Patent Application
20180163099
The invention relates to a pressure-sensitive adhesive strip.
Adhesive tapes are frequently used for the bonding of ultrasmall components, for example in devices in the consumer electronics industry. In order to enable this, it is necessary for the form of the adhesive tape section to be matched to the form of the component. In this case, difficult geometries are often also necessary, which are obtained by die-cutting of the adhesive tape. Thus, element widths in die-cut parts of a few millimeters or even less are by no means rare. On application of these sensitive adhesive tapes to the components, there is frequently deformation of the die-cut parts.
In order to suppress or at least reduce the deformation, it has been found to be advantageous to integrate a film, for example a PET film, into the adhesive tapes as a middle lamina in order to absorb the tensile forces on application.
Bonds with such adhesive tapes are increasingly also being used if the component is subject to shocks. Particularly shock-resistant bonds have been found to be those with pressure-sensitive adhesive strips having a viscoelastic, syntactically foamed core, a stabilizing film and, on the outer laminas, two self-adhesive bonding layers.
These pressure-sensitive adhesive strips are capable of such high performance that cohesive fracture within the pressure-sensitive adhesive strip is to be observed under shock. The bond between the foamed core and the stabilizing film fails, and foam and film are parted from one another.
Foamed pressure-sensitive adhesive composition systems have long been known and are described in the prior art.
In principle, polymer foams can be produced in two ways. One way is via the effect of a blowing gas, whether added as such or resulting from a chemical reaction, and a second way is via incorporation of hollow beads into the polymer matrix. Foams that have been produced by the latter route are referred to as syntactic foams.
In the case of a syntactic foam, hollow beads such as glass beads or hollow ceramic beads (microbeads) or microballoons are incorporated in a polymer matrix. As a result, in a syntactic foam, the voids are separated from one another and the substances (gas, air) present in the voids are divided from the surrounding matrix by a membrane.
Compositions foamed with hollow microbeads are notable for a defined cell structure with a homogeneous size distribution of the foam cells. With hollow microbeads, closed-cell foams without voids are obtained, the features of which include better sealing action against dust and liquid media compared to open-cell variants. Furthermore, chemically or physically foamed materials have a greater propensity to irreversible collapse under pressure and temperature, and frequently show lower cohesive strength.
Particularly advantageous properties can be achieved when the microbeads used for foaming are expandable microbeads (also referred to as “microballoons”). By virtue of their flexible, thermoplastic polymer shell, foams of this kind have higher adaptation capacity than those filled with non-expandable, non-polymeric hollow microbeads (for example hollow glass beads). They have better suitability for compensation for manufacturing tolerances, as is the rule, for example, in the case of injection-molded parts, and can also better compensate for thermal stresses because of their foam character.
Furthermore, it is possible to further influence the mechanical properties of the foam via the selection of the thermoplastic resin of the polymer shell. For example, even when the foam has a lower density than the matrix, it is possible to produce foams having higher cohesive strength than with the polymer matrix alone. For instance, typical foam properties such as adaptation capacity to rough surfaces can be combined with a high cohesive strength for self-adhesive foams.
Among the devices in the consumer electronics industry are electronic, optical and precision devices, in the context of this application especially those devices as classified in Class 9 of the International Classification of Goods and Services for the Registration of Marks (Nice classification); 10th edition (NCL(10-2013)), to the extent that these are electronic, optical or precision devices, and also clocks and time-measuring devices according to Class 14 (NCL(10-2013)),
such as, in particular,
Technical development is going increasingly in the direction of devices which are ever smaller and lighter in design, allowing them to be carried at all times by their owner, and usually being generally carried. This is now accomplished increasingly by realization of low weights and/or suitable size of such devices. Such devices are also referred to as mobile devices or portable devices for the purposes of this specification. In this development trend, precision and optical devices are increasingly being provided (also) with electronic components, thereby raising the possibilities for minimization. On account of the carrying of the mobile devices, they are subject to increased loads—in particular, to mechanical loads—as for instance by impact on edges, by being dropped, by contact with other hard objects in a bag, or else simply by the permanent motion involved in being carried per se. Mobile devices, however, are also subject to a greater extent to loads due to moisture exposure, temperature influences, and the like, than those “immobile” devices which are usually installed in interiors and which move little or not at all.
The invention accordingly refers with particular preference to mobile devices, since the pressure-sensitive adhesive strip used in accordance with the invention has a particular benefit here on account of the unexpectedly good, namely further improved, properties (very high shock resistance). Listed below are a number of portable devices, without wishing the representatives specifically identified in this list to impose any unnecessary restriction with regard to the subject-matter of the invention.
For these devices, a particular requirement is for adhesive tapes having high holding performance.
In addition, it is important that the holding performance of the adhesive tapes does not fail when the mobile device, for example a mobile phone, is dropped and hits the ground. The adhesive strip must thus have very high shock resistance.
EP 2 832 780 A1 relates to a pressure-sensitive adhesive foam comprising a rubber elastomer, at least one hydrocarbon tackifier and a crosslinker selected from the group of the polyfunctional (meth)acrylate compounds.
JP 2010/070,655 A relates to a composition comprising a styrene-based thermoplastic elastomer (A), a tackifier (B) and thermally expandable foaming agent in microcapsule form.
DE 10 2008 056 980 A1 relates to a self-adhesive composition consisting of a mixture comprising:
WO 2009/090119 A1 relates to a pressure-sensitive adhesive composition comprising expanded microballoons, wherein the bonding force of the adhesive composition comprising the expanded microballoons is reduced by not more than 30% compared to the bonding force of an adhesive composition of identical basis weight and formulation that has been defoamed by the destruction of the voids formed by the expanded microballoons.
WO 2003/011954 A1 relates to a foamed pressure-sensitive adhesive article, wherein the article comprises a) a polymer mixture comprising at least one styrenic block copolymer and at least one polyarylene oxide, and b) one or more foamable polymer microbeads.
DE 10 2015 206 076 A1 relates to a pressure-sensitive adhesive strip which can be detached again without residue or destruction through extensive stretching essentially in the plane of the bond, composed of one or more adhesive composition layers that all consist of a pressure-sensitive adhesive composition foamed with microballoons, and optionally of one or more intermediate carrier layers, wherein the pressure-sensitive adhesive strip consists exclusively of the adhesive composition layers mentioned and any intermediate carrier layers present, and one outer upper and one outer lower face of the pressure-sensitive adhesive strip are formed by said adhesive composition layer(s). The redetachable pressure-sensitive adhesive strip is notable for its marked shock resistance.
DE 10 2016 202 479, a patent application from the same applicant as this document that was still unpublished at the priority date of the present application, describes a four-layer adhesive tape in which a foamed inner layer is additionally strengthened by a PET stabilization film. By virtue of such a construction, it was possible to offer particularly shock-resistant adhesive tapes.
DE 10 2016 209 707, a patent application from the same applicant as this document that was likewise still unpublished at the priority date of the present application, describes a pressure-sensitive adhesive strip composed of three layers, comprising an inner layer F of a non-extensible film carrier, a layer SK1 composed of a self-adhesive composition arranged on one of the surfaces of the film carrier layer F and based on a foamed acrylate composition, and a layer SK2 composed of a self-adhesive composition arranged on the opposite surface of the film carrier layer F from the layer SK1 and based on a foamed acrylate composition. By virtue of such a construction, it was likewise possible to offer particularly shock-resistant adhesive tapes.
The problem addressed by the present invention with respect to the prior art is that of providing a pressure-sensitive adhesive strip having improved thermal shear strength coupled with high bond strength and high shock resistance. There is especially a need for such a pressure-sensitive adhesive composition in the production of mobile devices in which adhesive bonds with high shock resistance are to be implemented.
The problem is surprisingly solved in accordance with the invention by a pressure-sensitive adhesive strip of the generic type as set out in the main claim. The subject-matter of the dependent claims comprises advantageous embodiments of the pressure-sensitive adhesive strip.
Accordingly, the invention relates to a pressure-sensitive adhesive strip comprising at least one layer SK1, preferably exactly one layer SK1, of a self-adhesive composition based on a vinylaromatic block copolymer composition foamed with microballoons, where the mean diameter of the voids formed by the microballoons in the self-adhesive composition layer SK1 is 45 to 110 μm.
The pressure-sensitive adhesive strips of the invention, as well as high bond strength and high shock resistance, also have improved thermal shear strength. For instance, in the static shear test at elevated temperatures, they exhibit high shear strengths and also have high thermal stabilities, as apparent in the SAFT (“Shear Adhesion Failure Temperature”) test.
It has been found that, surprisingly, in self-adhesive composition layers based on a vinylaromatic block copolymer composition foamed with microballoons, it is possible to achieve improved thermal shear strengths by selecting the mean diameters of the voids formed by the microballoons in the self-adhesive composition layers at 45 to 110 μm. Pressure-sensitive adhesive strips comprising at least one such layer accordingly have improved thermal shear strengths.
Preferably, the pressure-sensitive adhesive strip consists of a single self-adhesive composition layer SK1, and so the pressure-sensitive adhesive strip is a one-layer system. Such a one-layer adhesive tape which is self-adhesive on both sides, i.e. double-sided adhesive tape, is also referred to as “transfer tape”. The self-adhesive composition layer of the transfer tape preferably has a thickness of 45 to 5000 μm, more preferably of 80 to 2500 μm, even more preferably of 100 μm to 2000 μm, especially of 100 to 300 μm, for example 150 μm.
In a further preferred embodiment, the pressure-sensitive adhesive strip comprises, as well as a layer SK1, also a layer F of a film carrier, where the layer SK1 is arranged on one of the surfaces of the film carrier layer F. Such a pressure-sensitive adhesive strip is a single-sided adhesive tape. More preferably, the single-sided adhesive tape consists exclusively of the layer SK1 and the film carrier layer F.
The layer F of a film carrier is also referred to synonymously in the context of this document simply as film carrier, film layer or film carrier layer.
In a particularly preferred embodiment, the pressure-sensitive adhesive strip further comprises a layer SK2 of a self-adhesive composition based on a vinylaromatic block copolymer composition arranged on the opposite surface of the film carrier layer F from the layer SK1. Preferably, the layer SK2 is based on a foamed composition, more preferably foamed with microballoons, where the mean diameter of the voids formed by the microballoons in the layer SK2 is especially 45 to 110 μm. Such a pressure-sensitive adhesive strip is a double-sided adhesive tape. More particularly, the double-sided adhesive tape consists exclusively of the layers SK1, SK2 and the film carrier layer F.
In the present application, “arrangement” of the layers SK1 and SK2 on the surfaces of the film carrier layer can mean an arrangement in which the layers SK1 and/or SK2 are in direct contact with the surfaces of the film carrier layer, i.e. are arranged directly on the surface. Alternatively, this can also mean an arrangement in which there is at least one further layer between the layer SK1 and one surface of the film carrier layer F and/or between the layer SK2 and the opposite surface of the film carrier layer F from the layer SK1. Preferably, in the pressure-sensitive adhesive strip of the invention having a film carrier layer F, the layers SK1 and, if present, SK2 are in direct contact with one of the surfaces of the film carrier layer F, or with the opposite surface of the film carrier layer F from the layer SK1.
In pressure-sensitive adhesive strips of the invention that have more than one layer of a self-adhesive composition, all self-adhesive composition layers included are preferably self-adhesive composition layers based on a vinylaromatic block copolymer composition foamed with microballoons, where the mean diameter of the voids formed by the microballoons in the self-adhesive composition layers is 45 to 110 μm in each case. Pressure-sensitive adhesive strips of this kind have particularly high thermal shear strengths.
Double-sided adhesive tapes of the invention having film carriers in which the two self-adhesive composition layers SK1 and SK2 have been foamed with microballoons in such a way that the mean diameter of the voids formed by the microballoons in each of the two self-adhesive composition layers SK1 and SK2 is 45 to 100 μm correspondingly have particularly high thermal shear strengths. If, in the double-sided adhesive tape, as well as layer SK1, layer SK2 has additionally also been foamed, this also leads to elevated shock resistance of the adhesive tape.
The layers SK1 and SK2 of self-adhesive composition, in the context of this document, are also referred to as self-adhesive composition layers SK1 and SK2, simply as layers SK1 and SK2, or else as outer layers, adhesive composition layers or pressure-sensitive adhesive composition layers SK1 and SK2. The term “outer” relates here to the preferably three-layer construction of the double-sided adhesive tape of the invention, composed of the film carrier and layers SK1 and SK2, regardless of any liner present on the outer faces of the self-adhesive composition layers (see further down).
In such a single-sided or double-sided adhesive tape, the film carrier layer preferably has a thickness between 5 and 125 μm, more preferably between 10 and 60 μm, even more preferably between 10 and 50 μm and more preferably between 10 and 40 μm. In addition, in such a single-sided or double-sided adhesive tape, the self-adhesive composition layer SK1 preferably has a thickness of 45 to 1000 μm, more preferably between 45 and 200 μm and especially from 60 to 150 μm. Moreover, in such a single-sided or double-sided adhesive tape, the self-adhesive composition layer SK2, if present, preferably has a thickness of 20 to 1000 μm, more preferably of 45 to 1000 μm, even more preferably between 45 and 200 μm and especially from 60 to 150 μm. The pressure-sensitive adhesive strip in the form of a single-sided adhesive tape preferably has a thickness of 50 μm to 1125 μm, more preferably of 100 to 1000 μm, and especially of 150 μm to 300 μm. The pressure-sensitive adhesive strip in the form of a double-sided adhesive tape with a film carrier preferably has a thickness of 70 μm to 2125 μm, more preferably of 95 μm to 2125 μm, even more preferably of 100 to 1000 μm, and especially of 150 μm to 300 μm.
In the double-sided adhesive tape with a film carrier, the self-adhesive composition layer SK2 has preferably been foamed with microballoons, where the mean diameter of the voids formed by the microballoons in the self-adhesive composition layer SK2 is preferably 45 to 110 μm. In a particularly preferred embodiment of the pressure-sensitive adhesive strip, this has symmetric construction in relation to the composition of the layers, in that the foamed vinylaromatic block copolymer compositions of the two self-adhesive composition layers SK1 and SK2 are chemically identical, and advantageously also, if additives are added thereto, these are identical and used in an identical amount. More particularly, the pressure-sensitive adhesive strip is of entirely symmetric construction, i.e. both with regard to the chemical composition of the two foamed self-adhesive vinylaromatic block copolymer composition layers SK1 and SK2 (including any additizations present therein) and with regard to the structural composition thereof, in that both surfaces of the film carrier F have been identically pretreated and the two self-adhesive composition layers SK1 and SK2 have the same thickness and density. “Entirely symmetric” relates especially to the z direction (“thickness”, direction perpendicular to the plane of the pressure-sensitive adhesive strip) of the pressure-sensitive adhesive strip, but may of course additionally also relate to the geometry in the surface plane (x and y directions, i.e. length and width, of the pressure-sensitive adhesive strip).
Preferably, the double-sided adhesive tape with a film carrier has a structurally symmetric construction in z direction, in that the two self-adhesive composition layers SK1 and SK2 are of equal thickness and/or have the same density. According to the invention, it is also possible to implement a double-sided adhesive tape in which the self-adhesive composition layers SK1 and SK2 are of equal thickness and/or have the same density but are chemically different.
The outer faces of the pressure-sensitive adhesive strip that are available for bonding are preferably formed by foamed self-adhesive composition layers, especially foamed with microballoons, because it is thus possible to implement the high shock resistance in the x,y plane and especially in the z plane in a particularly efficient manner. A particular factor of central significance for the shock resistance here is the voids formed in the self-adhesive composition layers.
Accordingly, the single-sided adhesive tape of the invention is preferably a pressure-sensitive adhesive strip consisting of the film carrier layer F and the self-adhesive composition layer SK1 arranged on one of the surfaces of the film carrier layer F. The outer face of the pressure-sensitive adhesive strip which is available for bonding is formed there by the self-adhesive composition layer SK1 foamed in accordance with the invention.
Accordingly, the double-sided adhesive tape of the invention with a film carrier is likewise preferably a pressure-sensitive adhesive strip consisting of the film carrier layer F, the self-adhesive composition layer SK1 arranged on one of the surfaces of the film carrier layer F, and the self-adhesive composition layer SK2 arranged on the opposite surface of the film carrier layer F from the layer SK1. One of the two outer faces of the pressure-sensitive adhesive strip which are available for bonding is formed there by the self-adhesive composition layer SK1 foamed in accordance with the invention. More preferably, the layer SK2 is based on a vinylaromatic block copolymer composition foamed with microballoons, where the mean diameter of the voids formed by the microballoons in the self-adhesive composition layer SK2 is especially 45 to 110 μm.
The remarks which follow relate explicitly and without exception also to the entirely symmetric execution variant of the double-sided adhesive tape of the invention.
The self-adhesive compositions of layers SK1 and SK2 are each a pressure-sensitive adhesive (PSA) composition. The terms “self-adhesive” and “pressure-sensitively adhesive” are used synonymously in this respect within the scope of this document.
Pressure-sensitive adhesive compositions are especially those polymeric compositions which—if appropriate by suitable additization with further components, for example tackifying resins—are permanently tacky and adhesive at the use temperature (unless defined otherwise, at room temperature) and adhere on contact to a multitude of surfaces, and especially adhere immediately (have so-called “tack” [tackiness or touch-tackiness]). They are capable, even at the use temperature, without activation by solvent or by heat—but typically via the influence of a greater or lesser pressure—of sufficiently wetting a substrate to be bonded such that sufficient interactions for adhesion can form between the composition and the substrate. Influencing parameters that are essential in this respect include the pressure and the contact time. The exceptional properties of the pressure-sensitive adhesive compositions derive, inter alia, especially from their viscoelastic properties. For example, it is possible to produce weakly or strongly adhering adhesive compositions; and also those that can be bonded just once and permanently, such that the bond cannot be parted without destruction of the adhesive and/or the substrates, or those that can readily be parted again and, if appropriate, bonded repeatedly.
Pressure-sensitive adhesive compositions can in principle be produced on the basis of polymers of different chemical nature. The pressure-sensitive adhesive properties are affected by factors including the nature and the ratios of the monomers used in the polymerization of the polymers underlying the pressure-sensitive adhesive composition, the mean molar mass and molar mass distribution thereof, and the nature and amount of the additives to the pressure-sensitive adhesive composition, such as tackifying resins, plasticizers and the like.
To achieve the viscoelastic properties, the monomers on which the polymers underlying the pressure-sensitive adhesive composition are based, and any further components present in the pressure-sensitive adhesive composition, are especially chosen such that the pressure-sensitive adhesive composition has a glass transition temperature (to DIN 53765) below the use temperature (i.e. typically below room temperature).
It may be advantageous in some cases, by suitable cohesion-enhancing measures, for example crosslinking reactions (formation of bridge-forming linkages between the macromolecules), to enlarge and/or to shift the temperature range in which a polymer composition has pressure-sensitive adhesive properties. The range of application of the pressure-sensitive adhesive compositions can thus be optimized via a setting between flowability and cohesion of the composition.
A pressure-sensitive adhesive composition has permanent pressure-sensitive adhesion at room temperature, i.e. has a sufficiently low viscosity and high touch-tackiness, such that it wets the surface of the respective adhesive substrate even at low contact pressure. The bondability of the adhesive composition is based on its adhesive properties, and the redetachability is based on its cohesive properties.
If reference is made in the remarks which follow relating to preferred embodiments of the invention to a “self-adhesive composition layer” or “self-adhesive composition layers” or to a “vinylaromatic block copolymer composition” or “vinylaromatic block copolymer compositions”, this may relate to layer SK1, to layer SK2 or else to both layers, unless explicitly stated otherwise.
Self-Adhesive Composition Layers Usable in Accordance with the Invention
The layer SK1 of the pressure-sensitive adhesive strip of the invention is based on a vinylaromatic block copolymer composition foamed with microballoons. The layer SK2 of the pressure-sensitive adhesive strip of the invention in the form of a double-sided adhesive tape with a film carrier is likewise based on a vinylaromatic block copolymer composition, and optionally on a vinylaromatic block copolymer composition foamed with microballoons.
(a) Self-Adhesive Composition Layers Based on a Vinylaromatic Block Copolymer Composition
Preferably, the vinylaromatic block copolymer used in the layer SK1 and/or in the layer SK2 is at least one synthetic rubber in the form of a block copolymer having an A-B, A-B-A, (A-B)n, (A-B)nX or (A-B-A)nX structure,
in which
More preferably, all synthetic rubbers in the self-adhesive composition layer of the invention are block copolymers having an A-B, A-B-A, (A-B)n, (A-B)nX or (A-B-A)nX construction as set out above. The self-adhesive composition layer of the invention may thus also comprise mixtures of various block copolymers having a construction as described above.
Suitable block copolymers (vinylaromatic block copolymers) thus comprise one or more rubber-like blocks B (soft blocks) and one or more glass-like blocks A (hard blocks). More preferably, at least one synthetic rubber in the self-adhesive composition layer of the invention is a block copolymer having an A-B, A-B-A, (A-B)2X, (A-B)3X or (A-B)4X construction, where the above meanings are applicable to A, B and X. Most preferably, all synthetic rubbers in the self-adhesive composition layer of the invention are block copolymers having an A-B, A-B-A, (A-B)2X, (A-B)3X or (A-B)4X construction, where the above meanings are applicable to A, B and X. More particularly, the synthetic rubber in the self-adhesive composition layer of the invention is a mixture of block copolymers having an A-B, A-B-A, (A-B)2X, (A-B)3X or (A-B)4X structure, preferably comprising at least diblock copolymers A-B and/or triblock copolymers A-B-A and/or (A-B)2X.
Also advantageous is a mixture of diblock and triblock copolymers and (A-B)n or (A-B)nX block copolymers with n not less than 3.
Also advantageous is a mixture of diblock and multiblock copolymers and (A-B)n or (A-B)nX block copolymers with n not less than 3.
Vinylaromatic block copolymers utilized may thus, for example, be diblock copolymers A-B in combination with others among the block copolymers mentioned. It is possible to use the proportion of diblock copolymers to adjust the adaptation characteristics of the self-adhesive compositions and the bond strength thereof. Vinylaromatic block copolymer used in accordance with the invention preferably has a diblock copolymer content of 0% to 70% by weight and more preferably of 15% to 50% by weight. A higher proportion of diblock copolymer in the vinylaromatic block copolymer leads to a distinct reduction in cohesion of the adhesive composition.
The self-adhesive compositions employed are preferably those based on block copolymers comprising polymer blocks (i) predominantly formed from vinylaromatics (A blocks), preferably styrene, and simultaneously (ii) those predominantly formed by polymerization of 1,3-dienes (B blocks), for example butadiene and isoprene or a copolymer of the two.
More preferably, self-adhesive compositions of the invention are based on styrene block copolymers; for example, the block copolymers of the self-adhesive compositions have polystyrene end blocks.
The block copolymers that result from the A and B blocks may contain identical or different B blocks. The block copolymers may have linear A-B-A structures. It is likewise possible to use block copolymers in radial form and star-shaped and linear multiblock copolymers. Further components present may be A-B diblock copolymers. All the aforementioned polymers can be utilized alone or in a mixture with one another.
In a vinylaromatic block copolymer used in accordance with the invention, such as a styrene block copolymer in particular, the proportion of polyvinylaromatics, such as polystyrene in particular, is preferably at least 12% by weight, more preferably at least 18% by weight and especially preferably at least 25% by weight, and likewise preferably at most 45% by weight and more preferably at most 35% by weight.
Rather than the preferred polystyrene blocks, vinylaromatics used may also be polymer blocks based on other aromatic-containing homo- and copolymers (preferably C8 to C12 aromatics) having glass transition temperatures of greater than 75° C., for example a methylstyrene-containing aromatic blocks. In addition, it is also possible for identical or different A blocks to be present.
Preferably, the vinylaromatics for formation of the A block include styrene, α-methylstyrene and/or other styrene derivatives. The A block may thus be in the form of a homo- or copolymer. More preferably, the A block is a polystyrene.
Preferred conjugated dienes as monomers for the soft block B are especially selected from the group consisting of butadiene, isoprene, ethylbutadiene, phenylbutadiene, piperylene, pentadiene, hexadiene, ethylhexadiene and dimethylbutadiene, and any desired mixtures of these monomers. The B block may also be in the form of a homopolymer or copolymer.
More preferably, the conjugated dienes as monomers for the soft block B are selected from butadiene and isoprene. For example, the soft block B is a polyisoprene, a polybutadiene or a partly hydrogenated derivative of one of these two polymers, such as polybutylene-butadiene in particular, or a polymer formed from a mixture of butadiene and isoprene. Most preferably, the B block is a polybutadiene.
A blocks are also referred to as “hard blocks” in the context of this invention. B blocks are correspondingly also called “soft blocks” or “elastomer blocks”. This is reflected by the inventive selection of the blocks in accordance with their glass transition temperatures (for A blocks at least 25° C., especially at least 50° C., and for B blocks at most 25° C., especially at most −25° C.).
The proportion of the vinylaromatic block copolymers, such as styrene block copolymers in particular, preferably based on the overall self-adhesive composition layer, totals at least 20% by weight, preferably at least 30% by weight, further preferably at least 35% by weight. Too low a proportion of vinylaromatic block copolymers results in relatively low cohesion of the pressure-sensitive adhesive composition.
The maximum proportion of the vinylaromatic block copolymers, such as styrene block copolymers in particular, based on the overall self-adhesive composition, totals at most 75% by weight, preferably at most 65% by weight, further preferably at most 55% by weight. Too high a proportion of vinylaromatic block copolymers in turn results in barely any pressure-sensitive adhesion in the pressure-sensitive adhesive composition.
Accordingly, the proportion of the vinylaromatic block copolymers, such as styrene block copolymers in particular, based on the overall self-adhesive composition, preferably totals at least 20% by weight, more preferably at least 30% by weight, further preferably at least 35% by weight, and simultaneously at most 75% by weight, more preferably at most 65% by weight, most preferably at most 55% by weight.
The pressure-sensitive adhesion of the self-adhesive compositions can be achieved by addition of tackifying resins that are miscible with the elastomer phase. The self-adhesive compositions generally include, as well as the at least one vinylaromatic block copolymer, at least one tackifying resin in order to increase the adhesion in the desired manner. The tackifying resin should be compatible with the elastomer block of the block copolymers.
A “tackifying resin”, in accordance with the general understanding of the person skilled in the art, is understood to mean an oligomeric or polymeric resin that increases the adhesion (tack, intrinsic tackiness) of the pressure-sensitive adhesive composition compared to the pressure-sensitive adhesive composition that does not contain any tackifying resin but is otherwise identical.
If tackifying resin is present in the self-adhesive compositions, correspondingly, a resin having a DACP (diacetone alcohol cloud point) of greater than 0° C., preferably greater than 10° C., and a softening temperature (ring & ball) of not less than 70° C., preferably not less than 100° C., is chosen to an extent of at least 75% by weight (based on the total resin content). More preferably, the tackifying resin mentioned simultaneously has a DACP value of not more than 45° C. if no isoprene blocks are present in the elastomer phase, or of not more than 60° C. if isoprene blocks are present in the elastomer phase. More preferably, the softening temperature of the tackifying resin mentioned is not more than 150° C.
More preferably, the tackifying resins comprise at least 75% by weight (based on the total resin content) of hydrocarbon resins or terpene resins or a mixture of the same.
It has been found that tackifiers advantageously usable for the pressure-sensitive adhesive composition(s) are especially nonpolar hydrocarbon resins, for example hydrogenated and non-hydrogenated polymers of dicyclopentadiene, non-hydrogenated, partly, selectively or fully hydrogenated hydrocarbon resins based on C5, C5/C9 or C9 monomer streams, and polyterpene resins based on α-pinene and/or β-pinene and/or δ-limonene. The aforementioned tackifying resins can be used either alone or in a mixture. It is possible to use either room temperature solid resins or liquid resins. Tackifying resins, in hydrogenated or non-hydrogenated form, which also contain oxygen, can optionally and preferably be used in the adhesive composition up to a maximum proportion of 25%, based on the total mass of the resins, for example rosins and/or rosin esters and/or terpene-phenol resins.
The proportion of the optionally usable resins or plasticizers that are liquid at room temperature, in a preferred variant, is up to 15% by weight, preferably up to 10% by weight, based on the overall self-adhesive composition.
In a preferred embodiment, 20% to 60% by weight of at least one tackifying resin, based on the total weight of the self-adhesive composition layer, preferably 30% to 50% by weight of at least one tackifying resin, based on the total weight of the self-adhesive composition, is present in the self-adhesive composition layers.
Further additives that can typically be utilized are:
preferably with a proportion of 0.2% to 5% by weight, based on the total weight of the self-adhesive composition,
preferably with a proportion of 0.2% to 1% by weight, based on the total weight of the self-adhesive composition,
preferably with a proportion of 0.2% to 1% by weight, based on the total weight of the self-adhesive composition,
preferably with a proportion of 0.2% to 1% by weight, based on the total weight of the self-adhesive composition,
preferably with a proportion of 0.2% to 1% by weight, based on the total weight of the self-adhesive composition,
preferably with a proportion of 0.2% to 1% by weight, based on the total weight of the self-adhesive composition,
preferably with a proportion of 0.2% to 10% by weight, based on the total weight of the self-adhesive composition, and
preferably with a proportion of 0.2% to 10% by weight, based on the total weight of the self-adhesive composition.
The nature and amount of the blend components can be selected as required.
It is also in accordance with the invention when the adhesive composition does not have some of and preferably any of the admixtures mentioned in each case.
In one embodiment of the present invention, the self-adhesive composition also comprises further additives; nonlimiting examples include crystalline or amorphous oxides, hydroxides, carbonates, nitrides, halides, carbides or mixed oxide/hydroxide/halide compounds of aluminum, of silicon, of zirconium, of titanium, of tin, of zinc, of iron or of the alkali metals/alkaline earth metals. These are essentially aluminas, for example aluminum oxides, boehmite, bayerite, gibbsite, diaspore and the like. Sheet silicates are very particularly suitable, for example bentonite, montmorillonite, hydrotalcite, hectorite, kaolinite, boehmite, mica, vermiculite or mixtures thereof. But it is also possible to use carbon blacks or further polymorphs of carbon, for instance carbon nanotubes.
The adhesive compositions may also be colored with dyes or pigments. The adhesive compositions may be white, black or colored.
The plasticizers metered in may, for example, be mineral oils, (meth)acrylate oligomers, phthalates, cyclohexanedicarboxylic esters, water-soluble plasticizers, plasticizing resins, phosphates or polyphosphates.
The addition of silicas, advantageously of precipitated silica surface-modified with dimethyldichlorosilane, can be utilized in order to further enhance the thermal shear strength of the self-adhesive composition.
In a preferred embodiment of the invention, the adhesive composition consists solely of vinylaromatic block copolymers, tackifying resins, microballoons and optionally the abovementioned additives.
Further preferably, the adhesive composition consists of the following composition:
Further preferably, the adhesive composition consists of the following composition:
Further preferably, the adhesive composition consists of the following composition:
The self-adhesive composition SK1 of the invention has been foamed, and the self-adhesive composition SK2 of the invention has preferably also been foamed. Preferably, the foaming is effected in each case by the introduction and subsequent expansion of microballoons.
“Microballoons” are understood to mean hollow microbeads that are elastic and hence expandable in their ground state, having a thermoplastic polymer shell. These beads have been filled with low-boiling liquids or liquefied gas. Shell material employed is especially polyacrylonitrile, PVDC, PVC or polyacrylates. Suitable low-boiling liquids are especially hydrocarbons from the lower alkanes, for example isobutane or isopentane, that are enclosed in the polymer shell under pressure as liquefied gas.
Action on the microballoons, especially by the action of heat, results in softening of the outer polymer shell. At the same time, the liquid blowing gas present within the shell is converted to its gaseous state. This causes irreversible extension and three-dimensional expansion of the microballoons. The expansion has ended when the internal and external pressure are balanced. Since the polymeric shell is conserved, what is achieved is thus a closed-cell foam.
A multitude of unexpanded microballoon types is commercially available, which differ essentially in terms of their size and the starting temperatures that they require for expansion (75 to 220° C.). One example of commercially available unexpanded microballoons is the Expancel® DU products (DU=dry unexpanded) from Akzo Nobel. In the product designation Expancel xxx DU yy (dry unexpanded), “xxx” represents the composition of the microballoon mixture, and “yy” the size of the microballoons in the expanded state.
Unexpanded microballoon products are also available in the form of an aqueous dispersion having a solids/microballoon content of about 40% to 45% by weight, and additionally also in the form of polymer-bound microballoons (masterbatches), for example in ethylene-vinyl acetate with a microballoon concentration of about 65% by weight. Both the microballoon dispersion and the masterbatches, like the DU products, are suitable for production of a foamed self-adhesive composition of the invention.
A foamed self-adhesive composition SK1 and/or SK2 of the invention can also be produced with what are called pre-expanded microballoons. In the case of this group, the expansion already takes place prior to mixing into the polymer matrix. Pre-expanded microballoons are commercially available, for example, under the Dualite® name or with the product designation Expancel xxx DE yy (dry expanded) from Akzo Nobel. “xxx” represents the composition of the microballoon mixture; “yy” represents the size of the microballoons in the expanded state.
In the processing of already expanded microballoon types, it is possible that the microballoons, because of their low density in the polymer matrix into which they are to be incorporated, will have a tendency to float, i.e. to rise “upward” in the polymer matrix during the processing operation. This leads to inhomogeneous distribution of the microballoons in the layer. In the upper region of the layer (z direction), more microballoons are to be found than in the lower region of the layer, such that a density gradient across the layer thickness is established.
In order to largely or very substantially prevent such a density gradient, preference is given in accordance with the invention to incorporating only a few, if any, pre-expanded microballoons into the polymer matrix of layer SK1 or of layer SK2 or preferably of both layers SK1 and SK2. Only after the incorporation into the layer are the microballoons expanded. In this way, a more homogeneous distribution of the microballoons in the polymer matrix is obtained.
Preferably, the microballoons are chosen such that the ratio of the density of the polymer matrix to the density of the (non-pre-expanded or only slightly pre-expanded) microballoons to be incorporated into the polymer matrix is between 1 and 1:6. Expansion then follows immediately after or occurs directly in the course of incorporation. In the case of solvent-containing compositions, the microballoons are preferably expanded only after incorporation, coating, drying (solvent evaporation). Preference is therefore given in accordance with the invention to using DU products.
According to the invention, the mean diameter of the voids formed by the microballoons in the foamed self-adhesive composition layer SK1 is 45 to 110 μm, and a self-adhesive composition layer SK2 foamed with microballoons preferably also has voids having a mean diameter in the range from 45 to 110 μm.
Preferably, the mean diameter of the voids formed by the microballoons in the foamed self-adhesive composition layer SK1 and/or SK2 is 60 to 100 μm, more preferably 70 to 90 μm, for example 80 μm. Within these ranges, particularly good thermal shear strengths can be achieved. Pressure-sensitive adhesive strips comprising self-adhesive composition layers of this kind are accordingly characterized by excellent thermal shear strengths.
Since it is the diameters of the voids formed by the microballoons in the foamed self-adhesive composition layers that are being measured here, the diameters are those diameters of the voids formed by the expanded microballoons. The mean diameter here is the arithmetic mean of the diameters of the voids formed by the microballoons in the respective self-adhesive composition layer SK1 or SK2.
The mean diameter of the voids formed by the microballoons in a self-adhesive composition layer is determined using cryofracture edges of the pressure-sensitive adhesive strip in a scanning electron microscope (SEM) with 500-fold magnification. The diameter of the microballoons in the self-adhesive composition layer to be examined that are visible in scanning electron micrographs of 5 different cryofracture edges of the pressure-sensitive adhesive strip is determined in each case by graphical means, and the arithmetic mean of all the diameters ascertained constitutes the mean diameter of the voids formed by the microballoons in the self-adhesive composition layer in the context of the present application. The diameters of the microballoons visible in the micrographs are determined by graphical means in such a way that the maximum extent in any (two-dimensional) direction is inferred from the scanning electron micrographs for each individual microballoon in the self-adhesive composition layer to be examined and regarded as the diameter thereof.
If foaming is effected by means of microballoons, the microballoons can then be supplied to the formulation as a batch, paste or unblended or blended powder. In addition, they may be suspended in solvents.
The proportion of the microballoons in the self-adhesive composition layer SK1 and/or the self-adhesive composition layer SK2, if the latter has been foamed with microballoons, in a preferred embodiment of the invention, is up to 12% by weight, preferably between 0.25% by weight and 5% by weight, more preferably between 0.5% and 4% by weight, even more preferably between 1% by weight and 3.5% by weight, and especially 2.0% to 3.0% by weight, based in each case on the overall composition of the self-adhesive composition layer. Within these ranges, it is possible to provide self-adhesive composition layers which, as well as particularly good shock resistances, especially have excellent thermal shear strengths. Pressure-sensitive adhesive strips comprising self-adhesive composition layers of this kind are thus characterized not only by particularly good shock resistances but especially by excellent thermal shear strengths.
A self-adhesive composition SK1 or SK2 of the invention, comprising expandable hollow microbeads, may additionally also contain non-expandable hollow microbeads. What is crucial is merely that virtually all gas-containing caverns are closed by a permanently impervious membrane, no matter whether this membrane consists of an elastic and thermoplastically extensible polymer mixture or, for instance, of elastic and—within the spectrum of the temperatures possible in plastics processing—non-thermoplastic glass.
Also suitable for the self-adhesive composition of the invention—selected independently of other additives—are solid polymer beads, hollow glass beads, solid glass beads, hollow ceramic beads, solid ceramic beads and/or solid carbon beads (“carbon microballoons”).
The absolute density of a foamed self-adhesive composition layer SK1 and/or SK2 of the invention is preferably 400 to 990 kg/m3, more preferably 450 to 900 kg/m3, more preferably 500 to 800 kg/m3 and especially 500 to 750 kg/m3, for example 600 to 700 kg/m3.
Within these ranges, it is possible to provide self-adhesive composition layers which, as well as very good shock resistances, especially possess excellent thermal shear strengths. The same applies to the pressure-sensitive adhesive strips of the invention, comprising self-adhesive composition layers having such absolute densities.
The relative density describes the ratio of the density of the foamed self-adhesive composition of the invention to the density of the unfoamed self-adhesive composition of the invention having an identical formulation. The relative density of a self-adhesive composition of the invention is preferably 0.35 to 0.99, more preferably 0.45 to 0.97, especially 0.50 to 0.90.
Film Carrier
The film carrier F optionally present in a pressure-sensitive adhesive strip of the invention may be a non-extensible film carrier or an extensible film carrier.
According to the invention, a “non-extensible film carrier” means a film carrier having, preferably both in longitudinal direction and in transverse direction, an elongation at break of less than 300%. The non-extensible film carrier preferably also has, preferably independently both in longitudinal direction and in transverse direction, an elongation at break of less than 200%, more preferably less than 150%, even more preferably of less than 100%, and especially of less than 70%, for example of less than 50%. The values reported are based in each case on the test method R1 specified later on.
According to the invention, an “extensible film carrier” means a film carrier having, preferably both in longitudinal direction and in transverse direction, an elongation at break of at least 300%. The extensible film carrier also has, preferably independently both in longitudinal direction and in transverse direction, an elongation at break of at least 500%, for example of at least 800%. The values reported are based in each case on the test method R1 specified later on.
The thickness of the film carrier layer, in a preferred embodiment, is between 5 and 125 μm, preferably between 10 and 60 μm, even more preferably between 10 and 50 μm and especially preferably between 10 and 40 μm.
For production of the film carrier, film-forming or extrudable polymers are used, which may additionally be mono- or biaxially oriented.
The film carriers may have a single layer or multiple layers, preferably a single layer. In addition, the film carriers may have outer layers, for example barrier layers, which prevent penetration of components from the adhesive composition into the film or vice versa. These outer layers may also have barrier properties in order thus to prevent through-diffusion of water vapor and/or oxygen.
The reverse side of the film carrier may have been subjected to anti-adhesive physical treatment or coating.
For production of a film carrier, it may be appropriate to add additives and further components that improve the film-forming properties, reduce the tendency to formation of crystalline segments and/or selectively improve or else, if appropriate, worsen the mechanical properties.
The use of a non-extensible film carrier in the pressure-sensitive adhesive strip of the invention facilitates the processibility of the resulting pressure-sensitive adhesive strip; more particularly, the die-cutting processes can be facilitated. In addition, the use of a non-extensible film carrier, for example composed of polyethylene terephthalate (PET), in the pressure-sensitive adhesive strip of the invention can lead to improved shock resistance compared to the use of an extensible film carrier. The shock resistance of the pressure-sensitive adhesive strip of the invention cannot only be affected by the foamed self-adhesive composition(s), but surprisingly also by the nature of the film carrier used and the thickness thereof.
Materials used for the film of the non-extensible film carrier F are preferably polyesters, especially polyethylene terephthalate (PET), polyamide (PA), polyimide (PI) or mono- or biaxially stretched polypropylene (PP). It is likewise possible also to use multilayer laminates or co-extrudates, especially composed of the aforementioned materials. Preferably, the non-extensible film carrier has a single layer.
More preferably, the non-extensible film carrier consists of polyethylene terephthalate and has a thickness between 10 and 50 μm.
In an advantageous procedure, one or both surfaces of the non-extensible film carrier layer F have been physically and/or chemically pretreated. Such a pretreatment can be effected, for example, by etching and/or corona treatment and/or plasma pretreatment and/or primer treatment, preferably by etching. If both surfaces of the film layer have been pretreated, the pretreatment of each surface may have been different or, more particularly, both surfaces may have been given the same pretreatment.
In order to achieve very good results for the roughening, it is advisable to use, as reagent for etching of the film, trichloroacetic acid (Cl3C—COOH) or trichloroacetic acid in combination with inert pulverulent compounds, preferably silicon compounds, more preferably [SiO2]x. The point of the inert compounds is to be incorporated into the surface of the film, especially the PET film, in order in this way to enhance the roughness and surface energy.
Corona treatment is a chemical/thermal process for enhancing the surface tension/surface energy of polymeric substrates. Electrons are greatly accelerated in a high-voltage discharge between two electrodes, which leads to ionization of the air. If a plastics substrate is introduced into the path of these accelerated electrons, the accelerated electrons thus produced hit the substrate surface with 2-3 times the energy that would be needed to break the molecular bonds at the surface of most substrates. This leads to formation of gaseous reaction products and of highly reactive free radicals. These free radicals can react rapidly in the presence of oxygen and the reaction products and form various chemical functional groups at the substrate surface. Functional groups that result from these oxidation reactions make the greatest contribution to increasing the surface energy. Corona treatment can be effected with two-electrode systems, or else with one-electrode systems. During the corona treatment, (as well as the usual air) it is possible to use different process gases such as nitrogen that form a protective gas atmosphere or promote the corona pretreatment.
The plasma treatment—especially low-pressure plasma treatment—is a known process for surface pretreatment of adhesive compositions. The plasma leads to activation of the surface in the sense of a higher reactivity. This results in chemical changes to the surface, as a result of which, for example, the characteristics of the adhesive composition with respect to polar and nonpolar surfaces can be influenced. This pretreatment essentially comprises surface phenomena.
Primers refer generally to coatings or basecoats which especially have an adhesion-promoting and/or passivating and/or corrosion-inhibiting effect. In the context of the present invention, it is the adhesion-promoting effect that is especially important.
Adhesion-promoting primers, often also called adhesion promoters, are in many cases known in the form of commercial products or from the technical literature.
A suitable non-extensible film carrier is available under the Hostaphan® RNK trade name. This film is highly transparent and biaxially oriented and consists of three co-extruded layers.
The tensile strength of a non-extensible film carrier, preferably in accordance with the invention, is greater than 100 N/mm2, more preferably greater than 150 N/mm2, even more preferably greater than 180 N/mm2 and especially greater than 200 N/mm2, for example greater than 250 N/mm2, in longitudinal direction, and preferably greater than 100 N/mm2, more preferably greater than 150 N/mm2, even more preferably greater than 180 N/mm2, and especially greater than 200 N/mm2, for example greater than 250 N/mm2, in transverse direction (values reported in each case in relation to the test method R1 specified further down). The film carrier is crucial in determining the tensile strength of the pressure-sensitive adhesive strip. Preferably, the pressure-sensitive adhesive strip has the same values for tensile strength as the film carrier used.
The modulus of elasticity of the non-extensible film carrier is preferably more than 0.5 GPa, preferably more than 1 GPa and especially more than 2.5 GPa, preferably both in longitudinal direction and in transverse direction.
If an extensible film carrier is used in the pressure-sensitive adhesive strip of the invention, the extensibility of the film carrier is preferably sufficient to ensure residue-free and nondestructive detachment of the pressure-sensitive adhesive strip through extensive stretching essentially in the plane of the bond. The intermediate carriers used may, for example, be very extensible films. Examples of advantageously usable extensible intermediate carriers are embodiments from WO 2011/124782 A1, DE 10 2012 223 670 A1, WO 2009/114683 A1, WO 2010/077541 A1, WO 2010/078396 A1.
In a preferred embodiment of an extensible film carrier, polyolefins are used. Preferred polyolefins are prepared from ethylene, propylene, butylene and/or hexylene, where it is possible in each case to polymerize the pure monomers or to copolymerize mixtures of the monomers mentioned. It is possible via the polymerization process and by the choice of monomers to control the physical and mechanical properties of the polymer film, for example the softening temperature and/or the elongation at break.
In addition, it is advantageously possible to use polyurethanes as starting materials for extensible film carriers. Polyurethanes are chemically and/or physically crosslinked polycondensates that are typically formed from polyols and isocyanates. According to the nature and use ratio of the individual components, extensible materials that can be used advantageously in the context of this invention are obtainable. Raw materials available to the formulator for this purpose are specified, for example, in EP 0 894 841 B1 and EP 1 308 492 B1. The person skilled in the art will be aware of further raw materials from which extensible film carriers of the invention can be formed. It is also advantageous to use rubber-based materials in extensible film carriers in order to achieve extensibility. As rubber or synthetic rubber or blends produced therefrom as starting material for extensible film carriers, the natural rubber may in principle be chosen from any available qualities, for example crepe, RSS, ADS, TSR or CV types, according to the required level of purity and viscosity, and the synthetic rubber(s) may be chosen from the group of the randomly copolymerized styrene-butadiene rubbers (SBR), the butadiene rubbers (BR), the synthetic polyisoprenes (IR), the butyl rubbers (IIR), the halogenated butyl rubbers (XIIR), the acrylate rubbers (ACM), the ethylene-vinyl acetate copolymers (EVA) and the polyurethanes and/or blends thereof.
Materials usable particularly advantageously for extensible film carriers are block copolymers. Individual polymer blocks here are covalently bonded to one another. The block bonding may be in a linear form, or else in a star-shaped or graft copolymer variant. One example of an advantageously usable block copolymer is a linear triblock copolymer, the two terminal blocks of which have a softening temperature of at least 40° C., preferably at least 70° C., and the middle block of which has a softening temperature of at most 0° C., preferably at most −30° C. Higher block copolymers, for instance tetrablock copolymers, are likewise usable. It is important that at least two polymer blocks of the same or different kinds that are present in the block copolymer each have a softening temperature of at least 40° C., preferably at least 70° C., and are separated from one another in the polymer chain by at least one polymer block having a softening temperature of not more than 0° C., preferably not more than −30° C. Examples of polymer blocks are polyethers, for example polyethylene glycol, polypropylene glycol or polytetrahydrofuran, polydienes, for example polybutadiene or polyisoprene, hydrogenated polydienes, for example polyethylene-butylene or polyethylene-propylene, polyesters, for example polyethylene terephthalate, polybutanediol adipate or polyhexanediol adipate, polycarbonate, polycaprolactone, polymer blocks of vinylaromatic monomers, for example polystyrene or poly-[α]-methylstyrene, polyalkyl vinyl ethers, polyvinyl acetate, polymer blocks of [α],[β]-unsaturated esters such as, in particular, acrylates or methacrylates. Corresponding softening temperatures are known to those skilled in the art. Alternatively, the person skilled in the art will look them up, for example, in the Polymer Handbook [J. Brandrup, E. H. Immergut, E. A. Grulke (eds.), Polymer Handbook, 4th ed. 1999, Wiley, New York]. Polymer blocks may be formed from copolymers.
Further conceivable extensible film carriers are foams in sheet form (for example composed of polyethylene and polyurethane), but these are not preferred in the context of the present invention.
For better anchoring of the self-adhesive compositions on the extensible film carriers, the film carriers may be pretreated by the known measures such as corona, plasma or flame. The utilization of a primer is also possible. Ideally, however, it is possible to dispense with pretreatment.
Particularly advantageously, the extensible film carrier is a single-layer film carrier, preferably composed of polyurethane, where the carrier has an elongation at break of at least 300%, preferably at least 500%, especially at least 800%, and, if appropriate, a resilience of more than 50%. Preferably, the film carrier has the elongation at break values specified and/or the resilience specified both in longitudinal direction and in transverse direction.
Preferably, the tensile strength of the extensible carrier material is adjusted such that the pressure-sensitive adhesive strip can be detached again in a nondestructive manner from an adhesive bond by virtue of extensive stretching.
Production and Configuration of the Pressure-Sensitive Adhesive Strip
The production and processing of the self-adhesive compositions SK1 and SK2 usable in accordance with the invention can be effected either from solution or from the melt. The application of the self-adhesive compositions SK1 and SK2 usable in accordance with the invention to film carrier layers can be effected by direct coating or by lamination, especially hot lamination.
Advantageously, the outer, exposed faces of the outer adhesive composition layers of the pressure-sensitive adhesive strips of the invention can be provided with materials having an anti-adhesive coating on both sides, such as a release paper or a release film, also called liner, specifically as a temporary carrier. A liner (release paper, release film) is not part of a pressure-sensitive adhesive strip, but merely an auxiliary for production and/or storage thereof and/or for further processing by die-cutting. Furthermore, a liner, by contrast with an adhesive tape carrier, is not firmly bonded to an adhesive layer.
Typical supply forms of the pressure-sensitive adhesive strips of the invention are adhesive tape rolls and adhesive strips as obtained, for example, in the form of die-cut parts.
Preferably, all layers are essentially in the shape of a cuboid. Further preferably, all layers are bonded to one another over the full area. This bond can be optimized by the pretreatment of the film surfaces.
The general expression “adhesive strip” (pressure-sensitive adhesive strip), or else synonymously “adhesive tape” (pressure-sensitive adhesive tape), in the context of this invention, encompasses all sheetlike structures such as films or film sections extending in two dimensions, tapes having extended length and limited width, tape sections and the like, and lastly also die-cut parts or labels.
The pressure-sensitive adhesive strip thus has a longitudinal extent (x direction) and a lateral extent (y direction). The pressure-sensitive adhesive strip also has a thickness (z direction) that runs perpendicular to the two extents, the lateral extent and longitudinal extent being several times greater than the thickness. The thickness is very substantially the same, preferably exactly the same, over the entire areal extent of the pressure-sensitive adhesive strip determined by its length and width.
The pressure-sensitive adhesive strip of the invention is especially in sheet form. A sheet is understood to mean an object, the length of which (extent in the x direction) is several times greater than its width (extent in the y direction), and the width over the entire length remains roughly and preferably exactly the same.
The use of a non-extensible film carrier in the pressure-sensitive adhesive strip of the invention leads to advantageous ease of use of the pressure-sensitive adhesive strip, especially including filigree die-cut parts. The non-extensible film carrier usable in the pressure-sensitive adhesive strip of the invention leads to marked stiffness in the die-cut parts, such that the die-cutting process and the positioning of the die-cut parts are simplified. A die-cut part formed from a pressure-sensitive adhesive strip of the invention and having a non-extensible film carrier may especially have an outer die-cut edge and an inner opening, such that it takes the form of a frame. It is possible here for individual elements to have a width of less than 5 mm or of less than 2.5 mm or even of less than 1 mm.
The use of an extensible film carrier in the pressure-sensitive adhesive strip of the invention allows other advantageous product configurations. Pressure-sensitive adhesive strips that can be detached in a nondestructive manner from a bond by virtue of extensive stretching become obtainable.
The pressure-sensitive adhesive strip, especially in sheet form, can be produced in the form of a roll, i.e. in the form of a rolled-up Archimedean spiral.
Properties of the Pressure-Sensitive Adhesive Strips of the Invention
The pressure-sensitive adhesive strips of the invention are notable for an excellent application profile, i.e. for very good application and adhesive properties.
More particularly, the object of the invention is achieved. Thus, it has been found that the pressure-sensitive adhesive strips of the invention, as well as high bond strength and high shock resistance, also possess improved thermal shear strength.
For instance, in the static shear test at elevated temperatures, they exhibit high shear strengths and also have high thermal stabilities, as apparent in the SAFT (“Shear Adhesion Failure Temperature”) test.
The high shock resistance of the pressure-sensitive adhesive strips of the invention is manifested in the form of high impact resistance in the z direction, but also in the x,y plane (i.e. transverse impact resistance). They also have very good values in the ball drop test (impact resistance). Moreover, they are notable for high push-out resistance (in the z plane).
In addition, the pressure-sensitive adhesive compositions of the invention have, for example, favorable indentation/hardness characteristics and very good compressibility.
Moreover, the pressure-sensitive adhesive compositions of the invention have good bond strength on rough substrates, good damping and/or sealing properties, and good adaptability to uneven substrates.
The thermal shear strength of the pressure-sensitive adhesive compositions of the invention will be more particularly elucidated in the examples.
With reference to the figures described hereinafter, particularly advantageous embodiments of the invention will be elucidated in detail, without any intention to unnecessarily restrict the invention thereby.
The strip comprises a non-extensible film carrier 1 (layer F) in the form of a PET film that has been etched on both sides. On the top side and on the bottom side of the PET film 1 there are two outer self-adhesive composition layers 2, 3 (layer SK1 and layer SK2). The self-adhesive composition layers 2, 3 (layers SK1 and SK2) are covered in turn by a liner 4, 5 on each side in the illustrative embodiment shown.
The strip comprises a self-adhesive composition layer 2 (layer SK1). The self-adhesive composition layer 2 (layer SK1) is covered by a liner 4, 5 on each side in the illustrative embodiment shown.
In addition, the invention encompasses a process for producing a self-adhesive composition layer of the invention (see
In addition, the invention encompasses a process for producing a self-adhesive composition layer of the invention (likewise see
The invention likewise encompasses a process for producing a self-adhesive composition layer of the invention (see
The invention likewise relates to a process for producing a self-adhesive composition layer of the invention (see
The processes for producing a self-adhesive composition layer of the invention that are illustrated in
If, in the processes from
If, in the three-layer system composed of film carrier layer F, self-adhesive composition layer and liner, a further self-adhesive composition layer is then applied to the opposite surface of the film carrier layer F from the self-adhesive composition layer, the result is a double-sided adhesive tape of the invention with a film carrier. Optionally, it is then possible to cover the opposite surface of the self-adhesive composition layer from the film carrier layer F with release material in sheet form, i.e. a liner.
In a preferred embodiment of the invention, the adhesive composition is shaped in a roll applicator and applied to the carrier material.
There is generally no need to degas compositions foamed with microballoons prior to coating in order to obtain a homogeneous, continuous coating. The expanded microballoons displace the air incorporated into the adhesive composition during compounding. In the case of high throughputs, it is nevertheless advisable to degas the compositions prior to coating in order to obtain a homogeneous feed of composition in the roll gap. The degassing is ideally effected directly upstream of the roll applicator at mixing temperature and with a pressure differential from ambient pressure of at least 200 mbar.
In addition, it is advantageous when
With the processes of the invention, solvent-free processing of all previously known components of adhesive compositions and those described in the literature, especially self-adhesive components, is possible.
The above-described processes within the concept of the invention in variants of particularly excellent configuration are illustrated hereinafter, without any intention to impose unnecessary restriction through the choice of the figures depicted.
The figures show:
In a continuous mixing unit, for example a planetary roll extruder (PRE), the pressure-sensitive adhesive composition is produced.
For this purpose, the reactants E that are to form the adhesive composition are introduced into the planetary roll extruder PRE 1. At the same time, the unexpanded microballoons MB are incorporated homogeneously into the self-adhesive composition during the compounding process.
The temperatures required for homogeneous production of the self-adhesive composition and for expansion of the microballoons are adjusted with respect to one another such that the microballoons at least begin to expand during mixing and preferably foam completely in the self-adhesive composition M on exit from the PRE 1 as a result of the pressure drop on exit from the die, and in so doing break through the surface of the composition.
With a roll applicator 3 as shaping unit, this foam-like adhesive composition M is calendered and coated onto a carrier material in sheet form, for example release paper TP; in some cases, further foaming can still take place in the roll gap. The roll applicator 3 consists of a doctor roll 31 and a coating roll 32. The release paper TP is guided onto the latter via a pick-up roll 33, such that the release paper TP takes up the adhesive composition K from the coating roll 32.
At the same time, the expanded microballoons MB are forced back into the polymer matrix of the adhesive composition K, and hence a smooth surface is generated. The drop in bonding force resulting from the microballoons can thus be distinctly reduced.
The planetary roll extruder PRE 1 has two successive mixing zones 11, 12 in which a central spindle rotates. In addition, there are six planetary spindles per heating zone. Further reactants are added to the injection ring 13, for example plasticizer or liquid resin.
An example of a suitable apparatus is the planetary roll extruder from Entex in Bochum.
Subsequently, the microballoons are incorporated homogeneously into the self-adhesive composition in a second mixing unit, for example a twin-screw extruder, heated above the expansion temperature and foamed.
For this purpose, the adhesive composition K formed from the reactants E is introduced here into the twin-screw extruder TSE 2; at the same time, the microballoons MB are introduced. The twin-screw extruder TSE has a total of four heating zones over its run length 21.
An example of a suitable apparatus is a twin-screw extruder from Kiener.
During the expansion caused by the pressure drop at the nozzle exit of TSE 2, the foamed microballoons MB break through the surface of the composition.
With a roll applicator 3, this foam-like adhesive composition M is calendered and coated onto a carrier material in sheet form, for example release paper TP; in some cases, further foaming can still take place in the roll gap. The roll applicator 3 consists of a doctor roll 31 and a coating roll 32. The release paper TP is guided onto the latter via a pick-up roll 33, such that the release paper TP takes up the adhesive composition K from the coating roll 32.
At the same time, the expanded microballoons MB are forced back into the polymer matrix of the adhesive composition K, and hence a smooth surface is generated. The drop in bonding force resulting from the microballoons can thus be distinctly reduced.
In a continuous mixing unit, for example a planetary roll extruder (PRE), the pressure-sensitive adhesive composition is produced.
Here, the reactants E that are to form the adhesive composition are introduced into the planetary roll extruder PRE 1. The planetary roll extruder PRE 1 has two successive mixing zones 11, 12 in which a central spindle rotates. In addition, there are 6 planetary spindles per heating zone.
Further reactants are added to the injection ring 13, for example plasticizer or liquid resin.
An example of a suitable apparatus is the planetary roll extruder from Entex in Bochum.
Subsequently, the microballoons are incorporated homogeneously under elevated pressure into the self-adhesive composition in a second mixing unit, for example a single-screw extruder, heated above the expansion temperature and foamed on exit.
For this purpose, the adhesive composition K formed from the reactants E is introduced here into the single-screw extruder TSE 2; at the same time, the microballoons MB are introduced. The single-screw extruder TSE has a total of four heating zones over its run length 21.
An example of a suitable apparatus is a single-screw extruder from Kiener.
During the expansion caused by the pressure drop at the nozzle exit of TSE 2, the microballoons MB break through the surface of the composition.
With a roll applicator 3, this foam-like adhesive composition M is calendered and coated onto a carrier material in sheet form, for example release paper TP; in some cases, further foaming can still take place in the roll gap. The roll applicator 3 consists of a doctor roll 31 and a coating roll 32. The release paper TP is guided onto the latter via a pick-up roll 33, such that the release paper TP takes up the adhesive composition K from the coating roll 32.
At the same time, the expanded microballoons MB are forced back into the polymer matrix of the adhesive composition K, and hence a smooth surface is generated. The drop in bonding force resulting from the microballoons can thus be distinctly reduced.
With falling gap pressure in the roll gap, there is a decrease in the bonding areas of the coated foamed self-adhesive compositions, since the microballoons are then forced back to a lesser degree, as can be inferred from
It has been found to be useful to adjust the temperature of the rolls to the expansion temperature of the microballoons. Ideally, the roll temperature of the first rolls is above the expansion temperature of the microballoons in order to enable further foaming of the microballoons without destroying them. The last roll should have a temperature equal to or below the expansion temperature in order that the microballoon shell can solidify and the smooth surface of the invention forms.
Many units for continuous production and processing of solvent-free polymer systems are known. Usually, screw machines such as single-screw and twin-screw extruders of different processing length and with different equipment are used. Alternatively, continuous kneaders of a wide variety of different designs, for example including combinations of kneaders and screw machines, or else planetary roller extruders, are used for this task.
Planetary roll extruders have been known for some time and were first used in the processing of thermoplastics, for example PVC, where they were used mainly for charging of the downstream units, for example calenders or roll systems. Their advantage of high surface renewal for material and heat exchange, with which the energy introduced via friction can be removed rapidly and effectively, and of short residence time and narrow residence time spectrum, has allowed their field of use to be broadened recently, inter alia, to compounding processes that require a mode of operation with exceptional temperature control.
Planetary roll extruders exist in various designs and sizes according to the manufacturer. According to the desired throughput, the diameters of the roll cylinders are typically between 70 mm and 400 mm.
Planetary roll extruders generally have a filling section and a compounding section.
The filling section consists of a conveying screw, into which all solid components are metered continuously. The conveying screw then transfers the material to the compounding section. The region of the filling section with the screw is preferably cooled in order to avoid caking of material on the screw. But there are also embodiments without a screw section, in which the material is applied directly between central and planetary spindles. However, this is of no significance for the efficacy of the process of the invention.
The compounding section consists of a driven central spindle and several planetary spindles that rotate around the central spindle within one or more roll cylinders having internal helical gearing. The speed of the central spindle and hence the peripheral velocity of the planetary spindles can be varied and is thus an important parameter for control of the compounding process.
The materials are circulated between the central and planetary spindles, i.e. between planetary spindles and the helical gearing of the roll section, such that the materials can be dispersed under the influence of shear energy and external temperature control to give a homogeneous compound.
The number of planetary spindles that rotate in each roll cylinder can be varied and hence adapted to the demands of the process. The number of spindles affects the free volume within the planetary roll extruder and the residence time of the material in the process, and additionally determines the size of the area for heat and material exchange. The number of planetary spindles affects the compounding outcome via the shear energy introduced. Given a constant roll cylinder diameter, it is possible with a greater number of spindles to achieve better homogenization and dispersion performance, or a greater product throughput.
The maximum number of planetary spindles that can be installed between the central spindle and roll cylinder is dependent on the diameter of the roll cylinder and on the diameter of the planetary spindles used. In the case of use of greater roll diameters as necessary for achievement of throughputs on the production scale, or smaller diameters for the planetary spindles, the roll cylinders can be equipped with a greater number of planetary spindles. Typically, up to seven planetary spindles are used in the case of a roll diameter of D=70 mm, while ten planetary spindles, for example, can be used in the case of a roll diameter of D=200 mm, and 24, for example, in the case of a roll diameter of D=400 mm.
It is proposed in accordance with the invention that the coating of the foamed adhesive compositions be conducted in a solvent-free manner with a multiroll applicator system. These may be applicator systems consisting of at least two rolls with at least one roll gap up to five rolls with three roll gaps.
Also conceivable are coating systems such as calenders (I, F, L calenders), such that the foamed adhesive composition is shaped to the desired thickness as it passes through one or more roll gaps.
It has been found to be particularly advantageous to choose the temperature regime for the individual rolls such that controlled further foaming can take place if appropriate, in such a way that transferring rolls can have a temperature above or equal to the foaming temperature of the microballoon type chosen, whereas receiving rolls should have a temperature below or equal to the foaming temperature, in order to prevent uncontrolled foaming, and where all rolls can be set individually to temperatures of 30 to 220° C.
In order to improve the transfer characteristics of the shaped composition layer from one roll to another, it is also possible to use anti-adhesively finished rolls or patterned rolls. In order to produce a sufficiently precisely shaped adhesive film, the peripheral speeds of the rolls may have differences.
The preferred 4-roll applicator is formed by a metering roll, a doctor roll, which determines the thickness of the layer on the carrier material and is arranged parallel to the metering roll, and a transfer roll disposed beneath the metering roll. At the lay-on roll, which together with the transfer roll forms a second roll gap, the composition and the material in sheet form are brought together.
Depending on the nature of the carrier material in sheet form which is to be coated, coating can be effected in a co-rotational or counter-rotational process.
The shaping system may also be formed by a gap formed between a roll and a fixed doctor. The fixed doctor may be a knife-type doctor or else a stationary (half-)roll.
In an alternative process for producing a self-adhesive composition layer of the invention, all constituents of the adhesive composition are dissolved in a solvent mixture (benzine/toluene/acetone). The microballoons are converted to a slurry in benzine and stirred into the dissolved adhesive composition. For this purpose, it is possible in principle to use the known compounding and stirring units, and it should be ensured that the microballoons do not yet expand in the course of mixing. As soon as the microballoons are distributed homogeneously in the solution, the adhesive composition can be coated, for which it is again possible to use prior art coating systems. For example, the coating can be accomplished by means of a doctor blade onto a conventional PET liner. In the next step, the coating composition applied is dried at 100° C. for 15 min. In none of the aforementioned steps is there any expansion of the microballoons. After the drying, the adhesive layer is covered with a second ply of PET liner or with a film carrier and foamed in the oven within an appropriate temperature/time window, for instance at 150° C. for 5 min or at 170° C. for 1 min, specifically covered between the two liners or between the liner and the film carrier, in order to produce a particularly smooth surface.
If the dried adhesive layer is foamed between the two liners, the result is a pressure-sensitive adhesive strip of the invention that consists of the self-adhesive layer. If the self-adhesive layer is foamed between the liner and the film carrier, the result is a pressure-sensitive adhesive strip of the invention in the form of a single-sided adhesive tape.
Alternatively, prior to the foaming of the dried self-adhesive layer localized between the liner and the film carrier, it is possible to laminate a second, likewise dried microballoon-containing self-adhesive layer that has in turn been applied to a liner onto the opposite surface of the film carrier from the dried self-adhesive layer, such that it is possible to provide an unfoamed three-layer composite composed of an inner film carrier and two self-adhesive layers that are in direct contact with the film carrier and have in turn been provided with liners on their outer faces. Such a three-layer composite can also be provided by directly coating the film carrier F simultaneously or successively with the unfoamed self-adhesive compositions containing microballoons, after which the self-adhesive composition layers are dried at 100° C. for 15 min and then covered with liners. After the drying, the adhesive layers are foamed in the oven within an appropriate temperature/time window, for instance at 150° C. for 5 min or at 170° C. for 1 min, specifically covered between the two liners, in order to produce a particularly smooth surface. The result is a pressure-sensitive adhesive strip of the invention in the form of a double-sided adhesive tape with carrier.
The surface of the self-adhesive layer thus produced has a roughness Ra of less than 15 μm, more preferably less than 10 μm, most preferably less than 3 μm.
The surface roughness Ra is a unit for the industrial standard for the quality of the final surface processing and constitutes the average height of the roughness, especially the average absolute distance from the center line of the roughness profile within the range of evaluation. In other words, Ra is the arithmetic mean roughness, i.e. the arithmetic mean of all profile values in the roughness profile. Ra is measured by means of laser triangulation.
The expansion temperature chosen is especially higher than the drying temperature in order to avoid the expansion of the microballoons in the course of drying.
The invention is elucidated in detail hereinafter by a few examples. With reference to the examples described hereinafter, particularly advantageous embodiments of the invention will be elucidated in detail, without any intention to unnecessarily restrict the invention thereby.
There follows a description of the production of pressure-sensitive adhesive strips of the invention, each of which consists of a single self-adhesive composition layer SK1 based on a vinylaromatic block copolymer composition foamed with Expancel 920 DU80 microballoons. The microballoon content of Expancel 920 DU80 was varied.
For this purpose, first of all, a 40% by weight adhesive solution in benzine/toluene/acetone was produced from 50.0% by weight of Kraton D1102AS, 45.0% by weight of Dercolyte A115, 4.5% by weight of Wingtack 10 and 0.5% by weight of Irganox 1010 aging stabilizer (also called adhesive solution 1). The proportions by weight of the dissolved constituents are each based on the dry weight of the resulting solution. Said constituents of the adhesive composition are characterized as follows:
The solution was subsequently admixed with 2% by weight or 3% by weight of unexpanded Expancel 920 DU80 microballoons, using the microballoons in the form of a slurry in benzine. The proportions by weight of the microballoons are based here in each case on the dry weight of the solution used to which they have been added (i.e. the dry weight of the solution used is fixed at 100%). The mixture obtained was then coated with a coating bar onto a PET liner provided with a silicone release agent in the desired layer thickness, then the solvent was evaporated off at 100° C. for 15 min and so the composition layer was dried.
Thereafter, a second PET liner was laminated in each case onto the free surface of the dried adhesive composition layer produced and the adhesive composition layer was then foamed between the two liners in an oven at 150° C. for 5 min. Through the foaming between two liners, products having particularly smooth surfaces are obtainable (with Ra values less than 15 μm). By die-cutting, pressure-sensitive adhesive strips of the invention with the desired dimensions were obtained (examples 1 and 2). The pressure-sensitive adhesive strips were produced such that they had a thickness of about 150 μm. The thickness is based on the pressure-sensitive adhesive strips without PET liner.
In comparative experiments, the production of the pressure-sensitive adhesive strips was repeated in the same way, except using unexpanded microballoons of the Expancel 920 DU20, Expancel 920 DU40 or Expancel 920 DU120 types in place of unexpanded Expancel 920 DU80 microballoons. The proportions by weight of the microballoons chosen, in the case of use of Expancel 920 DU20 or Expancel 920 DU40, were again 2% by weight and 3% by weight, and in the case of use of Expancel 920 DU120 were 0.9% by weight and 2% by weight, based in each case on the dry weight of the adhesive solution used (comparative examples 1 to 6). The pressure-sensitive adhesive strips were likewise produced such that they had a thickness of about 150 μm. The thickness is based on the pressure-sensitive adhesive strips without PET liner.
There also follows a description of the production of a pressure-sensitive adhesive strip of the invention which consists of a single self-adhesive composition layer SK1 likewise based on a vinylaromatic block copolymer composition foamed with Expancel 920 DU80 microballoons. However, a different adhesive solution was used (also called adhesive solution 2).
For this purpose, first of all, a 40% by weight adhesive solution in benzine/toluene/acetone was produced from 25.0% by weight of Kraton D1101AS, 25.0% by weight of Kraton D1118ES, 45.0% by weight of Dercolyte A115, 4.5% by weight of Wingtack 10 and 0.5% by weight of Irganox 1010 aging stabilizer (called adhesive solution 2). The proportions by weight of the dissolved constituents are each based on the dry weight of the resulting solution. Said constituents of the adhesive composition are characterized as follows:
The solution was subsequently admixed with 2% by weight of unexpanded Expancel 920 DU80 microballoons, using the microballoons in the form of a slurry in benzine. The proportion by weight of the microballoons is based on the dry weight of the solution used to which they have been added (i.e. the dry weight of the solution used is fixed at 100%). The mixture obtained was then coated with a coating bar onto a PET liner provided with a silicone release agent in the desired layer thickness, then the solvent was evaporated off at 100° C. for 15 min and so the composition layer was dried.
Thereafter, a second PET liner was laminated onto the free surface of the dried adhesive composition layer produced and the adhesive composition layer was then foamed between the two liners in an oven at 150° C. for 5 min. Through the foaming between two liners, products having particularly smooth surfaces are obtainable (with Ra values less than 15 μm). By die-cutting, an inventive pressure-sensitive adhesive strip of the desired dimensions was obtained (example 3). The pressure-sensitive adhesive strip was produced such that it has a thickness of about 150 μm. The thickness is based on the pressure-sensitive adhesive strip without PET liner.
In a comparative experiment, the production of the pressure-sensitive adhesive strip was repeated in the same way, except using unexpanded microballoons of the Expancel 920 DU20 type in place of unexpanded Expancel 920 DU80 microballoons. The proportion by weight of the microballoons chosen was again 2% by weight, based on the dry weight of the adhesive solution used (comparative example 7). The pressure-sensitive adhesive strip was likewise produced such that it had a thickness of about 150 μm. The thickness is based on the pressure-sensitive adhesive strip without PET liner.
Table 1 below shows the thermal shear strengths of the inventive pressure-sensitive adhesive strips (examples 1 to 3) and of the noninventive pressure-sensitive adhesive strips (comparative examples 1 to 7).
1MB = microballoons;
2SACL = self-adhesive composition layer;
3SSS = static shear strength;
4SAFT = shear adhesion failure temperature (tesa-SAFT), thermal stability.
Examples 1 to 3 show that, surprisingly, excellent static shear strengths and thermal stabilities can be achieved in pressure-sensitive adhesive strips when the self-adhesive composition layers based on vinylaromatic block copolymer are foamed with unexpanded Expancel 920 DU80 microballoons.
A comparison of the inventive pressure-sensitive adhesive strips with the pressure-sensitive adhesive strips from comparative examples, the self-adhesive composition layers of which based on vinylaromatic block copolymer are foamed with distinctly smaller microballoons or distinctly larger microballoons, shows that voids in the foamed adhesive composition layers obviously lead to distinctly improved thermal shear strengths when these have a mean diameter in the order of magnitude of about 80 μm.
A comparison of examples 1 and 2 shows that similarly good thermal shear strengths can be achieved in the pressure-sensitive adhesive strips of the invention with contents of microballoons of 2% by weight or 3% by weight.
Examples 1 to 3 also show that excellent thermal shear strengths are to be expected over a broad absolute density range from about 500 to 750 kg/m3 of the self-adhesive compositions in the pressure-sensitive adhesive strips of the invention.
A comparison of examples 1 and 3 also shows that the thermal shear strengths in pressure-sensitive adhesive strips of the invention can also be improved further via suitable selection of the vinylaromatic block copolymer composition.
Unless stated otherwise, all measurements were conducted at 23° C. and 50% rel. air humidity.
The mechanical and adhesive data were ascertained as follows:
To measure the resilience, the pressure-sensitive adhesive strips were extended by 100%, kept at this extension for 30 s and then released. After a wait time of 1 min, the length was measured again.
The resilience is then calculated as follows:
R=((L100−Lend)/L0)*100
with R=resilience in %
L100: length of the adhesive strip after extension by 100%
L0: length of the adhesive strip prior to extension
Lend: length of the adhesive strip after relaxation for 1 min.
The resilience corresponds here to the elasticity.
Tensile strength and elongation at break were measured in accordance with DIN 53504 using dumbbell specimens of size S3 at a separation speed of 300 mm per minute. The test conditions were 23° C. and 50% rel. air humidity.
Modulus of elasticity indicates the mechanical resistance that a material offers to elastic deformation. It is determined as the ratio of the strain a required to the elongation ϵ achieved, where ϵ is the quotient of the change in length ΔL and the length L0 in Hooke's regime of deformation of the specimen. The definition of the modulus of elasticity is elucidated, for example, in the Taschenbuch der Physik [Physics Handbook] (H. Stöcker (ed.), Taschenbuch der Physik, 2nd ed., 1994, Verlag Harri Deutsch, Frankfurt, p. 102-110).
To determine the modulus of elasticity of a film, the tensile strain characteristics were ascertained using a type 2 specimen (rectangular test film strip of length 150 mm and width 15 mm) according to DIN EN ISO 527-3/2/300 with a test speed of 300 mm/min, a clamping length of 100 mm and an initial force of 0.3 N/cm, the test strip for ascertainment of the data having been cut to size with sharp blades. A Zwick tensile tester (model Z010) was used. Tensile strain characteristics were measured in machine direction (MD). A 1000 N (Zwick Roell Kap-Z 066080.03.00) or 100 N (Zwick Roell Kap-Z 066110.03.00) load cell was used. Modulus of elasticity was ascertained by graphical means from the measurement curves by determining the slope of the starting region of the curve which is characteristic of the behavior in respect of Hooke's Law and is reported in GPa.
5.0 g of test substance (the tackifying resin sample to be examined) are weighed into a dry test tube, and 5.0 g of xylene (isomer mixture, CAS [1330-20-7], ≥98.5%, Sigma-Aldrich #320579 or comparable) are added. The test substance is dissolved at 130° C. and then cooled down to 80° C. Any xylene that escapes is made up for with fresh xylene, such that 5.0 g of xylene are present again. Subsequently, 5.0 g of diacetone alcohol (4-hydroxy-4-methyl-2-pentanone, CAS [123-42-2], 99%, Aldrich #H41544 or comparable) are added. The test tube is shaken until the test substance has dissolved completely. For this purpose, the solution is heated to 100° C. The test tube containing the resin solution is then introduced into a Novomatics Chemotronic Cool cloud point measuring instrument and heated therein to 110° C. It is cooled down at a cooling rate of 1.0 K/min. The cloud point is detected optically. For this purpose, that temperature at which the turbidity of the solution is 70% is registered. The result is reported in ° C. The lower the DACP value, the higher the polarity of the test substance.
The tackifying resin softening temperature is conducted by the relevant methodology, known as ring & ball and standardized in ASTM E28.
The mean diameter of the voids formed by the microballoons in a self-adhesive composition layer is determined using cryofracture edges of the pressure-sensitive adhesive strip in a scanning electron microscope (SEM) with 500-fold magnification. The diameter of the microballoons in the self-adhesive composition layer to be examined that are visible in scanning electron micrographs of 5 different cryofracture edges of the pressure-sensitive adhesive strip is determined in each case by graphical means, and the arithmetic mean of all the diameters ascertained in the 5 scanning electron micrographs constitutes the mean diameter of the voids formed by the microballoons in the self-adhesive composition layer in the context of the present application. The diameters of the microballoons visible in the micrographs are determined by graphical means in such a way that the maximum extent thereof in any (two-dimensional) direction is inferred from the scanning electron micrographs for each individual microballoon in the self-adhesive composition layer to be examined and regarded as the diameter thereof.
The density of the unfoamed and foamed adhesive composition layers is ascertained by forming the quotient of mass applied and thickness of the adhesive composition layer applied to a carrier or liner.
The mass applied can be determined by determining the mass of a section, defined in terms of its length and width, of such an adhesive composition layer applied to a carrier or liner, minus the (known or separately determinable) mass of a section of the same dimensions of the carrier or liner used.
The thickness of an adhesive composition layer can be determined by determining the thickness of a section, defined in terms of its length and width, of such an adhesive composition layer applied to a carrier or liner, minus the (known or separately determinable) thickness of a section of the same dimensions of the carrier or liner used. The thickness of the adhesive composition layer can be determined by means of commercial thickness measuring instruments (caliper test instruments) with accuracies of less than a 1 μm deviation. If variations in thickness are found, the mean of measurements at at least three representative sites is reported, i.e. more particularly not measured at creases, folds, specks and the like.
Like the thickness of an adhesive composition layer as above, it is also possible to ascertain the thickness of a pressure-sensitive adhesive strip or a film carrier layer by means of commercial thickness measuring instruments (caliper test instruments) with accuracies of less than a 1 μm deviation. If variations in thickness are found, the mean of measurements at at least three representative sites is reported, i.e. more particularly not measured at creases, folds, specks and the like.
Glass transition points—referred to synonymously as glass transition temperatures—are reported as the result of measurements by means of differential scanning calorimetry (DSC) according to DIN 53 765, especially sections 7.1 and 8.1, but with uniform heating and cooling rates of 10 K/min in all heating and cooling steps (cf. DIN 53 765; section 7.1; note 1). The sample weight is 20 mg.
This test serves for rapid testing of the shear strength of pressure-sensitive adhesive strips under thermal stress. For this purpose, the pressure-sensitive adhesive strip to be examined is stuck to a temperature-controllable steel plate and weighted down with a weight (50 g), and the shear distance is recorded.
Test Sample Preparation:
The pressure-sensitive adhesive strip to be examined, if it is a double-sidedly adhesive pressure-sensitive adhesive strip, is stuck by one of the adhesive composition sides to an aluminum foil of thickness 50 μm. The pressure-sensitive adhesive strip that has been prepared in this way if appropriate is cut to a size of 10 mm*50 mm.
The pressure-sensitive adhesive strip sample that has been cut to size is stuck by the other adhesive composition side to a polished, acetone-cleaned steel test plate (material 1.4301, DIN EN 10088-2, surface 2R, surface roughness Ra=30 to 60 nm, dimensions 50 mm*13 mm*1.5 mm), in such a way that the bonding surface of the sample is height*width=13 mm*10 mm, and the steel test plate projects by 2 mm at the upper edge. Subsequently, a 2 kg steel roll is rolled over six times at a speed of 10 m/min for fixing. The sample is reinforced flush at the top with a stable adhesive strip which serves as contact point for the distance sensor. Then the sample is suspended by means of the steel plate such that the longer protruding end of the adhesive tape points vertically downward.
Measurement:
The sample to be analyzed is weighted down at the lower end with a weight of 50 g. The steel test plate bonded to the sample, commencing at 25° C., is heated at a rate of 9 K/min, to the end temperature of 200° C.
What is observed is the distance that the sample has slipped by means of the distance sensor as a function of temperature and time. The maximum slip distance is fixed at 1000 μm (1 mm); if exceeded, the test is stopped and the failure temperature is noted.
Test conditions: room temperature 23+/−3° C., relative air humidity 50+/−5%.
A pressure-sensitive adhesive strip in a climate-controlled cabinet heated to 70° C. or 80° C. is applied to a defined rigid bonding substrate (steel here) and subjected to constant shear stress. The hold time in minutes is ascertained.
By means of suitable plate suspension (angle 179±1°), it is ensured that the pressure-sensitive adhesive strip does not peel off from the lower edge of the plate.
The test is intended primarily to give a statement as to the cohesiveness of the composition. However, this is only the case when the parameters of weight and temperature are chosen such that there is actually cohesive failure in the test.
Otherwise, the test gives information as to the adhesion to the bonding substrate or as to a combination of adhesion and cohesiveness of the composition.
A strip of width 13 mm of the pressure-sensitive adhesive strip to be tested is bonded to a polished steel plate (test substrate) over a length of 5 cm with a 2 kg roller by rolling it over 10 times. Double-sidedly adhesive pressure-sensitive adhesive strips are covered and hence reinforced with an aluminum foil of thickness 50 μm on the reverse side.
Subsequently, a belt loop is attached to the lower end of the adhesive tape. Then a nut and bolt are used to secure an adapter plate to the front side of the shear test plate in order to ensure the defined angle of 179±1°. The maturing time between rolling-on and stress should be between 10 and 15 minutes. The weights of 500 g or 1 kg are subsequently suspended smoothly with the aid of the belt loop.
An automatic stopwatch then ascertains the juncture at which the test specimens shear off.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2016 224 646.1 | Dec 2016 | DE | national |
| 10 2016 224 735.2 | Dec 2016 | DE | national |
