSA layer (each PSA layer if it has first and second PSA layers) disclosed herein is characterized by having a storage modulus at 25° C., G′(25° C.), of 0.15 MPa or greater. The use of PSA having such a G′(25° C.) value make it well suited for cutting. According to PSA having such a G′(25° C.) value, in an early stage after its application to adherend, good deformation resistance can be exhibited. The G′(25° C.) is preferably 0.17 MPa or greater, more preferably 0.2 MPa or greater, or yet more preferably 0.23 MPa or greater. The G′(25° C.) can be, for instance, 0.25 MPa or greater. The G′(25° C.) is usually suitably 1.0 MPa or less. From the standpoint of combining light-pressure initial adhesion and deformation resistance, it is preferably 0.6 MPa or less, more preferably 0.4 MPa or less, yet more preferably 0.3 MPa or less, or particularly preferably 0.25 MPa or less. The G′(25° C.) value can also be, for instance, 0.2 MPa or less. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the storage moduli G′(25° C.) of the first and second PSA layers can be equal or different.
The PSA layer (each PSA layer when it has two (first and second) PSA layers) disclosed herein suitably is characterized by having a loss modulus at 25° C., G″(25° C.), of 2.0 MPa or less. Having such a G″(25° C.) in addition to an aforementioned G′(25° C.), the PSA can achieve good suitability to cutting based on the G′(25° C.) at or above a certain value as well as blocking resistance based on the G″(25° C.) at or below a prescribed value. The G″(25° C.) is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, or yet more preferably 0.5 MPa or less. The G″(25° C.) can also be 0.3 MPa or less (e.g. 0.25 MPa or less). The G″(25° C.) is usually suitably 0.01 MPa or greater. From the standpoint of the ease of wetting the adherend surface as well as light-pressure initial adhesion, etc., it is preferably 0.05 MPa or greater, or more preferably 0.1 MPa or greater. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the loss moduli G″(25° C.) values of the first and second PSA layers can be equal or different.
The PSA layer (at least one PSA layer when it has two (first and second) PSA layers) disclosed herein suitably has a storage modulus at 85° C., G′(85° C.), of 0.02 MPa or greater. At such a G′(85° C.) value, continuous deformation resistance can be obtained. The G′(85° C.) value can be 0.022 MPa or greater. The G′(85° C.) is preferably 0.025 MPa or greater, or more preferably 0.027 MPa or greater. The G′(85° C.) can also be about 0.03 MPa or greater (e.g. 0.035 MPa or greater). The G′(85° C.) is usually suitably 1.0 MPa or less, for instance, 0.5 MPa or less, typically 0.1 MPa or less. The G′(85° C.) value can also be 0.05 MPa or less. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the storage moduli G′(85° C.) values of the first and second PSA layers can be equal or different.
At a temperature (press-bonding temperature) where the PSA sheet is press-bonded to adherend, the PSA layer (at least one PSA layer when it has two (first and second) PSA layers) disclosed herein preferably has a storage modulus G′(apply) of 0.6 MPa or less. Even when lightly press-bonded, PSA having such a G′(apply) value can wet the adherend surface well to show excellent initial adhesion. The G′(apply) is more preferably 0.4 MPa or less, yet more preferably 0.3 MPa or less, or particularly preferably 0.25 MPa or less. The G′(apply) can also be, for instance, 0.2 MPa or less. From the standpoint of combining light-pressure initial adhesion and deformation resistance, the G′(apply) is suitably greater than 0.12 MPa, preferably 0.15 MPa or greater, or more preferably 0.17 MPa or greater (e.g. 0.2 MPa or greater). The press-bonding temperature is selected from a range above 0° C. and below 60° C. in view of the ease of press-bonding, temperature management, etc. In case of a PSA sheet used for mobile electronics applications, because of the temperature limitation in these applications, the press-bonding temperature is desirably selected from a range between 20° C. and 45° C. (typically 25° C. or 40° C.). Unlike conventional press-bonding carried out at around 100° C., press-bonding in this temperature range is thermal press-bonding that can be applied to electronics and the like. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the storage moduli G′(apply) of the first and second PSA layers can be equal or different. In the art disclosed herein, the press-bonding temperature can be typically 25° C. or 40° C. Thus, a storage modulus G′(apply) can be read as a storage modulus at 25° C., G′(25° C.), or a storage modulus at 40° C., G′(40° C.).
In the art disclosed herein, the storage moduli G′(25° C.), G′(85° C.) and G′(apply) as well as the loss modulus G″(25° C.) of the PSA layer can be determined by dynamic elastic modulus measurement. In particular, several layers of the PSA of interest are layered to fabricate an approximately 2 mm thick PSA layer. A specimen obtained by punching out a disc of 7.9 mm diameter from the PSA layer is fixed between parallel plates. With a rheometer (e.g. ARES available from TA Instruments or a comparable system), dynamic elastic modulus measurement is carried out to determine storage moduli G′(25° C.), G′(85° C.) and G′(apply), and loss modulus G″(25° C.).
Measurement mode: shear mode
Temperature range: −70° C. to 150° C.
Heating rate: 5° C./min
Measurement frequency: 1 Hz
The same measurement method is also used in the working examples described later. The PSA layer subject to measurement can be formed by applying the corresponding PSA composition in layers and drying or curing them.
In the art disclosed herein, the type of PSA that constitutes the PSA layer (at least one PSA layer when it has two (first and second) PSA layers; the same applies hereinafter unless otherwise informed) is not particularly limited. For example, the PSA layer may be constituted, comprising one, two or more species of PSA selected among various known species of PSA, such as an acrylic PSA, rubber-based PSA (natural rubber-based, synthetic rubber-based, their mixture-based, etc.), silicone-based PSA, polyester-based PSA, urethane-based PSA, polyether-based PSA, polyamide-based PSA, fluorine-based PSA, etc. Herein, the acrylic PSA refers to a PSA comprising a (meth)acrylic polymer as the base polymer (the primary component among polymers, i.e. a component accounting for more than 50% by weight). The same applies to the rubber-based PSA and other PSA. In a PSA layer preferable from the standpoint of the transparency, weatherability, etc., the acrylic PSA content is 50% by weight or greater, more preferably 70% by weight or greater, or yet more preferably 90% by weight or greater. The acrylic PSA content can be greater than 98% by weight, or the PSA layer may be formed essentially of an acrylic PSA. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the types of PSA forming the first and second PSA layers can be the same or different. When the first and second PSA layers are formed from the same type of PSA, their PSA compositions can be the same or different.
While no particular limitations are imposed, in a preferable embodiment of the art disclosed herein, the PSA forming the PSA layer and the PSA composition for forming the PSA comprises an acrylic polymer as the base polymer. The acrylic polymer is preferably a polymer of a starting monomer mixture that comprises an alkyl (meth)acrylate as the primary monomer and may further comprise a copolymerizable secondary monomer. Here, the primary monomer refers to a component that accounts for more than 50% by weight of the starting monomers.
As the alkyl (meth)acrylate, for instance, a compound represented by the formula (1) below can be favorably used.
CH2═C(R1)COOR2 (1)
Here, R1 in the formula (1) is a hydrogen atom or a methyl group. R2 is an acyclic alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of the number of carbon atoms may be indicated as “C1-20”). From the standpoint of the PSA's storage modulus, etc., an alkyl (meth)acrylate wherein R2 is a C1-14 acyclic alkyl group is preferable, and an alkyl (meth)acrylate wherein R2 is a C1-10 acyclic alkyl group is more preferable. An alkyl (meth)acrylate wherein R2 is a butyl group or a 2-ethylhexyl group is particularly preferable.
Examples of an alkyl (meth)acrylate with R2 being a C1-20 acyclic alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. These alkyl (meth)acrylates can be used solely as one species or in a combination of two or more species. Particularly preferable (meth)acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
The art disclosed herein can be preferably implemented in an embodiment where the monomers forming the acrylic polymer include at least BA or 2EHA and the combined amount of BA and 2EHA accounts for 75% by weight or more (usually 85% by weight or more, e.g. 90% by weight or more, or even 95% by weight or more) of the alkyl (meth)acrylate in the monomers. For instance, the art disclosed herein can be implemented in embodiments where the monomers consist of, as the alkyl (meth)acrylate, solely BA, solely 2EHA, both BA and 2EHA, etc.
When the monomers include both BA and 2EHA, the BA to 2EHA weight ratio (BA/2EHA) is not particularly limited. For instance, it can be 1/99 or higher and 99/1 or lower. In a preferable embodiment, BA/2EHA can be 40/60 or lower (e.g. 1/99 or higher and 40/60 or lower), 20/80 or lower, or even 10/90 or lower (e.g. 1/99 or higher and 10/90 or lower).
The art disclosed herein can be preferably implemented in an embodiment where the monomers forming the acrylic polymer include at least 50% (by weight) C7-10 alkyl (meth)acrylate. In other words, it is preferable that the copolymerization ratio of the C7-10 alkyl (meth)acrylate in the acrylic polymer is 50% by weight or higher. With such use of the C7-10 alkyl (meth)acrylate as the primary monomer, the acrylic polymer can be preferably designed to achieve both light-pressure initial adhesion and deformation resistance to a continuous z-axial load. The ratio of the C7-10 alkyl (meth)acrylate in the monomers (i.e. its copolymerization ratio) is more preferably higher than 50% by weight, yet more preferably 60% by weight or higher, or particularly preferably 70% by weight or higher (e.g. 80% by weight or higher, or even 85% by weight or higher). The upper limit of the ratio of C7-10 alkyl (meth)acrylate in the monomers is not particularly limited. It is usually 97% by weight or lower; in relation to the ratio of acidic group-containing monomer used, it is suitably 92% by weight or lower, or preferably 90% by weight or lower (usually 88% by weight or lower, e.g. 85% by weight or lower). For the C7-10 alkyl (meth)acrylate, solely one species or a combination of two or more species can be used. Favorable examples of the C7-10 alkyl (meth)acrylate include 2EHA, isooctyl acrylate and isononyl acrylate. Among them, 2EHA is preferable.
In an embodiment using 2EHA as the primary monomer, the copolymerization ratio of 2EHA in the acrylic polymer is preferably 50% by weight or higher, more preferably higher than 50% by weight, yet more preferably 60% by weight or higher, or particularly preferably 70% by weight or higher (e.g. 80% by weight or higher, or even 85% by weight or higher). With the 2EHA having a low Tg and excellent adhesive properties copolymerized as the primary monomer, the PSA can bond to adherends strongly and tightly. The copolymerization ratio of 2EHA in the acrylic polymer is not particularly limited. It is usually 97% by weight or lower; in relation to the copolymerization ratio of acidic group-containing monomer, it is suitably 92% by weight or lower, or preferably 90% by weight or lower (usually 88% by weight or lower, e.g. 85% by weight or lower).
In a preferable embodiment of the art disclosed herein, an acidic group-containing monomer is used as a monomer that is copolymerizable with the alkyl (meth)acrylate which is the primary monomer. The acidic group-containing monomer can enhance cohesion based on its polarity and provide bonding strength relative to polar adherends. When a crosslinking agent such as isocyanate-based and epoxy-based crosslinking agents is used, the acidic group (typically a carboxyl group) serves as a crosslinking point in the acrylic polymer. These functions can favorably bring about deformation resistance to a continuous z-axial load. With the use of the acidic group-containing monomer at or above a prescribed ratio, the acrylic polymer can be preferably designed to bring about light-pressure initial adhesion and deformation resistance to a continuous z-axial load.
As the acidic group-containing monomer, a carboxy group-containing monomer is preferably used. Examples of the carboxy group-containing monomer include ethylenic unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, crotonic acid, and isocrotonic acid; and ethylenic unsaturated dicarboxylic acids such as maleic acid, itaconic acid and citraconic acid as well as their anhydrides (maleic acid anhydride, itaconic acid anhydride, etc.). The acidic group-containing monomer can be a monomer having a metal carboxylate (e.g. an alkali metal salt). In particular, AA and MAA are preferable, with AA being more preferable. When one, two or more species of acidic group-containing monomers are used, the ratio of AA in the acidic group-containing monomer is preferably 50% by weight or higher, more preferably 70% by weight or higher, or yet more preferably 90% by weight or higher. In a particularly preferable embodiment, the acidic group-containing monomer essentially consists of AA. For its multiple functions including its polarity based on its carboxy group and its function to provide crosslinking points as well as its Tg (106° C.), in the acidic group-containing monomer disclosed herein, AA is thought to be the most suitable monomer in view of balancing light-pressure initial adhesion and deformation resistance to a continuous z-axial load.
In the art disclosed herein, the acidic group-containing monomer content (typically the carboxy group-containing monomer content) in the monomers (i.e. the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer) is usually 3% by weight or higher, or suitably 5% by weight or higher. With the use of at least the prescribed amount of the acidic group-containing monomer, based on its cohesion-enhancing effect, etc., it is possible to preferably obtain an acrylic polymer that can provide both light-pressure initial adhesion and deformation resistance to a continuous z-axial load. The copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is preferably 8% by weight or higher, more preferably 10% by weight or higher, yet more preferably higher than 10% by weight, particularly preferably 11% by weight or higher, or most preferably 12% by weight or higher. In case of obtaining light-pressure initial adhesion by press-bonding at a temperature above room temperature, etc., the copolymerization ratio of acidic group-containing monomer in the acrylic polymer can be further increased. In this case, the copolymerization ratio is preferably 13% by weight or higher, for instance, 15% by weight or higher. The copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is usually suitably 20% by weight or lower; from the standpoint of maintaining the properties of the primary monomer, it is preferably 18% by weight or lower. The copolymerization ratio can be 15% by weight or lower, for instance, 13% by weight or lower. In an acrylic polymer having a monomer composition including a large amount of C7-10 alkyl (meth)acrylate (typically 2EHA), it is particularly effective that the monomers include the acidic group-containing monomer (e.g. AA) in an amount in these ranges.
In the monomers forming the acrylic polymer disclosed herein, the ratio of acidic group-containing monomer content CA to primary monomer (typically an alkyl (meth)acrylate) content CM, CA/CM (%) (determined by CA/CM×100), is usually 3% or higher, suitably 5% or higher, or preferably 8% or higher by weight. With the use of at least the prescribed amount of the acidic group-containing monomer relative to the primary monomer (typically an alkyl (meth)acrylate), based on the adhesive properties of the primary monomer and the effect of the acidic group-containing monomer to enhance cohesion, etc., it is possible to preferably obtain an acrylic polymer that can preferably achieve both light-pressure initial adhesion and deformation resistance to a continuous z-axial load. The CA/CM ratio is more preferably 10% or higher, yet more preferably 11% or higher, or particularly preferably 12% or higher. In case of obtaining light-pressure initial adhesion by press-bonding at a temperature above room temperature, etc., the copolymerization ratio of acidic group-containing monomer in the acrylic polymer can be further increased. In this case, the CA/CM ratio can be 15% or higher, for instance, 18% or higher. The CA/CM ratio is usually suitably 25% or lower; from the standpoint of keeping the properties of the primary monomer, it is preferably 20% or lower. The CA/CM ratio can be 15% or lower, for instance, 13% or lower. In an acrylic polymer having a monomer composition including a large amount of C7-10 alkyl (meth)acrylate (typically 2EHA), it is particularly effective that the monomers include the acidic group-containing monomer (e.g. AA) in an amount in these ranges.
In the art disclosed herein, as the secondary monomer copolymerizable with the alkyl (meth)acrylate that is the primary monomer, a copolymerizable monomer can be used excluding carboxy group-containing monomers. As the secondary monomer, for instance, functional group-containing monomers such as those shown below can be used.
Hydroxy group-containing monomers: e.g. hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol; and poly(propylene glycol mono(meth)acrylate).
Amide group-containing monomers: for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide.
Amino group-containing monomers: e.g. aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate and t-butylaminoethyl (meth)acrylate.
Epoxy group-containing monomers: e.g. glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and allyl glycidyl ether.
Cyano group-containing monomers: e.g. acrylonitrile, methacrylonitrile.
Keto group-containing monomers: e.g. diacetone (meth)acrylamide, diacetone (meth)acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate.
Monomers having nitrogen atom-containing rings: e.g. N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, and N-(meth)acryloyl morpholine.
Alkoxysilyl group-containing monomers: e.g. (3-(meth)acryloxypropyl)trimethoxysilane, (3-(meth)acryloxypropyl)triethoxysilane, (3-(meth)acryloxypropyl)methyldimethoxysilane, (3-(meth)acryloxypropyl)methyldiethoxysilane.
For the functional group-containing monomer, solely one species or a combination of two or more species can be used. When the monomers forming the acrylic polymer include a functional group-containing monomer, the ratio of the functional group-containing monomer in the monomers is suitably selected in accordance with required properties (e.g. light-pressure initial adhesion and deformation resistance to a continuous z-axial load). The ratio (copolymerization ratio) of the functional group-containing monomer is suitably about at least 0.1% by weight (e.g. at least 0.5% by weight, usually at least 1% by weight) of the monomers. Its upper limit is preferably about 40% by weight or lower (e.g. 30% by weight or lower, usually 20% by weight or lower). In a more preferable embodiment, the ratio of the functional group-containing monomer excluding the acidic group-containing monomer can be, for instance, 10% by weight or lower, or yet suitably 5% by weight or lower; it can be 1% by weight or lower. The monomers forming the acrylic polymer can be essentially free of a functional group-containing monomer besides the acidic group-containing monomer.
As for a monomer forming the acrylic polymer, to increase the cohesion of the acrylic polymer, etc., other comonomer(s) can be used besides the aforementioned acidic group-containing monomers. Examples of such comonomers include vinyl ester-based monomers such as vinyl acetate, vinyl propionate and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrenes (α-methylstyrene, etc.), and vinyl toluene; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, and isobornyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as aryl (meth)acrylate (e.g. phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (e.g. phenoxyethyl (meth)acrylate), and arylalkyl (meth)acrylate (e.g. benzyl (meth)acrylate); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; isocyanate group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; and vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether.
The amount of the other comonomer(s) can be suitably selected in accordance with the purpose and application and is not particularly limited. It is usually preferably 10% by weight or less of the monomers. For instance, when a vinyl ester-based monomer (e.g. vinyl acetate) is used as the other comonomer(s), its amount can be, for instance, about 0.1% by weight or more (usually about 0.5% by weight or more) of the monomers, or suitably about 20% by weight or less (usually about 10% by weight or less).
The acrylic polymer may comprise a polyfunctional monomer having at least two polymerizable functional groups (typically radically-polymerizable functional groups), each having an unsaturated double bond such as a (meth)acryloyl group and a vinyl group. The use of the polyfunctional monomer as a monomer can enhance the cohesion of the PSA layer. The polyfunctional monomer can be used as a crosslinking agent.
Examples of the polyfunctional monomer include an ester of a polyol and a (meth)acrylic acid such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaaerythritol hexa(meth)acrylate, 1,2-ethyleneglycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, etc.; allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, and the like. Among them, preferable examples are trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaaerythritol hexa(meth)acrylate. A particularly preferable examples is 1,6-hexanediol di(meth)acrylate. The polyfunctional monomers can be used solely as one species or in combination of two or more species. From the standpoint of the reactivity, etc., it is usually preferable to use a polyfunctional monomer having two or more acryloyl groups.
The amount of the polyfunctional monomer used is not particularly limited. It can be set to suitably achieve the purpose of use of the polyfunctional monomer. From the standpoint of combining a preferable storage modulus disclosed herein and other adhesive performance or other properties in a good balance, the polyfunctional monomer is used in an amount of preferably about 3% by weight or less, more preferably 2% by weight or less, or even more preferably about 1% by weight or less (e.g. about 0.5% by weight or less) of the monomers. When using a polyfunctional monomer, its lower limit of use should just be greater than 0% by weight and is not particularly limited. In usual, when the polyfunctional monomer used accounts for about 0.001% by weight or greater (e.g. about 0.01% by weight or greater) of the monomers, the effect of the use of the polyfunctional monomer can be suitably obtained.
It is suitable to design the composition of monomers forming the acrylic polymer so that the acrylic polymer has a glass transition temperature (Tg) of about −15° C. or lower (e.g. about −70° C. or higher and −15° C. or lower). Here, the acrylic polymer's Tg refers to the value determined by the Fox equation based on the composition of the monomers. As shown below, the Fox equation is a relational expression between the Tg of a copolymer and glass transition temperatures Tgi of homopolymers of the respective monomers constituting the copolymer.
1/Tg=Σ(Wi/Tgi)
In the Fox equation, Tg represents the glass transition temperature (unit: K) of the copolymer, Wi the weight fraction (copolymerization ratio by weight) of a monomer i in the copolymer, and Tgi the glass transition temperature (unit: K) of homopolymer of the monomer i.
As the glass transition temperatures of homopolymers used for determining the Tg value, values found in publicly known documents are used. For example, with respect to the monomers listed below, as the glass transition temperatures of homopolymers of the monomers, the following values are used:
With respect to the glass transition temperatures of homopolymers of monomers other than those listed above, values given in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., Year 1989) are used. When the literature provides two or more values for a certain monomer, the highest value is used.
With respect to monomers for which no glass transition temperatures of the corresponding homopolymers are given in the reference book, values obtained by the following measurement method are used.
In particular, to a reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet and a condenser, are added 100 parts by weight of monomer(s), 0.2 part by weight of 2,2′-azobisisobutyronitrile, and 200 parts by weight of ethyl acetate as a polymerization solvent, and the mixture is stirred for one hour under a nitrogen gas flow. After oxygen is removed in this way from the polymerization system, the mixture is heated to 63° C. and the reaction is carried out for 10 hours. Then, it is cooled to room temperature and a homopolymer solution having 33% by weight solid content is obtained. Subsequently, this homopolymer solution is applied onto a release liner by flow coating and allowed to dry to prepare a test sample (a homopolymer sheet) of about 2 mm thickness. This test sample is cut out into a disc of 7.9 mm diameter and is placed between parallel plates; and while applying a shear strain at a frequency of 1 Hz using a rheometer (available from TA Instruments Japan, Inc.; model name ARES), the viscoelasticity is measured in the shear mode over a temperature range of −70° C. to 150° C. at a heating rate of 5° C./min; and the temperature corresponding to the peak top temperature of the tan 6 curve is taken as the Tg of the homopolymer.
While no particular limitations are imposed, from the standpoint of the adhesion, the acrylic polymer's Tg is advantageously about −25° C. or lower, preferably about −35° C. or lower, more preferably about −40° C. or lower, yet more preferably −45° C. or lower, particularly preferably −50° C. or lower, or most preferably −55° C. or lower. From the standpoint of the cohesive strength of the PSA layer, the acrylic polymer's Tg is usually about −75° C. or higher, or preferably about −70° C. or higher. The art disclosed herein can be preferably implemented in an embodiment where the acrylic polymer's Tg is about −65° C. or higher and about −40° C. or lower (e.g. about −65° C. or higher and about −45° C. or lower). In a preferable embodiment, the acrylic polymer's Tg can be about −65° C. or higher and about −55° C. or lower. The acrylic polymer's Tg can be adjusted by suitably changing the monomer composition (i.e. the monomer species used in synthesizing the polymer and their ratio).
The dispersity (Mw/Mn) of the acrylic polymer disclosed herein is not particularly limited. The dispersity (Mw/Mn) here refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In a preferable embodiment, the acrylic polymer's dispersity (Mw/Mn) is 8 or higher and 40 or lower. For instance, with respect to an acrylic polymer obtainable by solution polymerization or emulsion polymerization, its Mw/Mn is preferably in this range. That the acrylic polymer has a Mw/Mn value of 8 or higher and 40 or lower may indicate a broad molecular weight distribution and considerable amounts of low-molecular-weight polymer and high-molecular-weight polymer. The low-molecular-weight polymer contributes to manifestation of light-pressure initial adhesion for its good wetting properties to adherends. The high-molecular-weight polymer exhibits resistance (deformation resistance) to a continuous deformation load for its cohesiveness. A Mw/Mn value of 8 or higher leads to preferable manifestation of initial adhesion. When the Mw/Mn is 40 or lower, the molecular weight distribution is preferably limited to a suitable range to obtain stable properties (light-pressure initial adhesion and deformation resistance). The Mw/Mn is preferably 10 or higher, more preferably 12 or higher, or yet more preferably 15 or higher. The Mw/Mn can also be 18 or higher (e.g. 20 or higher). The Mw/Mn is preferably 35 or lower, more preferably 30 or lower, or yet more preferably 25 or lower. The Mw, Mn and Mw/Mn can be adjusted through polymerization conditions (time, temperature, etc.), the use of chain transfer agent, the choice of a polymerization solvent based on the chain-transfer constant, etc.
The Mw of the acrylic polymer is not particularly limited. It can be, for instance, 10×104 or higher and 500×104 or lower. From the standpoint of the cohesion, the Mw is usually about 30×104 or higher, or suitably about 45×104 or higher (e.g. about 65×104 or higher). In a preferable embodiment, from the standpoint of the deformation resistance to a continuous z-axial load based on enhanced cohesion due to the high-molecular-weight polymer, the acrylic polymer's Mw is 70×104 or higher, more preferably about 75×104 or higher, yet more preferably about 90×104 or higher, or particularly preferably about 95×104 or higher. The Mw can also be about 100×104 or higher (e.g. about 110×104 or higher). The Mw is usually suitably 300×104 or lower (more preferably about 200×104 or lower, e.g. about 150×104 or lower). The Mw of the acrylic polymer can also be about 140×104 or lower. For instance, with respect to an acrylic polymer obtainable by solution polymerization or emulsion polymerization, its Mw is preferably in these ranges.
The Mw and Mn are determined from values based on standard polystyrene obtained by GPC (gel permeation chromatography). As the GPC system, for instance, model name HLC-8320 GPC (column: TSKgel GMH-H(S) available from Tosoh Corporation) can be used.
The PSA layer disclosed herein can be formed with a PSA composition that comprises monomers in a composition as described above as a polymerized product, in a non-polymerized form (i.e. in a form where the polymerizable functional groups are still unreacted), or as a mixture of these. The PSA composition may be in various forms such as a solvent-based PSA composition which comprises PSA (adhesive components) in an organic solvent; an aqueous PSA composition which comprises PSA dispersed in an aqueous solvent; an active energy ray-curable PSA composition prepared so as to form PSA when cured with active energy rays such as UV rays, radioactive rays, etc.; and a hot melt-type PSA composition which is heated to melting for application and allowed to cool to around room temperature to form PSA. From the standpoint of the adhesive properties, etc., the art disclosed herein can be implemented particularly preferably in an embodiment comprising a PSA layer formed from a solvent-based PSA composition or an active energy ray-curable PSA composition.
Herein, the term “active energy ray” in this description refers to an energy ray having energy capable of causing a chemical reaction such as polymerization, crosslinking, initiator decomposition, etc. Examples of the active energy ray herein include lights such as ultraviolet (UV) rays, visible lights, infrared lights, radioactive rays such as α rays, β rays, γ rays, electron beam, neutron radiation, and X rays.
The PSA composition typically comprises at least some of the monomers (possibly a certain species among the monomers or a fraction of its quantity) as a polymer. The polymerization method for forming the polymer is not particularly limited. Heretofore known various polymerization methods can be suitably used. For instance, thermal polymerization (typically carried out in the presence of a thermal polymerization initiator) such as solution polymerization, emulsion polymerization, bulk polymerization, etc.; photopolymerization carried out by irradiating light such as UV light, etc. (typically in the presence of a photopolymerization initiator); active energy ray polymerization carried out by irradiating radioactive rays such as β rays, γ rays, etc.; and the like. In particular, solution polymerization and photopolymerization is preferable. In these polymerization methods, the embodiment of polymerization is not particularly limited. It can be carried out with a suitable selection of a heretofore known monomer supply method, polymerization conditions (temperature, time, pressure, irradiance of light, irradiance of radioactive rays, etc.), materials (polymerization initiator, surfactant, etc.) used besides the monomers, etc.
For instance, in a preferable embodiment, the acrylic polymer can be synthesized by solution polymerization. The solution polymerization gives a polymerization reaction mixture in a form where an acrylic polymer is dissolved in an organic solvent. The PSA layer in the art disclosed herein may be formed from a PSA composition comprising the polymerization reaction mixture or an acrylic polymer solution obtained by subjecting the reaction mixture to a suitable work-up. For the acrylic polymer solution, the polymerization reaction mixture can be used after adjusted to suitable viscosity (concentration) as necessary. Alternatively, an acrylic polymer can be synthesized by a polymerization method (e.g. emulsion polymerization, photopolymerization, bulk polymerization, etc.) other than solution polymerization and an acrylic polymer solution prepared by dissolving the acrylic polymer in an organic solvent can be used as well.
As the method for supplying monomers in solution polymerization, all-at-once supply by which all starting monomers are supplied at once, continuous supply (addition), portion-wise supply (addition) and like method can be suitably employed. The polymerization temperature can be suitably selected in accordance with the species of monomers and the solvent used, the type of polymerization initiator and the like. It can be, for instance, about 20° C. to 170° C. (usually about 40° C. to 140° C.). In a preferable embodiment, the polymerization temperature can be about 75° C. or lower (more preferably about 65° C. or lower, e.g. about 45° C. to about 65° C.).
The solvent used for solution polymerization (polymerization solvent) can be suitably selected among heretofore known organic solvents. For instance, one species of solvent or a mixture of two or more species of solvents can be used, selected among aromatic compounds (e.g. aromatic hydrocarbons) such as toluene and xylene; acetic acid esters such as ethyl acetate and butyl acetate; aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane and methyl cyclohexane; halogenated alkanes such as 1,2-dichloroethane; lower alcohols (e.g. monovalent alcohols with 1 to 4 carbon atoms) such as isopropyl alcohol; ethers such as tert-butyl methyl ether; and ketones such as methyl ethyl ketone and acetone.
On the other hand, in another embodiment of the art disclosed herein, when an active energy ray-curable PSA composition (typically a photocuring PSA composition) is used, as the active energy ray-curable PSA composition, one essentially free of an organic solvent is preferable from the standpoint of the environmental health, etc. For instance, a PSA composition having about 5% by weight or less (more preferably about 3% by weight or less, e.g. about 0.5% by weight or less) organic solvent content is preferable. A PSA composition essentially free of a solvent (meaning to include an organic solvent and an aqueous solvent) is preferable because it is suitable for forming a PSA layer in an embodiment where a wet layer of the PSA composition is cured between a pair of release films as described later. For instance, a preferable PSA composition has a solvent content of about 5% by weight or less (more preferably about 3% by weight or less, e.g. about 0.5% by weight or less). The solvent herein refers to a volatile component that should be eliminated in the process of forming the PSA layer, that is, a volatile component that is not to be a component of the final PSA layer formed.
For the polymerization, depending on the polymerization method and embodiment of polymerization, etc., known or commonly-used thermal polymerization initiator or photopolymerization initiator can be used. These polymerization initiators can be used singly as one species or in a suitable combination of two or more species.
The thermal polymerization initiator is not particularly limited. For example, azo-based polymerization initiator, peroxide-based polymerization initiator, a redox-based polymerization initiator by combination of a peroxide and a reducing agent, substituted ethane-based polymerization initiator and the like can be used. More specific examples include, but not limited to, azo-based initiators such as 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2-methylpropionamidine) disulfate, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutylamidine), and 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate; persulfates such as potassium persulfate and ammonium persulfate; peroxide-based initiators such as benzoyl peroxide (BPO), t-butyl hydroperoxide, and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; redox-based initiators such as combination of a persulfate salt and sodium hydrogen sulfite, and combination of a peroxide and sodium ascorbate. Thermal polymerization can be preferably carried out at a temperature of, for instance, about 20° C. to 100° C. (typically 40° C. to 80° C.).
The photopolymerization initiator is not particularly limited. For instance, the following species can be used: ketal-based photopolymerization initiators, acetophenone-based photopolymerization initiators, benzoin ether-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzil-based photopolymerization initiators, benzophenone-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators.
Specific examples of ketal-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one (e.g. trade name “IRGACURE 651” available from BASF Corporation).
Specific examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (e.g. trade name “IRGACURE 184” available from BASF Corporation), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (e.g. trade name “IRGACURE 2959” available from BASF Corporation), and 2-hydroxy-2-methyl-1-phenyl-propane-1-one (e.g. trade name “DAROCUR 1173” available from BASF Corporation), methoxyacetophenone.
Specific examples of benzoin ether-based photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., as well as substituted benzoin ethers such as anisole methyl ether.
Specific examples of acylphosphine oxide-based photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (e.g. trade name “IRGACURE 819” available from BASF Corporation), bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (e.g. trade name “LUCIRIN TPO” available from BASF Corporation), and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.
Specific examples of α-ketol-based photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane-1-one. Specific examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride. Specific examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. Specific examples of benzoin-based photopolymerization initiators include benzoin. Specific examples of benzil-based photopolymerization initiators include benzil.
Specific examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenylketone.
Specific examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
Such thermal polymerization initiator or photopolymerization initiator can be used in a usual amount in accordance with the polymerization method, embodiment of polymerization, etc., and there are no particular limitations to the amount. For instance, relative to 100 parts by weight of monomers to be polymerized, about 0.001 part to 5 parts by weight (typically about 0.01 part to 2 parts by weight, e.g. about 0.01 part to 1 part by weight) of polymerization initiator can be used.
The PSA composition according to a preferable embodiment comprises the monomers as a fully-polymerized product. Such a PSA composition may be in a form of, for instance, a solvent-based composition comprising in an organic solvent an acrylic polymer which is the fully-polymerized product of the monomers, a water-dispersed PSA composition such that the acrylic polymer is dispersed in an aqueous solvent. As used herein, the term “fully-polymerized product” refers to a product whose monomer conversion is above 95% by weight.
The PSA composition according to another preferable embodiment comprises a polymerization product (or polymerization reactants mixture) of a monomer mixture comprising at least some of the monomers (starting monomers) that constitute the composition. Typically, of the monomers, some are included as a polymerized product and the rest are included as unreacted monomers. The polymerization product of the monomer mixture can be prepared by polymerizing the monomer mixture at least partially.
The polymerization product is preferably a partially-polymerized product of the monomer mixture. Such a partially-polymerized product is a mixture of a polymer formed from the monomer mixture and unreacted monomers, and it is typically in a form of syrup (viscous liquid). Hereinafter, a partially-polymerized product having such a form may be referred to as “monomer syrup” or simply “syrup.”
The polymerization method for obtaining the polymerization product from the monomers is not particularly limited. A suitable method can be selected and employed among various polymerization methods as those described earlier. From the standpoint of the efficiency and convenience, a photopolymerization method can be preferably employed. According to a photopolymerization, depending on the polymerization conditions such as irradiation light quantity, etc., the polymer conversion of the monomer mixture can be easily controlled.
With respect to the partially-polymerized product, the monomer conversion of the monomer mixture is not particularly limited. The monomer conversion can be, for instance, about 70% by weight or lower, or preferably about 60% by weight or lower. From the standpoint of facile preparation of the PSA composition comprising the partially-polymerized product and ease of application, etc., the monomer conversion is usually suitably about 50% by weight or lower, or preferably about 40% by weight or lower (e.g. about 35% by weight or lower). The lower limit of monomer conversion is not particularly limited. It is typically about 1% by weight or higher, or usually suitably about 5% by weight or higher.
The PSA composition comprising a partially-polymerized product of the monomer mixture can be easily obtained, for instance, by partially polymerizing a monomer mixture comprising all the starting monomers in accordance with a suitable polymerization method (e.g. photopolymerization). To the PSA composition comprising the partially-polymerized product, other components (e.g. photopolymerization initiator, polyfunctional monomer(s), crosslinking agent, acrylic oligomer described later, etc.) may be added as necessary. Methods for adding such other components are not particularly limited. For instance, they can be added to the monomer mixture in advance or added to the partially-polymerized product.
The PSA composition disclosed herein may also be in a form where a fully-polymerized product of a monomer mixture comprising certain species (starting monomers) among the monomers is dissolved in the rest of the monomers (unreacted) or a partially-polymerized product thereof. A PSA composition in such a form is also included in examples of the PSA composition comprising polymerized and non-polymerized (unreacted) monomers.
When forming PSA from a PSA composition comprising polymerized and non-polymerized monomers, a photopolymerization method can be preferably employed as the curing method (polymerization method). With respect to a PSA composition comprising a polymerization product prepared by a photopolymerization method, it is particularly preferable to employ photopolymerization as the curing method. A polymerization product obtained by photopolymerization already contains a photopolymerization initiator. When the PSA composition comprising the polymerization product is cured to form PSA, the photo-curing can be carried out without any additional photopolymerization initiator. Alternatively, the PSA composition may be obtained by adding a photopolymerization initiator as necessary to the polymerization product prepared by photopolymerization. The additional photopolymerization initiator may be the same as or different from the photopolymerization initiator used in preparing the polymerization product. If the PSA composition is prepared by a method other than photopolymerization, a photopolymerization initiator can be added to make it light-curable. The light-curable PSA composition is advantageous as it can readily form even a thick PSA layer. In a preferable embodiment, the PSA composition can be photopolymerized by UV irradiation to form a PSA. The UV irradiation may be performed using a commonly-known high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, or the like.
The PSA composition (preferably solvent-based PSA composition) used for forming the PSA layer preferably includes a crosslinking agent as an optional component. With the crosslinking agent content, the viscoelastic properties disclosed herein can be preferably obtained. The PSA layer in the art disclosed herein may include the crosslinking agent in a post-crosslinking-reaction form, a pre-crosslinking-reaction form, a partially crosslinked form, an intermediate or composite form of these, and so on. The PSA layer usually include the crosslinking agent mostly in the post-crosslinking-reaction form.
The type of crosslinking agent is not particularly limited. A suitable species can be selected and used among heretofore known crosslinking agents. Examples of such crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, carbodiimide-based crosslinking agents, hydrazine-based crosslinking agents, amine-based crosslinking agents, peroxide-based crosslinking agents, metal chelate-based crosslinking agents, metal alkoxide-based crosslinking agents, and metal salt-based crosslinking agents. For the crosslinking agent, solely one species or a combination of two or more species can be used. Examples of crosslinking agents that can be preferably used in the art disclosed herein include isocyanate-based crosslinking agents and epoxy-based crosslinking agents.
As the epoxy-based crosslinking agent, a compound having at least two epoxy groups per molecule can be used without particular limitations. A preferable epoxy-based crosslinking agent has three to five epoxy groups per molecule. For the epoxy-based crosslinking agent, solely one species or a combination of two or more species can be used.
Specific examples of the epoxy-based crosslinking agent include, but are not particularly limited to, N,N,N′,N′-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polyglycerol polyglycidyl ether. Commercial epoxy-based crosslinking agents include trade names TETRAD-C and TETRAD-X available from Mitsubishi Gas Chemical Co., Inc.; trade name EPICLOM CR-5L available from DIC Corporation; trade name DENACOL EX-512 available from Nagase ChemteX Corporation; and trade name TEPIC-G available from Nissan Chemical Industries, Ltd.
In an embodiment using an epoxy-based crosslinking agent, its amount used is not particularly limited. The epoxy-based crosslinking agent used can be used in an amount of, for instance, more than 0 part by weight and about 1 part by weight or less (preferably about 0.001 part to 0.5 part by weight) to 100 parts by weight of the acrylic polymer. From the standpoint of favorably obtaining the effect to enhance cohesion, the epoxy-based crosslinking agent is used in an amount of usually suitably about 0.002 part by weight or greater to 100 parts by weight of the acrylic polymer, preferably about 0.005 part by weight or greater, more preferably about 0.01 part by weight or greater, yet more preferably about 0.02 part by weight or greater, or particularly preferably about 0.03 part by weight or greater. From the standpoint of avoiding insufficient light-pressure initial adhesion due to excessive crosslinking, the epoxy-based crosslinking agent is used in an amount of usually suitably about 0.2 part by weight or less to 100 parts by weight of the acrylic polymer, or preferably about 0.1 part by weight or less.
As the isocyanate-based crosslinking agent, a polyfunctional isocyanate (which refers to a compound having an average of two or more isocyanate groups per molecule, including a compound having an isocyanurate structure) can be preferably used. For the isocyanate-based crosslinking agent, solely one species or a combination of two or more species can be used.
A preferable example of the polyfunctional isocyanate has an average of three or more isocyanate groups per molecule. Such a tri-functional or higher polyfunctional isocyanate can be a multimer (e.g. a dimer or a trimer), a derivative (e.g., an addition product of a polyol and two or more polyfunctional isocyanate molecules), a polymer or the like of a di-functional, tri-functional, or higher polyfunctional isocyanate. Examples include polyfunctional isocyanates such as a dimer and a trimer of a diphenylmethane diisocyanate, an isocyanurate (a cyclic trimer) of a hexamethylene diisocyanate, a reaction product of trimethylol propane and a tolylene diisocyanate, a reaction product of trimethylol propane and a hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, and polyester polyisocyanate. Commercial polyfunctional isocyanates include trade name DURANATE TPA-100 available from Asahi Kasei Chemicals Corporation and trade names CORONATE L, CORONALE HL, CORONATE HK, CORONATE HX, and CORONATE 2096 available from Tosoh Corporation.
In an embodiment using an isocyanate-based crosslinking agent, its amount used is not particularly limited. The isocyanate-based crosslinking agent can be used in an amount of, for instance, about 0.5 part by weight or greater and about 10 parts by weight or less to 100 parts by weight of the acrylic polymer. From the standpoint of the cohesion, the isocyanate-based crosslinking agent is used in an amount of usually suitably about 1 part by weight or greater to 100 parts by weight of the acrylic polymer, or preferably about 1.5 parts by weight or greater. The isocyanate-based crosslinking agent is used in an amount of usually suitably about 8 parts by weight or less to 100 parts by weight of the acrylic polymer, or preferably about 5 parts by weight or less (e.g. less than about 4 parts by weight).
The art disclosed herein can be preferably implemented in an embodiment using an epoxy-based crosslinking agent as the crosslinking agent. The epoxy group of the epoxy-based crosslinking agent may react with an acidic group possibly introduced in the acrylic polymer to form a crosslinked structure. The crosslinking reaction leads to greater cohesion of the PSA, giving rise to more preferable deformation resistance to a continuous z-axial load. Examples of such an embodiment include an embodiment using solely an epoxy-based crosslinking agent and an embodiment using an epoxy-based crosslinking agent in combination with other crosslinking agent(s). In a preferable embodiment, the PSA composition includes an epoxy-based crosslinking agent as the crosslinking agent, but it is essentially free of an isocyanate-based crosslinking agent. In another preferable embodiment, the PSA composition includes both an epoxy-based crosslinking agent and an isocyanate-based crosslinking agent as the crosslinking agent. From the standpoint of enhancing the anchoring to the substrate layer, the use of the isocyanate-based crosslinking agent is beneficial.
The crosslinking agent content (its total amount) in the PSA composition disclosed herein is not particularly limited. From the standpoint of the cohesion, the crosslinking agent content is usually about 0.001 part by weight or greater to 100 parts by weight of the acrylic polymer, suitably about 0.002 part by weight or greater, preferably about 0.005 part by weight or greater, more preferably about 0.01 part by weight or greater, yet more preferably about 0.02 part by weight or greater, or particularly preferably about 0.03 part by weight or greater. From the standpoint of avoiding insufficient light-pressure initial adhesion, the crosslinking agent content in the PSA composition is usually about 20 parts by weight or less to 100 parts by weight of the acrylic polymer, suitably about 15 parts by weight or less, or preferably about 10 parts by weight or less (e.g. about 5 parts by weight or less).
In a preferable embodiment, the PSA composition (and even the PSA layer) includes a tackifier resin. As the tackifier resin possibly included in the PSA composition, one, two or more species can be selected and used among various known tackifier resins such as phenolic tackifier resins, terpene-based tackifier resins, modified terpene-based tackifier resins, rosin-based tackifier resins, hydrocarbon-based tackifier resins, epoxy-based tackifier resins, polyamide-based tackifier resins, elastomer-based tackifier resins, and ketone-based tackifier resins. The use of tackifier resin enhances adhesive strength including light-pressure initial adhesive strength.
Examples of the phenolic tackifier resin include terpene-phenol resin, hydrogenated terpene-phenol resin, alkylphenol resin and rosin-phenol resin.
The terpene-phenol resin refers to a polymer comprising a terpene residue and a phenol residue, and its concept encompasses copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin) as well as a terpene or its homopolymer or copolymer modified with phenol (phenol-modified terpene resin). Preferable examples of a terpene forming such terpene-phenol resin include monoterpenes such as α-pinene, β-pinene, limonenes (including d limonene, 1 limonene and d/1 limonene (dipentene)). The hydrogenated terpene-phenol resin refers to a hydrogenated terpene-phenol resin having a hydrogenated structure of such terpene-phenol resin. It is sometimes called hydrogenated terpene-phenol resin.
The alkylphenol resin is a resin (oil phenol resin) obtainable from an alkylphenol and formaldehyde. Examples of the alkylphenol resin include a novolac type and a resol type.
The rosin-phenol resin is typically a resin obtainable by phenol modification of a rosin or one of the various rosin derivatives listed above (including a rosin ester, an unsaturated fatty acid-modified rosin and an unsaturated fatty acid-modified rosin ester). Examples of the rosin-phenol resin include a rosin-phenol resin obtainable by acid catalyzed addition of a phenol to a rosin or one of the various rosin derivatives listed above followed by thermal polymerization, etc.
Among these phenolic tackifier resins, terpene-phenol resin, hydrogenated terpene-phenol resin and alkyl phenol resin are preferable; terpene-phenol resin and hydrogenated terpene-phenol resin are more preferable; in particular, terpene-phenol resin is preferable.
Examples of terpene-based tackifier resin include terpenes (typically monoterpenes) such as α-pinene, β-pinene, d-limonene, l-limonene, and dipentene. It can be homopolymer of one species of terpene or copolymer of two or more species of terpene. Examples of the homopolymer of one species of terpene include α-pinene polymer, β-pinene polymer, and dipentene polymer.
Examples of modified terpene resin include resins obtainable by modification of the terpene resins. Specific examples include styrene-modified terpene resin and hydrogenated terpene resins.
The concept of rosin-based tackifier resin here encompasses both rosins and rosin derivative resins. Examples of rosins include unmodified rosins (raw rosins) such as gum rosin, wood rosin, and tall-oil rosin; and modified rosins obtainable from these unmodified rosins via modifications such as hydrogenation, disproportionation, and polymerization (hydrogenated rosins, disproportionated rosins, polymerized rosins, other chemically-modified rosins, etc.).
The rosin derivative resin is typically a derivative of a rosin as those listed above. The concept of rosin-based resin herein encompasses a derivative of an unmodified rosin and a derivative of a modified rosin (including a hydrogenated rosin, a disproportionated rosin, and a polymerized rosin). Examples of the rosin derivative resin include rosin esters such as an unmodified rosin ester which is an ester of an unmodified rosin and an alcohol, and a modified rosin ester which is an ester of a modified rosin and an alcohol; an unsaturated fatty acid-modified rosin obtainable by modifying a rosin with an unsaturated fatty acid; an unsaturated fatty acid-modified rosin ester obtainable by modifying a rosin ester with an unsaturated fatty acid; rosin alcohols obtainable by reduction of carboxy groups in rosins or aforementioned various rosin derivatives (including rosin esters, unsaturated fatty acid-modified rosin, and an unsaturated fatty acid-modified rosin ester);and metal salts of rosins or aforementioned various rosin derivatives. Specific examples of rosin esters include a methyl ester of an unmodified rosin or a modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, etc.), triethylene glycol ester, glycerin ester, and pentaerythritol ester.
Examples of hydrocarbon-based tackifier resin include various types of hydrocarbon-based resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene-olefin-based copolymer, etc.), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone-indene-based resins.
The softening point of the tackifier resin is not particularly limited. From the standpoint of obtaining greater cohesion, it is preferable to use a tackifier resin having a softening point (softening temperature) of about 80° C. or higher (preferably about 100° C. or higher). For instance, a phenolic tackifier resin (terpene-phenol resin, etc.) having such a softening point can be preferably used. In a preferable embodiment, a terpene-phenol resin having a softening point of about 135° C. or higher (or even about 140° C. or higher) can be used. The maximum softening point of the tackifier resin is not particularly limited. From the standpoint of the tightness of adhesion to adherend and substrate layer, it is preferable to use a tackifier resin having a softening point of about 200° C. or lower (more preferably about 180° C. or lower). The softening point of a tackifier resin can be determined based on the softening point test method (ring and ball method) specified in JIS K2207.
In a preferable embodiment, the tackifier resin includes one, two or more species of phenolic tackifier resins (e.g. terpene-phenol resin). The art disclosed herein can be preferably implemented, for instance, in an embodiment where the terpene-phenol resin accounts for about 25% by weight or more (more preferably about 30% by weight or more) of the total amount of the tackifier resin. The terpene-phenol resin may account for about 50% by weight or more of the total amount of the tackifier resin, or about 80% by weight or more (e.g. about 90% by weight or more) thereof. Essentially all (e.g. about 95% by weight or more and 100% by weight or less, or even about 99% by weight or more and 100% by weight or less) of the tackifier resin can be the terpene-phenol resin.
The amount of phenolic tackifier resin (e.g. terpene-phenol resin) included is not particularly limited as long as expected viscoelastic properties are satisfied. From the standpoint of the adhesive strength (e.g. light-pressure initial adhesion), the amount of phenolic tackifier resin (e.g. terpene-phenol resin) included is suitably about 5 parts by weight or greater to 100 parts by weight of the acrylic polymer, or preferably about 8 parts by weight or greater (typically 10 parts by weight or greater, e.g. 15 parts by weight or greater). From the standpoint of the deformation resistance, etc., the phenolic tackifier resin content is suitably about 45 parts by weight or less to 100 parts by weight of the acrylic polymer, preferably about 35 parts by weight or less, or more preferably about 30 parts by weight or less (e.g. 25 parts by weight or less).
While no particular limitations are imposed, as the tackifier resin in the art disclosed herein, a tackifier resin having a hydroxyl value less than 30 mgKOH/g (e.g. less than 20 mgKOH/g) can be used. Hereinafter, a tackifier resin having a hydroxyl value less than 30 mgKOH/g may be referred to as a “low-hydroxyl-value resin.” The hydroxyl value of the low-hydroxyl-value resin can be about 15 mgKOH/g or less, or even about 10 mgKOH/g or less. The minimum hydroxyl value of the low-hydroxyl-value resin is not particularly limited. It can be essentially 0 mgKOH/g. Such a low-hydroxyl-value resin (e.g. terpene-phenol resin) can be preferably used, for instance, in combination with an acrylic polymer whose primary monomer is a C7-10 alkyl (meth)acrylate to provide good adhesion to adherend.
While no particular limitations are imposed, as the tackifier resin in the art disclosed herein, a tackifier resin having a hydroxyl value of 30 mgKOH/g or greater can be used as well. Hereinafter, a tackifier resin having a hydroxyl value of 30 mgKOH/g or greater may be referred to as a “high-hydroxyl-value resin.” The maximum hydroxyl value of the high-hydroxyl-value resin is not particularly limited. From the standpoint of the compatibility with the acrylic polymer, the hydroxyl value of the high-hydroxyl-value resin is usually suitably about 200 mgKOH/g or less, preferably about 180 mgKOH/g or less, more preferably 160 mgKOH/g or less, or yet more preferably about 140 mgKOH/g or less.
As the hydroxyl value, can be used a value measured by the potentiometric titration method specified in JIS K0070:1992. Details of the method are described below.
The hydroxyl value is calculated by the following equation:
Hydroxyl value (mgKOH/g)=[(B−C)×f×28.05]/S+D
wherein:
B is the volume (mL) of the 0.5 mol/L KOH ethanol solution used in the blank titration;
C is the volume (mL) of the 0.5 mol/L KOH ethanol solution used to titrate the analyte;
f is the factor of the 0.5 mol/L KOH ethanol solution;
S is the weight of analyte (g);
D is the acid value;
28.05 is one half the molecular weight of KOH.
In an embodiment using a tackifier resin, the tackifier resin content is not particularly limited as long as expected viscoelastic properties are satisfied. The tackifier resin content can be about 5 parts by weight or greater to 100 parts by weight of the acrylic polymer; it can also be about 8 parts by weight or greater (e.g. about 10 parts by weight or greater). The art disclosed herein can be preferably implemented in an embodiment where the tackifier resin content to 100 parts by weight of the acrylic polymer is about 15 parts by weight or greater. The maximum tackifier resin content is not particularly limited. From the standpoint of the compatibility with the acrylic polymer and deformation resistance, the tackifier resin content relative to 100 parts by weight of the acrylic polymer is suitably about 70 parts by weight or less, preferably about 55 parts by weight or less, or more preferably about 45 parts by weight or less (e.g. about 40 parts by weight or less, typically about 30 parts by weight or less).
From the standpoint of increasing the adhesive strength, etc., the PSA composition disclosed herein can comprise a (meth)acrylic oligomer. For the (meth)acrylic oligomer, it is preferable to use a polymer having a higher Tg value than the Tg value of the copolymer corresponding to the composition of monomers (which typically, approximately corresponds to the Tg value of the (meth)acrylic polymer contained in PSA formed from the PSA composition). The inclusion of the (meth)acrylic oligomer can increase the adhesive strength of the PSA.
The (meth)acrylic oligomer has a Tg of about 0° C. to about 300° C., preferably about 20° C. to about 300° C., or more preferably about 40° C. to about 300° C. When the Tg falls within these ranges, the adhesive strength can be preferably increased. The Tg value of the (meth)acrylic oligomer is determined by the Fox equation, similarly to the Tg of the copolymer corresponding to the composition of monomers.
The (meth)acrylic oligomer may have a weight average molecular weight (Mw) of typically about 1,000 or larger, but smaller than about 30,000, preferably about 1,500 or larger, but smaller than about 20,000, or more preferably about 2,000 or larger, but smaller than about 10,000. A weight average molecular weight within these ranges is preferable in obtaining good adhesive strength and good holding properties. The weight average molecular weight of a (meth)acrylic oligomer can be determined by gel permeation chromatography (GPC) as a value based on standard polystyrene. More specifically, it can be determined with HPLC 8020 available from Tosoh Corporation, using two TSKgel GMH-H (20) columns and tetrahydrofuran as an eluent at a flow rate of about 0.5 ml/min.
Examples of monomers forming the (meth)acrylic oligomer include an alkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate; an ester of (meth)acrylic acid and an alicyclic alcohol, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aryl (meth)acrylate such as phenyl (meth)acrylate and benzyl (meth)acrylate; and a (meth)acrylate derived from a terpene compound derivative alcohol. These (meth)acrylates may be used solely as one species or in combination of two or more species.
From the standpoint of further increasing the adhesiveness of the PSA layer, the (meth)acrylic oligomer preferably comprises, as a monomeric unit, an acrylic monomer having a relatively bulky structure, typified by an alkyl (meth)acrylate having a branched alkyl group, such as isobutyl (meth)acrylate, tert-butyl (meth)acrylate, etc.; an ester of a (meth)acrylic acid and an alicyclic alcohol, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc.; or an aryl (meth)acrylate such as phenyl (meth)acrylate, benzyl (meth)acrylate, etc. When UV light is used in synthesizing the (meth)acrylic oligomer or forming the PSA layer, a saturated oligomer is preferable because it is less likely to inhibit polymerization. An alkyl (meth)acrylate having a branched alkyl group or an ester of an alicyclic alcohol is preferably used as a monomer constituting the (meth)acrylic oligomer.
From the same standpoint, preferable examples of the (meth)acrylic oligomer include the respective homopolymers of dicyclopentanyl methacrylate (DCPMA), cyclohexylmethacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentanyl acrylate (DCPA), 1-adamanthyl methacrylate (ADMA), and 1-adamanthyl acrylate (ADA); as well as a copolymer of CHMA and isobutyl methacrylate (IBMA), copolymer of CHMA and IBXMA, copolymer of CHMA and acryloyl morpholine (ACMO), copolymer of CHMA and diethylacrylamide (DEAA), copolymer of ADA and methyl methacrylate (MMA), copolymer of DCPMA and IBXMA, and copolymer of DCPMA and MMA.
The (meth)acrylic oligomer content, if any, in the PSA composition is not particularly limited as long as expected viscoelastic properties are satisfied. From the standpoint of increasing the likelihood of obtaining a PSA layer having a preferable storage modulus disclosed herein, the (meth)acrylic oligomer content is preferably about 20 parts by weight or less relative to 100 parts by weight of the monomers in the PSA composition, more preferably about 15 parts by weight or less, or even more preferably about 10 parts by weight or less. The art disclosed herein can be implemented preferably also in an embodiment using no (meth)acrylic oligomers.
(Other additives)
The PSA composition may comprise, as necessary, various additives generally known in the field of PSA, such as leveling agent, crosslinking accelerator, plasticizer, softener, anti-static agent, anti-aging agent, UV absorber, antioxidant and photo-stabilizer. With respect to these various additives, heretofore known species can be used by typical methods. As they do not characterize the present invention in particular, details are omitted.
The PSA layer disclosed herein can be formed by a heretofore known method. For instance, it is possible to employ a direct method where the PSA composition is directly provided (typically applied) to a non-releasable substrate and allowed to dry or cure to form a PSA layer. Alternatively, it is possible to employ a transfer method where the PSA composition is provided to a releasable surface (e.g. a release face) and allowed to dry or cure to form a PSA layer on the surface and the PSA layer is transferred to a non-releasable substrate. From the standpoint of the productivity, the transfer method is preferable. As the release face, the surface of a release liner, the substrate's back side treated with release agent, or the like can be used. The PSA layer disclosed herein are not limited to, but typically formed in a continuous form. For instance, the PSA layer may be formed in a regular or random pattern of dots, stripes, etc.
The PSA composition can be applied by various known methods. Specific examples include methods such as roll coating, kiss roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, and extrusion coating with a die coater or the like.
In an embodiment of the art disclosed herein, from the standpoint of accelerating the crosslinking reaction and increasing the productivity of manufacturing, the PSA composition is preferably dried with heating. The drying temperature can be, for instance, about 40° C. to 150° C., or usually preferably about 60° C. to 130° C. After dried, the PSA composition may be aged for purposes such as adjusting the migration of components in the PSA layer and the progress of the crosslinking reaction, and lessening deformation possibly present in the substrate layer and the PSA layer.
The PSA sheet disclosed herein can be preferably produced by a method that includes allowing a wet layer of the PSA composition on a release face of a release film to dry or cure to form a PSA layer in which the face cured on the release face is a first adhesive face. This method allows more precise control of the smoothness of the PSA layer surface formed in contact with the release face by means of drying or curing a fluid PSA composition (wet layer) in contact with the release face. For instance, with the use of a release film having a suitably smooth release face, the first adhesive face can be consistently (reproducibly) produced to have desirable smoothness.
The PSA sheet disclosed herein can be preferably produced by a method that includes allowing a wet layer of the PSA composition to dry or cure between release faces of a pair of release films to form a PSA layer. By adhering the PSA layer thus obtained to a non-releasable face of a support substrate, a substrate-supported, single-faced or double-faced PSA sheet can be produced. As the method for placing the wet layer of the PSA composition between release faces of a pair of release films, it is possible to use a method that applies the fluid PSA composition to a release face of the first release film and then covers the wet layer of the PSA composition with the second release film. In another method cited, the first and second release films are placed between a pair of rolls, with their release faces facing each other; and the fluid PSA composition is supplied between their release faces.
There are no limitations to the thickness of the PSA layer (each PSA layer when it has two (first and second) PSA layers) as long as the TS/TPSA ratio value is greater than 0.3. The thickness of the PSA layer is not particularly limited. The thickness of the PSA layer is usually suitably about 300 μm or less, preferably about 200 μm or less, more preferably about 150 μm or less, or yet more preferably about 100 μor less. In the PSA sheet according to a preferable embodiment, the PSA layer has a thickness of about 50 μm or less (typically 40 μm or less). The minimum thickness of the PSA layer is not particularly limited. From the standpoint of the adhesion and adherend conformability, it is advantageously about 3 μm or greater, preferably about 6 μm or greater, or more preferably about 10 μm or greater (e.g. about 15 μor greater). For instance, the art disclosed herein can be favorably implemented in a PSA sheet form that comprises a PSA layer having a thickness of about 10 μor greater and about 150 μor less (preferably about 15 μor greater and about 50 μor less). The PSA layers according to a preferable embodiment have thicknesses of 35 μor less (30 μm or less). By limiting the thickness of the PSA layer, with respect to the PSA layer that has been put through a cutting process, the influence of blocking can be reduced. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the thicknesses of the first and second PSA layers can be equal or different.
While no particular limitations are imposed, the gel fraction (by weight) of the PSA layer (each PSA layer when it has two (first and second) PSA layers) disclosed herein can be, for instance, 20% or higher, usually suitably 30% or higher, or preferably 35% or higher. With increasing gel fraction of the PSA layer in a suitable range, deformation resistance to a continuous z-axial load tends to be more likely obtained. In the art disclosed herein, the PSA layer more preferably has a gel fraction of 40% or higher. The gel fraction is yet more preferably 45% or higher, or particularly preferably 50% or higher. The gel fraction can also be, for instance, 55% or higher. On the other hand, an excessively high gel fraction may result in insufficient light-pressure initial adhesion. From such a standpoint, the gel fraction of the PSA layer is preferably 90% or lower, more preferably 80% or lower, or yet more preferably 70% or lower (e.g. 65% or lower). When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the gel fractions of the first and second PSA layers can be equal or different.
Here, the “gel fraction of a PSA layer” refers to the value determined by the next method. The gel fraction is thought as the weight ratio of the ethyl acetate-insoluble part of the PSA layer.
A PSA sample (weight: Wg1) weighing approximately 0.1 g is wrapped into a pouch with a porous polytetrafluoroethylene membrane (weight: Wg2) having an average pore diameter of 0.2 μm, and the opening is tied with twine (weight: Wg3). As the porous polytetrafluoroethylene (PTFE) membrane, trade name NITOFLON® NTF 1122 available from Nitto Denko Corp. (0.2 μm average pore diameter, 75% porosity, 85 μthick) or an equivalent product is used.
The resulting pouch is immersed in 50 mL of ethyl acetate and stored at room temperature (typically 23° C.) for 7 days to extract sol in the PSA layer out of the membrane. Subsequently, the pouch is collected, and any residual ethyl acetate is wiped off the outer surface. The pouch is dried at 130° C. for 2 hours and the pouch's weight (Wg4) is measured. The gel fraction FG of the PSA layer is determined by substituting the respective values into the equation shown below. The same method is used in the working examples described later.
Gel Fraction FG=[(Wg4−Wg2−Wg3)/Wg1]×100
The art disclosed herein is implemented in an embodiment of an on-substrate PSA sheet having the PSA layer on at least one face of a substrate layer (support). For instance, it can be made in an embodiment of an on-substrate double-faced PSA sheet having the PSA layer on each face of a substrate layer. As the substrate layer supporting (backing) the PSA layer, a resin film, foam sheet, paper, fabrics, metal foil, a composite of these and the like can be used.
A preferable substrate layer includes resin film as its base film. The base film is typically a component capable of holding its shape by itself (self-standing). The substrate layer in the art disclosed herein may be formed essentially of such base film. Alternatively, the substrate layer may include a secondary layer besides the base film. Examples of the secondary layer include a primer layer, an antistatic layer, a colored layer and the like provided to the surface of the base film.
The resin film comprises a resin material as its primary component (a component accounting for more than 50% by weight of the resin film). Examples of the resin film include polyolefmic resin film such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer; polyester-based resin film such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); polyvinylic resin film; vinyl acetate-based resin film; polyimide-based resin film; polyamide-based resin film; fluororesin film; and cellophane. The resin film can be rubber-based film such as natural rubber film and butyl rubber film. Among them, from the standpoint of the ease of handling and processing, polyester film is preferable. In particular, PET film is especially preferable. As used herein, the “resin film” is typically a non-porous sheet and its concept is distinguished from so-called non-woven fabrics and woven fabrics (in other words, its concept excludes non-woven fabrics and woven fabrics).
The resin film may have a mono-layer structure or a multi-layer structure with two, three or more layers. From the standpoint of the shape stability, the resin film preferably has a mono-layer structure. In case of a multi-layer structure, at least one layer (preferably each layer) has a continuous structure formed of the resin (e.g. polyester-based resin). The method for producing the resin film is not particularly limited and a heretofore known method can be suitably employed. For instance, heretofore known general film formation methods can be suitably employed, such as extrusion molding, inflation molding, T-die casting and calendar rolling.
In another embodiment, as the substrate material, paper, fabrics and metal are used. Examples of the paper that can be used in the substrate layer include Japanese paper, Kraft paper, glassine paper, high-grade paper, synthetic paper, and top-coated paper. Examples of fabrics include woven fabrics and nonwoven fabrics of pure or blended yarn of various fibrous materials. Examples of fibrous materials include cotton, staple cloth, Manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and polyolefin fiber. Examples of metal foil that can be used in the substrate layer include aluminum foil and copper foil.
The concept of non-woven fabric as used herein primarily refers to non-woven fabric for PSA sheets used in the field of PSA tapes and other PSA sheets, typically referring to non-woven fabric (or so-called “paper”) fabricated using a general paper machine. Resin film herein is typically a non-porous resin sheet and its concept is distinct from, for instance, non-woven fabric (i.e. excludes non-woven fabric). The resin film may be any of non-stretched film, uni-axially stretched film and bi-axially stretched film. The faces of the substrate layer to which the PSA layers are provided may be subjected to a surface treatment such as primer coating, corona discharge treatment, and plasma treatment.
The resin film (e.g. PET film) may include, as necessary, various additives such as filler (inorganic filler, organic filler, etc.), colorant, dispersing agent (surfactant, etc.), anti-aging agent, antioxidant, UV absorber, antistatic agent, slip agent and plasticizer. The ratio of the various additives is usually below about 30% by weight (e.g. below about 20% by weight, preferably below about 10% by weight).
The surface of the substrate layer may be subjected to heretofore known surface treatment such as corona discharge treatment, plasma treatment, UV irradiation, acid treatment, base treatment, and primer coating. Such surface treatment may enhance the tightness of adhesion between the substrate layer and the PSA layer, that is, the anchoring of the PSA layer onto the substrate layer.
The thickness of the substrate layer disclosed herein is not particularly limited as long as the TS/TPSA ratio value is greater than 0.3. From the standpoint of the ease of handling and processing of the PSA sheet, etc., the thickness of the substrate layer can be about 6 μm or greater, preferably about 8 μm or greater, or more preferably about 10 μm or greater (e.g. 15 μor greater). In a more preferable embodiment, the substrate layer has a thickness of 20 μm or greater. With the use of the substrate layer having such a thickness, the TS/TPSA ratio value can be preferably obtained and further, great ease of processing can be obtained. From the standpoint of avoiding making the PSA sheet excessively thick, the thickness of the substrate layer (e.g. resin film) can be, for instance, about 200 μm or less, preferably about 150 μor less, or more preferably about 100 μor less. In accordance with the purpose and the way of using the PSA sheet, the thickness of the substrate layer can be about 70 μm or less, about 50 μor less, or even about 30 μor less (e.g. about 25 μor less).
In another preferable embodiment, a foam sheet is used as the substrate layer. The foam sheet disclosed herein is a substrate that comprises some part having pores (a pore structure), typically a substrate that includes at least one layer of foam (a foam layer). The foam sheet may be formed of one, two or more foam layers. For instance, the foam sheet can be a substrate layer essentially formed of one, two or more foam layers solely. While no particular limitations are imposed, a favorable example of the foam sheet in the art disclosed herein is a foam sheet formed of a single (one) foam layer.
The thickness of the foam sheet is not particularly limited as long as the TS/TPSA ratio value is greater than 0.3 and can be suitably selected in accordance with the strength, flexibility and purpose of the PSA sheet, etc. In view of making thinner products, the thickness of the foam sheet is usually 1 mm or less, suitably 0.70 mm or less, preferably 0.40 mm or less, or more preferably 0.30 mm or less. From the standpoint of the ease of processing, etc., the art disclosed herein can be preferably implemented in an embodiment where the foam sheet has a thickness of 0.25 mm or less (typically 0.18 mm or less, e.g. 0.16 mm or less). From the standpoint of the impact resistance of the PSA sheet, etc., the thickness of the foam sheet is usually 0.04 mm or greater, suitably 0.05 mm or greater, preferably 0.06 mm or greater, or more preferably 0.07 mm or greater (e.g. 0.08 mm or greater). The art disclosed herein can be preferably implemented in an embodiment where the foam sheet has a thickness of 0.10 mm or greater (typically greater than 0.10 mm, preferably 0.12 mm or greater, e.g. 0.13 mm or greater). With increasing thickness of the foam sheet, the impact resistance tends to be improved.
The density (apparent density; the same applies hereinafter unless otherwise noted) of the foam sheet is not particularly limited. It can be, for instance, 0.1 g/cm3 to 0.9 g/cm3. From the standpoint of the impact resistance, the density of the foam sheet is suitably 0.8 g/cm3 or less, or preferably 0.7 g/cm3 or less (e.g. 0.6 g/cm3 or less). In an embodiment, the density of the foam sheet can be 0.5 g/cm3 or less (e.g. less than 0.5 g/cm3). From the standpoint of the impact resistance, the density of the foam sheet is preferably 0.12 g/cm3 or greater, more preferably 0.15 g/cm3 or greater, or yet more preferably 0.2 g/cm3 or greater (e.g. 0.3 g/cm3 or greater). In an embodiment, the density of the foam sheet can be 0.4 g/cm3 or greater, 0.5 g/cm3 or greater (e.g. greater than 0.5 g/cm3), or even 0.55 g/cm3 or greater. The density (apparent density) of a foam sheet can be determined based on JIS K 6767.
The mean pore diameter of the foam sheet is not particularly limited. From the standpoint of stress dispersion, it is preferably 300 μm or less, more preferably 200 μm or less, or yet more preferably 150 μm or less. The minimum mean pore diameter is not particularly limited. From the standpoint of the conformability to contours, it is usually suitably 10 μm or greater, preferably 20 μm or greater, more preferably 30 μm or greater, or yet more preferably 40 μm or greater (e.g. 50 μm or greater). In an embodiment, the mean pore diameter can be 55 μm or greater, or even 60 μm or greater. As used herein, the mean pore diameter refers to the mean pore diameter based on equivalent spheres, determined by electron microscopy analysis of a cross section of the foam sheet.
The pore structure of the foam forming the foam sheet disclosed herein is not particularly limited. The pore structure can be formed of connected pores, disconnected pores, or half-connected half-disconnected pores. From the standpoint of the impact absorption, a disconnected pore structure and a half-connected half-disconnected pore structure are preferable.
The 25% compressive strength C25 of the foam sheet is not particularly limited. For instance, it can be 20 kPa or greater (typically 30 kPa or greater, or even 40 kPa or greater). C25 is usually suitably 250 kPa or greater, or preferably 300 kPa or greater (e.g. 400 kPa or greater). The PSA sheet having such a foam sheet may exhibit good resistance to impact by dropping, etc. For instance, impact tearing of the PSA sheet may be better prevented. The maximum C25 is not particularly limited; it is usually suitably 1300 kPa or less (e.g. 1200 kPa or less). In an embodiment, C25 can be 1000 kPa or less, 800 kPa or less, 600 kPa or less (e.g. 500 kPa or less), or even 360 kPa or less. In another preferable embodiment, the C25 of the foam sheet can be 20 kPa to 200 kPa (typically 30 kPa to 150 kPa, e.g. 40 kPa to 120 kPa). The PSA sheet comprising such a foam sheet may have excellent cushioning properties. For instance, the foam sheet can absorb dropping impact to better prevent peeling of the PSA sheet.
The 25% compressive strength C25 of a foam sheet refers to the load required to compress a specimen placed between a pair of flat plates by a thickness equivalent to 25% of the initial thickness (load at 25% compressibility), with the specimen obtained by layering 30 mm square cut pieces of the foam sheet to a thickness of about 2 mm. That is, it refers to the load required to compress the specimen to a thickness equivalent to 75% of the initial thickness. The compressive strength is determined based on JIS K 6767. In specific procedures, the specimen is set at the center of the pair of flat plates, the flat plates are moved to narrow the inter-plate distance and continuously compress the specimen to the prescribed compressibility, and the load at 10 seconds after the flat plates are stopped is measured. The compressive strength of the foam sheet can be controlled, for instance, through the degree of crosslinking and the density of the material forming the foam sheet as well as sizes and shapes of pores, etc.
The tensile elongation of the foam sheet is not particularly limited. For instance, a foam sheet having a machine direction (MD) tensile elongation of 200% to 800% (more preferably 400% to 600%) can be favorably used. A preferable foam sheet has a transverse direction (TD) tensile elongation of 50% to 800% (more preferably 200% to 500%). The elongation of a foam sheet is determined based on JIS K 6767. The elongation of the foam sheet can be controlled through, for instance, the degree of crosslinking, apparent density (expansion rate), etc.
The tensile strength of the foam sheet is not particularly limited. For instance, a foam sheet having a machine direction (MD) tensile strength of 5 MPa to 35 MPa (preferably 10 MPa to 30 MPa) can be favorably used. A preferable foam sheet has a transverse direction (TD) tensile strength of 1 MPa to 25 MPa (more preferably 5 MPA to 20 MPa). The tensile strength of a foam sheet is determined based on JIS K 6767. The tensile strength of the foam sheet can be controlled through, for instance, the degree of crosslinking, apparent density (expansion ratio), etc.
The material of the foam sheet is not particularly limited. Usually, a foam sheet including a foam layer formed of foam of a plastic material (plastic foam). There are no particular limitations to the plastic material (including a rubber material) for forming the plastic foam. A suitable species can be selected among known plastic materials. For the plastic material, solely one species or a suitable combination of two or more species can be used.
Specific examples of the plastic foam include polyolefinic resin foam such as PE foam and PP foam; polyester-based resin foam such as PET foam, PEN foam and PBT foam; polyvinyl chloride-based resin foam such as polyvinyl chloride foam; vinyl acetate-based resin foam; polyphenylene sulfide resin foam; amide-based resin foam such as aliphatic polyamide (nylon) resin foam and all aromatic polyamide (aramide) resin foam; polyimide resin foam; polyether ether ketone (PEEK) foam; styrene-based resin foam such as polystyrene foam; and urethane-based resin foam such as polyurethane resin foam. As the plastic foam, rubber-based resin foam such as polychloroprene rubber foam can be used as well.
Examples of preferable foam include polyolefinic resin foam (or polyolefinic foam, hereinafter). As the plastic material (i.e. a polyolefinic resin) constituting the polyolefinic foam, various known or conventional polyolefinic resins can be used without any particular limitations. Examples include PE such as low density polyethylenes (LDPE), linear low density polyethylenes (LLDPE), and high density polyethylenes (HDPE); PP; ethylene-propylene copolymers; and ethylene-vinyl acetate copolymers. Examples of LLDPE include Ziegler-Natta catalyst-based linear low density polyethylenes and metallocene-catalyst-based linear low density polyethylenes. These polyolefinic resins can be used singly as one species or in a combination of two or more species.
From the standpoint of the impact resistance, waterproof properties, anti-dust properties, etc., favorable examples of the foam sheet in the art disclosed herein include polyolefinic foam sheets such as a PE-based foam sheet formed essentially of PE-based resin foam and a PP-based foam sheet formed essentially of PP-based resin foam. Here, the PE-based resin refers to a resin wherein ethylene is the primary monomer (i.e., the primary component among monomers), possibly including HDPE, LDPE and LLDPE as well as ethylene-propylene copolymers and ethylene-vinyl acetate copolymers each having a copolymerization ratio of ethylene above 50% by weight, and the like. Similarly, the PP-based resin refers to a resin wherein propylene is the primary monomer. As the foam sheet in the art disclosed herein, a PE-based foam sheet can be preferably used.
The method for producing the plastic foam (typically polyolefinic foam) is not particularly limited. Various known methods can be suitably employed. For instance, it can be produced by a method that includes a molding step, a crosslinking step and a foaming step of the plastic foam. It may also include a stretching step as necessary.
Examples of the method for crosslinking the plastic foam include a chemical crosslinking method that uses an organic peroxide, etc.; and an ionizing radiation crosslinking method involving irradiation of ionizing radiation. These methods can be used together. Examples of the ionizing radiation include electron beam, α rays, β rays and γ rays. The dose of ionizing radiation is not particularly limited. It can be set at a suitable irradiation dose in view of target physical properties (e.g. degree of crosslinking) of the foam sheet, etc.
The foam sheet may comprise various additives as necessary such as filler (inorganic filler, organic filler, etc.), anti-aging agent, antioxidant, UV absorber, anti-static agent, slipping agent, plasticizers, flame retardant, and surfactant.
The foam sheet in the art disclosed herein may be colored to black, white, etc., in order to bring about desirable design or optical properties (e.g. light-blocking properties, light-reflecting properties, etc.) in a PSA sheet comprising the foam sheet. For the coloring, among known organic or inorganic colorants, solely one species or a combination of two or more species can be used.
The surface of the foam sheet may be subjected to suitable surface treatment as necessary. The surface treatment can be, for instance, chemical or physical treatment to increase the tightness of adhesion with the adjacent material (e.g. a PSA layer). Examples of such surface treatment include corona discharge treatment, chromic acid treatment, ozone exposure, flame exposure, UV irradiation, plasma treatment, and primer coating.
In the art disclosed herein, a release liner can be used during formation of a PSA layer; fabrication of a PSA sheet; storage, distribution and shape machining of a PSA sheet prior to use, etc. The release liner is not particularly limited. For example, a release liner having a release layer on the surface of a liner substrate such as resin film and paper; a release liner formed from a low adhesive material such as a fluoropolymer (polytetrafluoroethylene, etc.) or a polyolefinic resin (PE, PP, etc.); or the like can be used. The release layer can be formed, for instance, by subjecting the liner substrate to a surface treatment with a release agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum disulfide-based release agent.
The PSA sheet disclosed herein preferably satisfies at least one of the following features: having a 180° peel strength at 23° C. (23° C. light-pressure initial adhesive strength) of 8 N/20 mm or greater when determined within one minute after press-bonded at a press-bonding load of 0.1 kg or having a 180° peel strength at 40° C. (40° C. light-pressure initial adhesive strength) of 8 N/20 mm or greater when determined within one minute after press-bonded at 0.05 MPa for 3 seconds. The PSA sheet satisfying this feature may show excellent initial adhesion to an adherend surface when lightly press-bonded at around room temperature or at a limited heating temperature. The PSA sheet can achieve desirable light-pressure initial adhesion in the aforementioned press-bonding temperature range; and therefore, even for purposes (e.g. for electronics) for which heating at a temperature above 60° C. is not plausible, it can be preferably used in an embodiment where it is applied at around room temperature or with mild heating. Such a PSA sheet is superior in handling properties as well when compared to conventional thermal press-bonding. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the 23° C. light-pressure initial adhesive strength and 40° C. light-pressure initial adhesive strength values are determined with respect to at least one (preferably each) of the two surfaces (first and second adhesive faces) of the first and second PSA layers.
Determined within one minute after press-bonded at 23° C. at a press-bonding load of 0.1 kg, the PSA sheet disclosed herein preferably exhibits a 180° peel strength (23° C. light-pressure initial adhesive strength) of 8 N/20 mm or greater. Satisfying this feature, it may show excellent light-pressure initial adhesion to various types of adherends (e.g. materials used as components of mobile electronics). The PSA sheet with excellent light-pressure initial adhesion is also advantageous as it is easily applied to brittle adherends that may be damaged by typical press-bonding. The 23° C. light-pressure initial adhesive strength is more preferably 10 N/20 mm or greater, yet more preferably 12 N/20 mm or greater, or particularly preferably 14 N/20 mm or greater. The maximum 23° C. light-pressure initial adhesive strength is not particularly limited; it is usually suitably about 30 N/20 mm or less (e.g. about 20 N/20 mm or less). In particular, the 23° C. light-pressure initial adhesive strength is determined by the method described later in the working examples. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the 23° C. light-pressure initial adhesive strength value is determined with respect to at least one (preferably each) of the two surfaces (first and second adhesive faces) of the first and second PSA layers. The 23° C. light-pressure initial adhesive strength values of the first and second adhesive faces can be equal or different.
Determined within one minute after press-bonded at 40° C. at 0.05 MPa for 3 seconds, the PSA sheet disclosed herein preferably exhibits a 180° peel strength (40° C. light-pressure initial adhesive strength) of 8 N/20 mm or greater. Satisfying this feature, it may show excellent light-pressure initial adhesion by thermal press-bonding with heating at around 40° C. (i.e. by mild thermal press-bonding). Unlike conventional thermal press-bonding carried out at around 100° C., this thermal press-bonding can be applied to electronics. The 40° C. light-pressure initial adhesive strength is more preferably 10 N/20 mm or greater, yet more preferably 12 N/20m or greater, particularly preferably 14 N/20 mm or greater, or most preferably 18 N/20 mm or greater. The maximum 40° C. light-pressure initial adhesive strength is not particularly limited; it is usually suitably about 30 N/20 mm or less (e.g. about 25 N/20 mm or less). In particular, the 40° C. light-pressure initial adhesive strength is determined by the method described later in the working examples. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the 40° C. light-pressure initial adhesive strength value is determined with respect to at least one (preferably each) of the two surfaces (first and second adhesive faces) of the first and second PSA layers. The 40° C. light-pressure initial adhesive strength values of the first and second adhesive faces can be equal or different.
The PSA sheet disclosed herein may preferably have a passing level of deformation resistance (i.e. it may not peel off) in the z-axial deformation resistance test (at 23° C. or 40° C.), determined by the method described later in the working examples. The PSA sheet satisfying this feature shows excellent light-pressure adhesion and deformation resistance to a peel load applied essentially only in the thickness direction (z-axial direction) of the PSA sheet and is less likely to deform under a continuous peel load applied in this direction.
The PSA sheet disclosed herein preferably exhibits a 30-min aged adhesive strength of 8 N/20 mm or greater, determined based on JIS Z 0237:2000. A PSA sheet showing such 30-min aged adhesive strength exhibits good adhesion to adherend. The PSA sheet having such adhesive strength tends to show good adhesion to resin materials used for electronics, such as polycarbonate (PC) and polyimide (PI). The 30-min aged adhesive strength is more preferably 10 N/20 mm or greater, yet more preferably 12 N/20 mm or greater, or particularly preferably 14 N/20 mm or greater (e.g. 18 N/20 mm or greater). The maximum 30-min aged adhesive strength is not particularly limited; it is usually suitably about 30 N/20 mm or less (e.g. about 25 N/20 mm or less). In particular, the 30-min aged adhesive strength is determined by the method described later in the working examples. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the 30-min aged adhesive strength value is determined with respect to at least one (preferably each) of the two surfaces (first and second adhesive faces) of the first and second PSA layers. The 30-min aged adhesive strength values of the first and second adhesive faces can be equal or different.
The PSA sheet according to a preferable embodiment preferably has a manifestation rate of 23° C. light-pressure initial adhesive strength above 50%. The manifestation rate of 23° C. light-pressure initial adhesive strength can be determined by the equation: manifestation rate of 23° C. light-pressure initial adhesive strength (%)=(23° C. light-pressure initial adhesive strength/30-min aged adhesive strength)×100. The 23° C. light-pressure initial adhesive strength and the 30-min aged adhesive strength are in the same unit (typically in N/20 mm). The PSA sheet showing such a manifestation rate shows greater 23° C. light-pressure initial adhesive strength relative to its aged adhesive strength; and therefore, it is preferably used for an application that requires good adhesion immediately after its application with light pressure. The manifestation rate of 23° C. light-pressure initial adhesive strength is more preferably 55% or higher, yet more preferably 60% or higher, or particularly preferably 65% or higher. Certain techniques disclosed herein can be combined to raise the manifestation rate to 70% or above, or even to 75% or above. The maximum manifestation rate of 23° C. light-pressure initial adhesive strength is ideally 100%, but it can be about 90% or lower (e.g. 85% or lower) as well. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the manifestation rates of 23° C. light-pressure initial adhesive strength can be equal or different between the two surfaces (first and second adhesive faces) of the first and second PSA layers.
The PSA sheet according to another preferable embodiment preferably has a manifestation rate of 40° C. light-pressure initial adhesive strength above 50%. The manifestation rate of 40° C. light-pressure initial adhesive strength can be determined by the equation: manifestation rate of 40° C. light-pressure initial adhesive strength (%)=(40° C. light-pressure initial adhesive strength/30-min aged adhesive strength)×100. The 40° C. light-pressure initial adhesive strength and the 30-min aged adhesive strength are in the same unit (typically in N/20 mm). Satisfying this feature, by thermal press-bonding with heating at around 40° C., the PSA sheet may show excellent light-pressure initial adhesion. The manifestation rate of 40° C. light-pressure initial adhesive strength is more preferably 55% or higher, yet more preferably 60% or higher, or particularly preferably 65% or higher. Certain techniques disclosed herein can be combined to raise the manifestation rate to 70% or above, or even to 75% or above. The maximum manifestation rate of 40° C. light-pressure initial adhesive strength is ideally 100%, but it can be about 90% or lower (e.g. 85% or lower) as well. When the PSA sheet disclosed herein is a substrate-supported double-faced PSA sheet, the manifestation rates of 40° C. light-pressure initial adhesive strength can be equal or different between the two surfaces (first and second adhesive faces) of the first and second PSA layers.
The total thickness of the PSA sheet disclosed herein (excluding any release liner) is not particularly limited. The PSA sheet can have a total thickness of, for instance, about 500 μm or less; it is usually suitably about 350 μor less, or preferably about 250 μor less (e.g. about 200 μor less). The art disclosed herein can be preferably implemented as a PSA sheet (typically a double-faced PSA sheet) having a total thickness of about 150 μor less (more preferably about 100 μor less). The minimum total thickness of the PSA sheet is not particularly limited; it is usually suitably about 10 μm or greater, preferably about 20 μor greater, or more preferably about 30 μm or greater, yet more preferably about 50 μm or greater, or particularly preferably about 70 μm or greater (e.g. 80 μm or greater). When the PSA sheet comprises a foam sheet, the maximum total thickness of the PSA sheet is usually suitably 1.5 mm or less, preferably 1 mm or less, or more preferably 0.5 mm or less.
The PSA sheet disclosed herein is highly suited for cutting and shows excellent handling properties and removal efficiency. Because of these properties, the PSA sheet can be used in various applications that require processability. For instance, after subjected to a cutting process such as punching and formed in shapes (ribbon shapes, frame shapes, etc.) corresponding to bonding areas of various parts as adherends, the PSA sheet pieces can be preferably used for fixing the various parts. The fixing can be carried out under light pressure. A typical example of the application of such a PSA sheet include fixing parts of mobile electronic devices. In this application, because of the mass production, the takt time is strictly managed. Excellent ease of processing such as ease of handling and removal is also advantageous in view that it can contribute to greater productivity of manufacturing. In addition, for instance, by using the PSA sheet according to a preferable embodiment disclosed herein for fixing parts in various types of mobile devices (portable devices), it is possible to take advantage of the light-pressure initial adhesion obtained at room temperature or with limited heating (at below 60° C., typically mild heating at around 40° C.) that can be applied to electronics, whereby the tact time for manufacturing mobile electronics can be reduced to contribute to an increase in productivity. Non-limiting examples of the mobile electronics include mobile phones, smartphones, tablet PCs, notebook PCs, various wearable devices (e.g. wrist wearables put on wrists such as wrist watches; modular devices attached to bodies with clips, straps, etc.; eye wears including eye glass types (monocular or binocular, including head-mounted pieces); clothing types worn as, for instance, accessories on shirts, socks, hats/caps, etc.; ear-mounted pieces put on ears such as earphones), digital cameras, digital video cameras, acoustic equipment (portable music players, IC recorders, etc.), calculators (e.g. pocket calculators), handheld game devices, electronic dictionaries, electronic notebooks, electronic books, vehicle navigation devices, portable radios, portable TVs, portable printers, portable scanners, and portable modems. In this description, to be “mobile (portable),” it is unsatisfactory to be simply capable of being carried. Instead, it indicates a level of mobility (portability) that allows for relatively easy carriage by hand of an individual (a typical adult).
The PSA sheet (typically a double-faced PSA sheet) disclosed herein can be processed to obtain bonding materials in various shapes and used for fixing parts constituting mobile electronics such as those listed earlier. In particular, it can be preferably used in mobile electronics having liquid crystal displays. For instance, the PSA sheet disclosed herein is preferably used for fixing a flexible adherend in an electronic device (typically a mobile electronic device such as a smartphone) with a screen such as a touch display (possibly a liquid crystal display screen), wherein a flexible part such as FPC is folded and placed in its internal space for purposes of obtaining a larger screen, etc. With the use of the PSA sheet according to a preferable embodiment disclosed herein, even by light press-bonding, the flexible adherend can be fixed in a folded position and continuously held fixed in the same position. By this, the flexible part housed in the folded position in the limited internal space of a mobile electronic device can be precisely in place and stably held fixed with the PSA sheet disclosed herein. Examples of the material placed inside mobile electronics such as those listed above include a material that is polar and rigid, such as PC and PI. The PSA sheet disclosed herein can bond well to this type of material (a polar and rigid resin material).
Matters disclosed by this description include the following:
the substrate layer has a thickness TS and the PSA layer has a total thickness TPSA at a TS/TPSA ratio value of greater than 0.3, and
the PSA layer has a storage modulus at 25° C., G′(25° C.) of 0.15 MPa or greater as well as a loss modulus at 25° C., G″(25° C.), of 2.0 MPa or less.
Several working examples related to the present invention are described below, but the present invention is not intended to be limited to these examples. In the description below, “parts” and ‘%’ are by weight unless otherwise specified.
In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet, reflux condenser and addition funnel, were placed 90 parts of 2EHA and 10 parts of AA as monomers as well as ethyl acetate and toluene at about 1:1 (volume ratio) as polymerization solvents. The resulting mixture was stirred under a nitrogen flow for two hours. After oxygen was removed from the polymerization system in such a manner, was added 0.2 part of BPO as a polymerization initiator. Polymerization was carried out at 60° C. for 6 hours to obtain an acrylic polymer solution according to this Example.
To the resulting acrylic polymer solution, were added 0.05 part of epoxy-based crosslinking agent (product name TETRAD-C, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, available from Mitsubishi Gas Chemical Co., Ltd.) and 20 parts of terpene-phenol resin (product name TAMANOL 803L, available from Arakawa Chemical Industries, Ltd.; softening point: around 145° C. to 160° C.; hydroxyl value: 1 mgKOH/g to 20 mgKOH/g) to 100 parts of acrylic polymer in the solution. The resultant was mixed with stirring to prepare a PSA composition according to this Example.
As release liners A and B, were obtained polyester release film (product name DIAFOIL MRV, 75 μthick, Mitsubishi Polyester) treated with release agent to have a release face on one side and polyester release film (product name DIAFOIL MRF, 38 μthick, Mitsubishi Polyester) treated with release agent to have a release face on one side, respectively. To the release face of release liner A, the PSA composition obtained above was applied and allowed to dry at 100° C. for 2 minutes to form a 30 μthick PSA layer. The exposed adhesive face of the PSA layer was covered with release liner B with its release face on the PSA layer side to fabricate a substrate-free double-faced PSA sheet according to this Example.
The monomer compositions were modified as shown in Table 1. Otherwise in the same manner as in Reference Example 1, were prepared acrylic polymer solutions according to the respective Reference Examples. Using the resulting acrylic polymers, in the same manner as in Reference Example 1, were prepared PSA compositions according to the respective Reference Examples and were fabricated substrate-free double-faced PSA sheets according to the respective Reference Examples.
To a monomer mixture of 90 parts of 2EHA and 10 parts of AA, were admixed 0.05 part of 2,2-dimethoxy-1,2-diphenylethane-1-one (available from BASF Corporation, trade name IRGACURE 651) and 0.05 part of 1-hydroxycyclohexyl phenyl ketone (available from BASF Corporation, trade name IRGACURE 184) as photopolymerization initiators. The resulting mixture was irradiated with UV to a viscosity of about 15 Pa·s to obtain a partially-polymerized product (monomer syrup). To this monomer syrup, was added 0.1 part by weight of 1,6-hexanediol diacrylate and uniformly mixed to prepare a PSA composition. The viscosity was determined using a BH viscometer with a rotor (No. 5 rotor) at a frequency of rotation of 10 rpm at a measurement temperature of 30° C.
The same release liners A (75 μthick) and B (38 μthick) were obtained as in Reference Example 1. To the release face of release liner A, was applied the PSA composition obtained above. The applied amount of the PSA composition was adjusted so that the resulting PSA layer has a final thickness of 150 μm. Subsequently, release liner B was placed atop the coating of the PSA composition so that its release face was in contact with the coating. The coating was thus blocked from oxygen. The two faces of the coating of the PSA composition were irradiated with UV (product name BLACK LIGHT, available from Toshiba Corporation) having an irradiance of 5 mW/cm2 for 3 minutes to allow polymerization to proceed, whereby the PSA composition was cured to form a PSA layer. A substrate-free double-faced PSA sheet consisting of the PSA layer (i.e. the UV-cured coating) was thus obtained according to this Example. The irradiance was determined with an industrial UV checker (available from Topcon Corporation, product name UVR-T1 with light detector model number UD-T36) with peak sensitivity at 350 nm in wavelength.
The monomer composition was modified as shown in Table 1. Otherwise in the same manner as in Reference Example 6, was fabricated a substrate-free double-faced PSA sheet according to this Example.
The PSA sheet according to each Reference Example was cut 20 mm wide and 100 mm long to fabricate a test piece. The PSA sheet had been backed with 50 μm thick PET film adhered to one of its adhesive faces. It is noted that the backing film is not necessary for measurement of a single-faced PSA sheet on a substrate. In an environment at 23° C. and 50% RH, the adhesive face of the test piece was press-bonded to a stainless steel plate (SUS304BA plate) to fabricate a measurement sample. The press-bonding was achieved with a 0.1 kg roller moved back and forth once. In an environment at 23° C. and 50% RH, using a tensile tester, peel strength (N/20 mm) of the measurement sample was determined at a tensile speed of 300 mm/min at a peel angle of 180°. The peel strength was determined at less than one minute after the test piece was applied to the stainless steel plate. As the tensile tester, Precision Universal Tensile Tester Autograph AG-IS 50N available from Shimadzu Corporation was used, but an equivalent product can be used to obtain comparable measurement results.
The PSA sheets according to Reference Examples 4 and 5 were cut 20 mm wide and 100 mm long to prepare test pieces. Each of these PSA sheets had been backed with 50 μm thick PET film adhered to one of its adhesive faces. It is noted that the backing film is not necessary for measurement of a single-faced PSA sheet on a substrate. In an environment at 23° C. and 50% RH, using a pressing machine set at a temperature of 40° C., adhesive faces of the test pieces were press-bonded to a stainless steel plate (SUS304BA plate) at 0.05 MPa for 3 seconds to prepare measurement samples. In an environment at 23° C. and 50% RH, using a tensile tester, peel strength (N/20 mm) of these measurement samples was determined at a tensile speed of 300 mm/min at a peel angle of 180°. The peel strength was determined at less than one minute after the test pieces were press-bonded to the stainless steel plate. As the tensile tester, Precision Universal Tensile Tester Autograph AG-IS 50N available from Shimadzu Corporation was used, but an equivalent product can be used to obtain comparable measurement results.
The PSA sheet according to each Reference Example was cut 20 mm wide and 100 mm long to prepare a test piece. The PSA sheet had been backed with 50 μPET film adhered to one of its adhesive faces. It is noted that the backing film is not necessary for measurement of a single-faced PSA sheet on a substrate. In an environment at 23° C. and 50% RH, the adhesive face of the test piece was press-bonded to a stainless steel plate (SUS304BA plate) to fabricate a measurement sample. The press-bonding was achieved with a 2 kg roller moved back and forth once. The measurement sample was left standing in an environment at 23° C. and 50% RH for 30 min. Subsequently, using a tensile tester, based on JIS Z 0237:2000, peel strength (N/20 mm) was determined at a tensile speed of 300 mm/min at a peel angle of 180° and the resulting value was recorded as the 30-min aged adhesive strength. As the tensile tester, Precision Universal Tensile Tester Autograph AG-IS 50N available from Shimadzu Corporation was used, but an equivalent product can be used to obtain comparable measurement results.
As shown in
The PSA sheet according to each Reference Example with the two adhesive faces protected with two release liners was cut 3 mm wide and 10 mm long to obtain a PSA sheet test piece 70. PC plate 50 was placed with its surface opposite of the face to which the PET film had been fixed facing upward (i.e. with its PET film-bearing face at the bottom). One release liner was removed from test piece 70. Test piece 70 was placed atop PC plate 50 and adhesively fixed to the top face of PC plate 50 while the length direction of test piece 70 was oriented in the width direction of PC plate 50 and the two lengthwise edges of test piece 70 were aligned with 7 mm and 10 mm lines from the second end of PC plate 50. Test piece 70 was fixed with a 2 kg roller moved back and forth over its top face protected with the second release liner.
Subsequently, in an environment at 23° C. and 50% RH, the second release liner was removed from test piece 70 adhered on PC plate 50. As shown in
With respect to the PSA sheets according to Reference Examples 4 and 5, 40° C. z-axial deformation resistance was further evaluated. In this evaluation method, the adhesion of PSA sheet test piece 70 and PET film 60 was carried out at 0.05 MPa for 3 seconds using a pressing machine set at a temperature of 40° C. instead of with a 0.1 kg roller moved back and forth once. Otherwise in the same manner as above, their 40° C. z-axial deformation resistance was evaluated.
Unlike conventional repulsion resistance evaluation, this evaluation method allows assessment of light-pressure adhesion and deformation resistance relative to a peel load applied essentially solely in the thickness direction (z-axis direction) of the PSA sheet; and furthermore, by chronological observations, continuous deformation resistance can be evaluated as well.
With respect to each Reference Example, Table 1 shows the monomer composition of the acrylic polymer as well as the acrylic polymer's Mw and Mw/Mn, the PSA layer's G′(25° C.), G′(85° C.), G′(40° C.), G″(25° C.) (all in MPa) and gel fraction (%), the PSA sheet's 23° C. light-pressure initial adhesive strength (N/20 mm), 40° C. light-pressure initial adhesive strength (N/20 mm) and 30-min aged adhesive strength (N/20 mm) as well as its z-axial deformation resistance test results (at 23° C. and 40° C.).
As shown in Table 1, the PSA sheets according to Reference Examples 1 to 7 all showed light-pressure initial adhesion at the prescribed press-bonding temperatures and exhibited a passing level of performance in the z-axial deformation resistance test, wherein the PSA layer had storage moduli G′(25° C.)≥0.15 MPa and G′(85° C.)≥0.02 MPa as well as 23° C. or 40° C. light-pressure initial adhesive strength≥8 N/20 mm. In particular, the PSA sheets according to Reference Examples 1 to 3, 6 and 7 with 23° C. light-pressure initial adhesive strength≥8 N/20 mm showed good initial adhesion by light press-bonding at 23° C. as well as deformation resistance to a continuous z-axial load by light press-bonding at 23° C. As for Reference Examples 4 and 5, their light-pressure initial adhesive strength was not measurable at 23° C., but they showed good 40° C. light-pressure initial adhesion as well as passing levels of deformation resistance in the z-axial deformation resistance test (40° C.). It is noted that in Reference Examples 4 and 5, the backing PET film peeled in determining both the 40° C. light-pressure initial adhesive strength and 30-min aged adhesive strength, indicating that they had powerful adhesive strength exceeding 20 N/20 mm.
In the same manner as Reference Example 1 above, a PSA composition was prepared, applied to one face (first face) of a 38 μthick polyester resin film (substrate layer), and allowed to dry at 100° C. for 2 minutes to form a 23 μthick first PSA layer. As a release liner, was obtained polyester release film (product name DIAFOIL MRF, 38 μthick, available from Mitsubishi Polyester Film Group) having a release agent-treated release face on each side. To one release face of the release liner, was applied the PSA composition prepared above and allowed to dry at 100° C. for 2 minutes to form a 23 μm thick second PSA layer. The second PSA layer was transferred to the PSA layer-free face of the substrate layer bearing the first PSA layer to fabricate an on-substrate double-faced PSA sheet according to this Example.
Substrate layers varying in thickness were used. The thicknesses of the PSA layers (the first and second PSA layers) were changed. Otherwise in the same manner as Example 1, were fabricated on-substrate double-faced PSA sheets according to the respective Examples.
With respect to the on-substrate double-faced PSA sheets according to the respective Examples, Table 2 shows the thickness (μm) of each PSA layer, the thickness (μm) of substrate layer, and the TS/TPSA ratio value (the ratio of the substrate layer's thickness TS to the PSA layer's total thickness TPSA).
To an exposed adhesive face of the on-substrate double-faced PSA sheet according to each Example, was applied polyester release film (trade name DIAFOIL MRF, 75 μthick, available from Mitsubishi Polyester). The resultant was cut 20 mm by 150 mm to obtain a test piece. The test piece was punched through with a blade entering from the reverse side of the face bearing the 75 μthick polyester release film to fabricate a measurement sample (3 mm wide, 10 mm long). In the measurement sample, the 75 μthick release film was removed from the waste part outside the punched lines and the processability of the on-substrate double-faced PSA sheet according to each Example was evaluated. When the measure of precision in cut width was (3 mm)±0.5 mm and the part inside the punched lines (the punched-out part) remained unmoved upon removal of the waste part (i.e. when the surface area of the test piece peeled off the release film was less than 0.5% of the bonding area), it was rated “A”; when the measure of precision in cut width was (3 mm)±0.5 mm and the part inside the punched lines (the punched-out part) moved slightly upon removal of the waste part (i.e. when the surface area of the test piece peeled off the release film was 0.5% or more and less than 5% of the bonding area), it was rated “B”; and when the measure of precision in cut width was greater than (3 mm)±0.5 mm and the part inside the punched lines (the punched-out part) moved upon removal of the waste part (i.e. when the surface area of the test piece peeled off the release film was 5% or more of the bonding area), it was rated “C.” The results are shown in Table 2. When a test piece results in “A” or “B” in the conformability test, it can be thought to have a passing level of processability.
As shown in Table 2, with respect to the on-substrate double-faced PSA sheet according to Examples 1 and 2, their substrate layer's thickness TS to the first and second PSA layers' combined thickness TPSA ratio (TS/TPSA) values were both greater than 0.3 and their processability test results were both at passing levels. In these PSA sheets, the PSA layers had storage moduli G′(25° C.) of 0.15 MPa or greater and loss moduli G″(25° C.) of 2.0 MPa or less. On the other hand, with respect to Examples 3 and 4 using an on-substrate double-faced PSA sheet having a TS/TPSA ratio value of 0.3 or less, good processability was not obtained.
These results indicate that, with respect to a PSA sheet having a substrate layer and a PSA layer provided to at least one face of the substrate layer wherein the substrate layer has a thickness TS and the PSA layer has a total thickness TPSA at a TS/TPSA ratio value greater than 0.3 with the PSA layer having a storage modulus G′(25° C.) of 0.15 MPa or greater and a loss modulus G″(25° C.) of 2.0 MPa or less, excellent suitability to cutting and ease of handling are displayed, with the good suitability to cutting possibly combined with blocking resistance. In other words, the PSA sheet in this embodiment has excellent processability.
Although specific embodiments of the present invention have been described in detail above, these are merely for illustrations and do not limit the scope of claims. The art according to the claims includes various modifications and changes made to the specific embodiments illustrated above.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-229864 | Nov 2017 | JP | national |
