Laminate for application to wallpaper and article using same

Abstract

The present disclosure provides a wallpaper laminate that can maintain good holding power when applied to wallpaper and can be peeled off from the wallpaper with reduced or suppressed pressure-sensitive adhesive residue and damage to the wallpaper, as well as an article, an intermediate member for wallpaper laminate, and a roll body using the same. The wallpaper laminate according to an embodiment of the present disclosure comprises a first release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer, a first pressure-sensitive adhesive layer containing modified silicone, and a 12 g / m 2 The wallpaper laminate comprises, in this order, a nonwoven fabric layer having the above basis weight, a second pressure-sensitive adhesive layer containing modified silicone, and a second release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer. The wallpaper laminate has an embossed pattern, and the first pressure-sensitive adhesive layer is applicable to and removable from the wallpaper.

Description

[Technical field]

[0001] The present invention relates to a wallpaper laminate, an article using the same, and an intermediate member and a roll body for a wallpaper laminate. [Background technology]

[0002] In recent years, adhesive articles that are attached to wall surfaces have been developed.

[0003] Patent Document 1 (JP 2020-531641 A) is an adhesive article for attaching an object to a wall surface, comprising: a first adhesive layer; a nonwoven fabric layer adjacent to the first adhesive layer and defining a periphery, the nonwoven fabric layer comprising a nonwoven fabric layer material and comprising a first main surface and a second main surface; a first arrangement pattern of recesses on at least the first main surface of the nonwoven fabric layer, each of the recesses terminating in a film comprising the nonwoven fabric layer material; and an adhesive interface on a bottom wall surface, the adhesive interface including a contact portion between the first adhesive layer and the film.

[0004] Patent Document 2 (JP 2016-002403 A) discloses a self-adhesive hook in which the back surface of a hook body having a hook piece integrally formed at the lower end of its front surface is self-adhesive and can be detachably attached to a target wall surface, and an adhesive sheet is provided on the back surface of the hook body, the adhesive sheet having an acrylic foam adhesive layer with its front surface adhered to the back surface and a polyurethane self-adhesive layer with its front surface adhered to the back surface of the acrylic foam adhesive layer, and the adhesive sheet is attached in a state in which the upper, lower, left and right peripheral edges of the back surface of the hook body are non-adhesive and the bottom end has a non-adhesive portion with a glue-inhibiting portion that is non-adhesive to the target wall surface. Summary of the Invention

[0005] For example, wallpaper is often applied to the walls inside a house. Usually, wallpaper has a concave-convex pattern formed on the surface to impart a design, or is made of various materials such as polyvinyl chloride resin containing a plasticizer that may adversely affect adhesion, or polyolefin resin that is difficult to adhere to. Therefore, it has been difficult to apply an adhesive article to wallpaper while maintaining a good holding power, compared to the case of applying an adhesive article to a concrete wall surface, a painted wall surface, etc.

[0006] In some cases, wallpaper is made of, for example, a foam, which is more fragile and susceptible to damage, such as tearing, than concrete or painted walls, etc. Therefore, even if an adhesive article can be attached to the wallpaper while maintaining a good holding power, it is difficult to remove the adhesive article from the wallpaper without leaving any pressure-sensitive adhesive residue and without damaging the wallpaper.

[0007] An object of the present invention is to provide a wallpaper laminate that can maintain good holding power when attached to wallpaper and can be removed from the wallpaper with reduced or minimal residual pressure-sensitive adhesive and damage to the wallpaper, as well as an article, an intermediate member for the wallpaper laminate, and a roll body using the same.

[0008] One embodiment of the present invention is a wallpaper laminate, comprising a first release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer, a first pressure-sensitive adhesive layer containing a modified silicone, and a 12 g / m 2 The present invention provides a wallpaper laminate comprising, in this order, a nonwoven fabric layer having the above basis weight, a second pressure-sensitive adhesive layer containing modified silicone, and a second release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer, the wallpaper laminate having an embossed pattern, and the first pressure-sensitive adhesive layer being applyable to and peelable from the wallpaper.

[0009] Another embodiment of the present disclosure provides an article including a base having a wallpaper laminate attached to a backside base surface of the article via a second pressure-sensitive adhesive layer, the base surface having at least one recess.

[0010] Another embodiment of the present disclosure provides a wallpaper laminate comprising, in this order, a first release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer, a first pressure-sensitive adhesive layer containing a modified silicone, a foam layer, a second pressure-sensitive adhesive layer containing a modified silicone, and a second release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer, wherein the first pressure-sensitive adhesive layer is applyable to and peelable from the wallpaper.

[0011] Another embodiment of the present disclosure provides an intermediate member for use in a wallpaper laminate, the intermediate member comprising, in this order, a release liner having a release layer, a pressure-sensitive adhesive layer containing a modified silicone, and a release liner having a release layer, wherein either one of the two release liners constitutes a first release liner or a second release liner, and the pressure-sensitive adhesive layer constitutes a first pressure-sensitive adhesive layer or a second pressure-sensitive adhesive layer.

[0012] Another embodiment of the present disclosure provides a roll for use in a wallpaper laminate, comprising, in this order, a release liner having release layers on both sides and a pressure-sensitive adhesive layer containing a modified silicone, wherein the release liner constitutes a first release liner or a second release liner, and the pressure-sensitive adhesive layer constitutes a first pressure-sensitive adhesive layer or a second pressure-sensitive adhesive layer.

[0013] The present disclosure can provide a wallpaper laminate that can maintain good holding power when attached to wallpaper and can be removed from the wallpaper with reduced or minimal residual pressure-sensitive adhesive and damage to the wallpaper, as well as an article using the same, an intermediate member for a wallpaper laminate, and a roll body.

[0014] The above description is not intended to mean that all embodiments of the invention and all advantages of the invention are disclosed. [Brief description of the drawings]

[0015] [Figure 1]1 is a schematic cross-sectional view of a wallpaper laminate according to an embodiment of the present disclosure. [Diagram 2] FIG. 2 is a schematic cross-sectional view of a wallpaper laminate having an embossed pattern according to an embodiment of the present disclosure with the release liner removed. [Diagram 3] FIG. 2 is a schematic diagram of an embossing pattern according to one embodiment of the present disclosure. [Figure 4] FIG. 2 is a schematic diagram of an embossing pattern according to another embodiment of the present disclosure. [Diagram 5] FIG. 2 is a schematic diagram of an article according to an embodiment of the present disclosure when peeled from wallpaper. [Figure 6a] FIG. 2(a) is a rear view of the article prior to application of a wallpaper laminate according to one embodiment of the present disclosure. [Figure 6b] FIG. 2 is a plan view of an article prior to application of a wallpaper laminate according to one embodiment of the present disclosure. [Figure 6c] FIG. 2 is a front view of an article prior to application of a wallpaper laminate according to one embodiment of the present disclosure. [Figure 6d] FIG. 2 is a side view of an article prior to application of a wallpaper laminate according to one embodiment of the present disclosure. [Figure 6e] FIG. 2 is a bottom view of the article prior to application of a wallpaper laminate according to one embodiment of the present disclosure. [Figure 7a] FIG. 2 is a side view of an article prior to application of a wallpaper laminate according to another embodiment of the present disclosure. [Figure 7b] FIG. 2 is a bottom view of an article prior to application of a wallpaper laminate according to another embodiment of the present disclosure. [Figure 8] FIG. 2 is a schematic diagram of an article according to an embodiment of the present disclosure when removed from wallpaper. [Figure 9] 1 is a schematic cross-sectional view of an intermediate member according to an embodiment of the present disclosure. [Figure 10] 1 is a schematic cross-sectional view of a roll body according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Representative embodiments of the present invention will be described in detail below with reference to the drawings as necessary, but the present invention is not limited to these embodiments.

[0017] In this disclosure, "applicable to wallpaper and removable" means that when the wallpaper laminate is attached to the wallpaper via the first pressure-sensitive adhesive layer, the wallpaper laminate exhibits a desired holding power and is retained without peeling off from the wallpaper, while when the wallpaper laminate is peeled off from the wallpaper, the wallpaper laminate can be peeled off without leaving any pressure-sensitive adhesive on the wallpaper surface after peeling, while reducing or suppressing damage to the wallpaper. In one embodiment, "removable" can mean that the wallpaper laminate can be peeled off with a moderate force (e.g., the force of an adult woman) without the use of a special tool and without tearing the wallpaper.

[0018] In the present disclosure, the term "sea-island structure" refers to a structure in which discontinuous non-embossed portions that become islands are arranged in a continuous embossed portion that becomes a sea portion, as shown in FIG. 3, as well as a structure in which there are at least two linear or non-linear continuous embossed portions (sea portions) in at least one direction, and non-embossed portions (island portions) are arranged between the embossed portions, as shown in FIG. 4.

[0019] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0020] In the present disclosure, "non-fluorine-based and non-silicone-based" means that the material is non-fluorine-based and non-silicone-based, i.e. the material used is neither a fluorine-based material nor a silicone-based material.

[0021] As used herein, "curing" may also encompass the concept commonly referred to as "crosslinking."

[0022] As used herein, "film" also encompasses articles referred to as "sheets."

[0023] In this disclosure, the term "substantially" means including variations due to manufacturing errors and the like, and is intended to allow variations of about ±20%.

[0024] In the present disclosure, for example, the term "on" in the phrase "a release layer disposed on a substrate" means that the release layer is disposed directly on the substrate, or that the release layer is disposed indirectly on the substrate through another layer.

[0025] In the present disclosure, for example, "in this order" in "a laminate comprising (including) a first release liner, a first pressure-sensitive adhesive layer, and a nonwoven fabric layer in this order" means that the three components, i.e., the first release liner, the first pressure-sensitive adhesive layer, and the nonwoven fabric layer, are included in this order. Another layer, such as a printed layer, may be interposed between these components, for example, between the first release liner and the first pressure-sensitive adhesive layer.

[0026] Figure 1 is a schematic cross-sectional view of a wallpaper laminate (sometimes simply referred to as a "laminate") according to an embodiment of the present disclosure. The wallpaper laminate 100 of Figure 1 includes, in this order, a first release liner 101, a first pressure-sensitive adhesive layer 103, a core layer 105 as a nonwoven fabric layer or a foam layer, a second pressure-sensitive adhesive layer 107, and a second release liner 109. When the core layer is a nonwoven fabric layer, the wallpaper laminate of the present invention has an embossed pattern, as illustrated in Figures 2 to 4.

[0027] In an embodiment, both the first release liner and the second release liner of the present disclosure have a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer disposed on a base, and are applied to the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer via the release layer. Such a release layer can exhibit superior release performance for the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer of the present invention containing modified silicone, compared to a typical silicone-based release layer. In particular, from the viewpoint of lifting or peeling of the release liner in the embossed laminate, manufacturing costs, etc., a non-fluorine-based and non-silicone-based release layer (also referred to as an "NSNF release layer") is preferable.

[0028] The release layers in the first release liner and the second release liner may be the same or different. Examples of configurations in which the release layers are different include a configuration in which the release layer of the first release liner is a fluorine-based release layer and the release layer of the second release liner is a non-fluorine-based and non-silicone-based release layer, or a configuration in which the release layer of the first release liner is a non-fluorine-based and non-silicone-based release layer and the release layer of the second release liner is a fluorine-based release layer. The release layers of the first release liner and the second release liner are both fluorine-based release layers (or non-fluorine-based and non-silicone-based release layers), but also include a configuration in which the peel strength of the first pressure-sensitive adhesive layer relative to the release layer of the first release liner is different from the peel strength of the second pressure-sensitive adhesive layer relative to the release layer of the second release liner.

[0029] From the viewpoint of usability of the wallpaper laminate, the peel strength of the first pressure-sensitive adhesive layer to the release layer of the first release liner and the peel strength of the second pressure-sensitive adhesive layer to the release layer of the second release liner preferably differ by at least about 2.0 times, at least about 2.5 times, or at least about 3.0 times, and at most about 20 times, and at most about 10 times, at most about 5.0 times, at most about 4.5 times, or at most about 4.0 times. With regard to the peel strengths of both pressure-sensitive adhesive layers, the peel strength of the first pressure-sensitive adhesive layer to the release layer of the first release liner may be higher, or the peel strength of the second pressure-sensitive adhesive layer to the release layer of the second release liner may be higher.

[0030] The fluorine-based release layer is not particularly limited, but can be formed by using at least one of fluorine-based release agents such as fluorocarbon-containing materials such as perfluoroalkyl group-containing vinyl ether polymers, fluorosilicone-containing materials, and coating agents in which fluorine resins such as tetrafluoroethylene and trifluoroethylene are dispersed in binder resins.As such a fluorine-based release layer, the fluorine-based release layer described in U.S. Patent No. 4,472,480, U.S. Patent No. 4,980,443, and U.S. Patent No. 4,736,048 can be suitably used.

[0031] For example, by appropriately adjusting the type and amount of the fluorine-based release agent used in each release layer, the above-mentioned peel strength can be differentiated by using the fluorine-based release agent.

[0032] The non-fluorine-based and non-silicone-based release layer is not particularly limited, but may be formed using, for example, at least one of (meth)acrylic release agents.

[0033] In an embodiment, the (meth)acrylic release agent contains a poly(meth)acrylic acid ester, and has a viscosity of about 1.0×10 at 20° C. and a frequency of 1 Hz. 2 Pa ~ approx. 3.0×10 6 The (meth)acrylic release agent may be used to form a release layer having a storage modulus of 1 Pa and a contact angle of about 15° or more with a methanol / water mixed solution (volume ratio 90 / 10) having a wet tension of 25.4 mN / m. This contact angle is advantageous because it tends to effectively inhibit the wetting and spreading of the pressure-sensitive adhesive onto the surface of the release layer of the acrylic release agent, thereby reducing the affinity with the pressure-sensitive adhesive.

[0034] The storage modulus is approximately 5.0 × 10 2 Pa or more, approximately 1.0×10 3 Pa or more, or about 1.5 x 10 3 Pa or more, and may be about 3.0×10 6 Pa or less, approximately 1.0×10 5Pa or less, or about 1.0 x 10 4 It may be less than Pa.

[0035] Here, in the present disclosure, the storage modulus (G') of the (meth)acrylic release agent is a value measured in shear mode at 20°C and a frequency of 1 Hz using a viscoelasticity device (e.g., rotary rheometer ARES-G2, TA Instruments Japan Inc.).

[0036] For example, the contact angle can be about 20° or more, about 25° or more, or about 30° or more, or can be about 55° or less, about 50° or less, or about 45° or less.

[0037] In the present invention, the "contact angle" is defined as the contact angle measured with a mixed solution of methanol and water (volume ratio 90 / 10) having a wetting tension of 25.4 mN / m, as described in JIS K6768: 1999. This measurement is performed under conditions of a temperature of 23±1° C. and a relative humidity of 50±5%.

[0038] The (meth)acrylic release agent is a polymer composition that contains a polymer such as a poly(meth)acrylic acid ester.

[0039] Examples of poly(meth)acrylic acid esters include copolymers of (meth)acrylic monomer components including a (meth)acrylate having an alkyl group with 12 or more carbon atoms (also referred to as a "first alkyl (meth)acrylate") and a (meth)acrylate having an alkyl group with 12 or fewer carbon atoms (also referred to as a "second alkyl (meth)acrylate"). The first alkyl (meth)acrylate and the second alkyl (meth)acrylate may both have alkyl groups with 12 carbon atoms.

[0040] The alkyl group of the first alkyl (meth)acrylate is typically such that it can form a relatively long side chain in such a copolymer. Such a long alkyl side chain is effective in reducing the surface energy of the release layer, where the surface energy is estimated by the contact angle as described above. The number of carbon atoms in the alkyl group of the first alkyl (meth)acrylate can be 14 or more, 18 or more, 20 or more, or 24 or more. The upper limit of the number of carbon atoms can be, for example, 36 or less, 34 or less, 32 or less, or 30 or less.

[0041] From the viewpoint of peeling force, the long-chain alkyl side chain preferably does not contain a polar functional group such as a carboxyl group, a hydroxyl group, a nitrogen- or phosphorus-containing group, etc. Preferred examples of the first alkyl (meth)acrylate include lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and behenyl (meth)acrylate. The first alkyl (meth)acrylate may be used alone or in combination of two or more thereof.

[0042] The alkyl group of the second alkyl (meth)acrylate is typically such that it can form a relatively short side chain in the copolymer. Such a short alkyl side chain can lower the glass transition temperature of the release agent to about 30° C. or less. This also reduces the storage modulus to about 1×10 2 From about 3 × 10 6 Pa, and a release layer formed by the (meth)acrylic release agent can be peeled off without rattle between the pressure-sensitive adhesive layer and the release layer. The number of carbon atoms in the alkyl group of the second alkyl (meth)acrylate can be 10 or less, 8 or less, or 6 or less. The lower limit of the carbon number can be, for example, 1 or more, 2 or more, or 3 or more.

[0043] From the viewpoint of peeling force and the like, the short alkyl side chain preferably does not contain the above-mentioned polar functional group, similar to the alkyl side chain of the first alkyl (meth)acrylate.

[0044] The ratio of the above-mentioned two (meth)acrylic monomer components in the copolymer is not particularly limited. For example, it is preferable to contain 10% by mass to 90% by mass of the first alkyl (meth)acrylate or the second alkyl (meth)acrylate with respect to the total mass of the first alkyl (meth)acrylate and the second alkyl (meth)acrylate from the viewpoint of peelability without rattling. For example, the peel strength can be varied by adjusting the ratio of the first alkyl (meth)acrylate to the second alkyl (meth)acrylate. For example, the peel strength can be controlled by appropriately adjusting the ratio of each of the first alkyl (meth)acrylate and the second alkyl (meth)acrylate within a range selected from about 10% by mass or more, about 20% by mass or more, about 30% by mass or more, or about 40% by mass or more, and about 90% by mass or less, about 80% by mass or less, about 70% by mass or less, or about 60% by mass or less.

[0045] In one embodiment, the poly(meth)acrylic acid ester is derived from a monomer component including an alkyl(meth)acrylate having a branched alkyl group having 8 or more carbon atoms. The number of carbon atoms in the branched alkyl group can be 10 or more, 14 or more, 18 or more, 20 or more, or 24 or more. The upper limit of the number of carbon atoms can be, for example, 36 or less, 34 or less, 32 or less, or 30 or less.

[0046] Examples of alkyl (meth)acrylates having a branched alkyl group with 8 or more carbon atoms include 2-ethylhexyl (meth)acrylate, 2-hexyldodecyl (meth)acrylate, 2-heptylundecyl (meth)acrylate, 2-octyldecyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, 2-dodecylhexadecyl (meth)acrylate, 2-tetradecyloctadecyl (meth)acrylate, and isononyl (meth)acrylate. Such (meth)acrylates having a branched side chain can reduce the storage modulus and surface energy because of their own reduced crystallinity. Therefore, when using an alkyl (meth)acrylate having a branched alkyl group with 8 or more carbon atoms, it is not necessary to use the two components of the first alkyl (meth)acrylate and the second alkyl (meth)acrylate described above. Among these, 2-hexyldodecyl (meth)acrylate, 2-octyldecyl (meth)acrylate, 2-dodecylhexadecyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, 2-tetradecyloctadecyl (meth)acrylate, and isostearyl (meth)acrylate are preferred. Poly(meth)acrylic acid esters prepared using these (meth)acrylates can easily reduce the surface energy of the release layer.

[0047] From the viewpoints of release force, ease of handling in polymerization reaction, etc., the polymer contained in the (meth)acrylic release agent preferably has a weight average molecular weight of about 100,000 or more, about 300,000 or more, or about 500,000 or more, and about 2,000,000 or less, about 1,500,000 or less, or about 1,000,000 or less. Here, in the present disclosure, the "weight average molecular weight" refers to the weight average molecular weight in terms of polystyrene when measured by gel permeation chromatography (GPC).

[0048] The polymerizable precursor composition containing the above-mentioned monomer components is generally polymerized in the presence of a polymerization initiator.Polymerization methods can be varied, but the polymer with high molecular weight that is advantageous for coating formation can be obtained, and therefore solution polymerization in which polymerizable components are dissolved in a solvent is preferred.When using solution polymerization, after polymerization is completed, the solution of the polymerization product can be used as it is as a (meth)acrylic polymer release agent.

[0049] As the polymerization solvent, an aliphatic hydrocarbon such as n-hexane or n-heptane, an ester such as ethyl acetate or butyl acetate, a ketone such as methyl ethyl ketone or methyl isobutyl ketone, or a mixture of these solvents can be used. In addition, from the viewpoint of molecular weight control, a chain transfer agent or a chain extender can also be used.

[0050] Examples of chain transfer agents include thiol compounds such as 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2-propanol, 3-mercapto-1-propanol, dodecanethiol, isooctyl thioglycolate, and 2-mercapto-ethylamine.

[0051] Examples of chain extenders include divalent (meth)acrylic monomers such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0052] In addition, the (meth)acrylic release agent may further contain a (meth)acrylic monomer having an ionizing radiation active group in the side chain, such as a (meth)acrylic monomer having a benzophenone structure or an acetophenone structure in the side chain. Such a monomer may be blended together with the monomer component into the polymerizable precursor composition to form a part of the polymer. The ionizing radiation active group (e.g., benzophenone structure, acetophenone structure) generates a radical upon irradiation with ionizing radiation such as an electron beam or ultraviolet light. The generated radical promotes crosslinking of the polymerization product of the polymerizable precursor composition and bonding of the cured product obtained from the crosslinking to the base. By using a (meth)acrylic monomer having an ionizing radiation active group in the side chain, for example, the production efficiency of the release layer can be improved. The (meth)acrylic monomer having an ionizing radiation active group in the side chain may be used alone, or two or more of them may be used in combination.

[0053] The solution polymerization of the polymerizable precursor composition can typically be carried out at a reaction temperature of about 50° C. to about 100° C. in an atmosphere of an inert gas such as nitrogen gas for about 2 hours to about 100 hours.

[0054] As the polymerization initiator, a general polymerization initiator can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate)dimethyl(dimethyl 2,2'-azobis(2-methylpropionate)), and peroxides such as benzoyl peroxide and lauroyl peroxide.

[0055] The amount of the polymerization initiator used is preferably about 0.005 parts by mass or more and about 0.5 parts by mass or less, based on 100 parts by mass of the alkyl (meth)acrylate monomer component. By setting the amount of the polymerization initiator used to about 0.005 parts by mass or more, a practical polymerization rate can be ensured. By setting the amount of the polymerization initiator used to about 0.5 parts by mass or less, the molecular weight of the polymerization product can be increased to a level sufficient for forming a coating.

[0056] In embodiments, the release liner is formed by coating the release agent described above onto a base and optionally drying, curing by heat, curing by ionizing radiation (eg, electron beam or ultraviolet light), or the like.

[0057] The base may be, but is not limited to, a plastic film such as polyester (e.g., polyethylene terephthalate, polyethylene naphthalate, or polybutylene terephthalate), polyolefin (e.g., polyethylene), paper (e.g., kraft paper), or a paper base coated with these plastic materials.

[0058] The thickness of the base is not particularly limited, and may be, for example, about 10 micrometers or more, about 15 micrometers or more, or about 20 micrometers or more, and may be about 300 micrometers or less, about 200 micrometers or less, or about 150 micrometers or less.

[0059] The amount of the above-mentioned release agent applied can vary depending on the base.For example, the release agent is generally applied so that the dry thickness is about 0.01 micrometers or more and about 10 micrometers or less.For the base being a paper base coated with a plastic film such as polyester or polyolefin, or a paper base coated with a plastic material, the dry thickness is generally about 0.05 micrometers or more and about 1 micrometer or less.For the base having absorbency or low smoothness such as paper, the dry thickness is generally about 0.1 micrometers or more and about 5 micrometers or less.

[0060] In an embodiment, the peel strength of the pressure-sensitive adhesive layer to the release layer of the release liner (without embossing) is about 10 N / 25 mm or less, about 7.5 N / 25 mm or less, about 5.0 N / 25 mm or less, about 3.0 N / 25 mm or less, or about 1.5 N / 25 mm or less, and about 0.01 N / 25 mm or more, about 0.02 N / 25 mm or more, about 0.05 N / 25 mm or more, about 0.10 N / 25 mm or more, or about 0.20 N / 25 mm or more. Here, the peel strength is the peel strength when the release liner is peeled at 300 mm / min in a 180° direction according to JIS Z0237. For example, a release liner that exhibits a peel strength of less than about 0.3 N / 25 mm before embossing can be used as a light release liner, and a release liner that exhibits a peel strength of about 0.3 N / 25 mm or more can be used as a heavy release liner. Further, in embodiments, the peel strength of the pressure-sensitive adhesive layer to the release layer of the release liner (with embossing) is about 5.0 N / 25 mm or less, about 4.0 N / 25 mm or less, about 3.0 N / 25 mm or less, about 2.5 N / 25 mm or less, or about 1.5 N / 25 mm or less, and about 0.01 N / 25 mm or more, about 0.02 N / 25 mm or more, about 0.05 N / 25 mm or more, about 0.10 N / 25 mm or more, or about 0.20 N / 25 mm or more.

[0061] In the wallpaper laminate of the present invention, a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer containing modified silicone are disposed on both sides of the nonwoven fabric layer or the foam layer. The surface of the wallpaper to which the wallpaper laminate is applied is formed from various materials (e.g., polyvinyl chloride resin, generally polyolefin resin containing a plasticizer). Since the pressure-sensitive adhesive layer of the present invention contains modified silicone, the wallpaper laminate can be attached to wallpaper of various materials as described above, and the pressure-sensitive adhesive does not remain on the wallpaper, and it is effective in peeling the wallpaper laminate from the wallpaper without causing damage such as tearing. Here, in the present disclosure, "modified silicone" means silicone in which a functional group (e.g., a functional group having a urethane structure) is added to the main chain of silicone. The modified silicone may be used alone or in combination of two or more of them. The adhesive layer and the nonwoven fabric layer or the foam layer may be in direct contact with each other, or another layer may be independently present between the adhesive layer and the nonwoven fabric layer or the foam layer. In an embodiment, a resin layer (e.g., a thermoplastic film) is present between the adhesive layer and the foam layer.

[0062] The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer can be the same or different. The first pressure-sensitive adhesive layer can be applied to the wallpaper and peeled off. The "different pressure-sensitive adhesive layers" configuration includes a configuration in which the pressure-sensitive adhesive layers have different material types, such as the first pressure-sensitive adhesive layer contains a silicone polyurea block copolymer and the second pressure-sensitive adhesive layer contains a silicone polyoxamide block copolymer, as well as a configuration in which both the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer contain a silicone polyurea block copolymer but have different pressure-sensitive adhesive strengths.

[0063] In an embodiment, the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are made of the same material to prevent the risk of product failure due to the mix-up of the pressure-sensitive adhesive surface. In addition, when different pressure-sensitive adhesives are used for the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, for example, the second release liner is peeled off first, and the second pressure-sensitive adhesive layer that appears by peeling off the second release liner can be used as the pressure-sensitive adhesive surface that contacts hooks, posters, etc., taking into account the actual use of the resulting laminate. In this case, the peel strength or adhesive strength of the second pressure-sensitive adhesive layer can be designed to be lower than the peel strength or adhesive strength of the first pressure-sensitive adhesive layer (the pressure-sensitive adhesive surface that contacts the wallpaper).

[0064] In an embodiment, the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer each independently have a modulus of elasticity at −20° C. of about 2×10 5 Pa or more, approximately 5×10 5 Pa or more, or about 1×10 6 Pa or more and approximately 7×10 7 Pa or less, approximately 3×10 7 Pa or less, or about 2×10 7 The elastic modulus is a value measured using a viscoelasticity measuring device Discovery HR2 (TA Instrument, DE, USA) under the following conditions: parallel plate: φ8 mm, heating rate: 3°C / min, measurement temperature range: -65°C to 150°C, frequency: 1 Hz (6.28 radians / sec).

[0065] In an embodiment, the weight average molecular weight of the soft segments (silicone portions) of the modified silicone contained in the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is, independently, about 5,000 or more, about 10,000 or more, about 15,000 or more, and about 70,000 or less, about 60,000 or less, or about 50,000 or less.

[0066] The modified silicone is a silicone having a functional group (e.g., a functional group having a urethane structure) added to the silicone main chain, and typically, the silicone portion constituting this main chain constitutes a soft segment, and the functional group portion constitutes a hard segment. In an embodiment, the mass ratio of the soft segment to the hard segment in the modified silicone contained in each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is independently soft segment:hard segment=about 1000:about 1 to about 50:about 1, about 900:about 1 to about 100:about 1, or about 600:about 1 to about 200:about 1.

[0067] The amount of modified silicone blended in each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may independently be, for example, about 30% by weight or more, about 35% by weight or more, about 40% by weight or more, about 45% by weight or more, or about 50% by weight or more, and about 80% by weight or less, about 75% by weight or less, about 70% by weight or less, about 65% by weight or less, about 60% by weight or less, or about 55% by weight or less, relative to the total amount of the pressure-sensitive adhesive layer.

[0068] In embodiments, the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer contain an MQ resin (sometimes referred to as an "MQ tackifying resin").

[0069] Useful MQ resins include, for example, at least one selected from the group consisting of MQ silicone resins, MQD silicone resins, and MQT silicone resins. These MQ resins may have a number average molecular weight of about 100 or more, or about 500 or more, and about 50,000 or less, or about 20,000 or less, and may have methyl substituents. Here, in the present disclosure, "number average molecular weight" refers to the number average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

[0070] MQ silicone resins can include both non-functional and functional resins. Functional silicone resins have one or more functional groups including, for example, silicon-bonded hydrogen, silicon-bonded alkenyl, or silanol groups.

[0071] MQ silicone resin is R'3SiO 1 / 2 Units (M units) and SiO 4 / 2 It is a copolymerizable silicone resin having units (Q units). Such resins are described, for example, in Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley & Sons, New York, (1989), pp. 265-270, as well as in U.S. Pat. No. 2,676,182 (Daudt et al.), U.S. Pat. No. 3,627,851 (Brady), U.S. Pat. No. 3,772,247 (Flannigan), and U.S. Pat. No. 5,248,739 (Schmidt et al.). MQ silicone resins having functional groups are disclosed, for example, in U.S. Pat. No. 4,774,310 (Butler) (discussing silyl hydride groups), U.S. Pat. No. 5,262,558 (Kobayashi et al.) (discussing vinyl and trifluoropropyl groups), and U.S. Pat. No. 4,707,531 (Shirahata) (discussing silyl hydride and vinyl groups). The above resins can generally be prepared in a solvent. Dry or solvent-free MQ silicone resins can be prepared by the methods described in U.S. Patent No. 5,319,040 (Wengrovius et al.), U.S. Patent No. 5,302,685 (Tsumura et al.), and WO 4,935,484 (Wolfgruber et al.).

[0072] MQD silicone resins are, for example, R'SiO 1 / 2 Unit (M unit), SiO 4 / 2 Units (Q units), and R'2SiO 2 / 2 It is a terpolymer having units (D units).

[0073] MQT silicone resin is R'3SiO 1 / 2 Unit (M unit), SiO 4 / 2 Units (Q units), and R'SiO 3 / 2 It is a terpolymer (MQT resin) having units (T units).

[0074] MQ silicone resins are typically supplied in organic solvents. Commercially available MQ silicone resins include SilGrip® SR-545 MQ resin in toluene, available from Momentive Performance Materials Japan LLC, and MQOH resin in toluene, available from PCR, Inc. (Gainesville, Fla.). These organic solutions of MQ silicone resins may be used as provided by the supplier, or may be dried by any number of techniques known in the art to provide MQ silicone resins with 100 percent non-volatile content. Suitable drying methods include, but are not limited to, spray drying, oven drying, steam separation drying, and the like.

[0075] For example, the amount of MQ resin blended in the pressure-sensitive adhesive layer may be about 20% by mass or more, about 25% by mass or more, about 35% by mass or more, or about 45% by mass or more, and may be about 70% by mass or less, about 65% by mass or less, about 60% by mass or less, or about 55% by mass or less, based on the total amount of the pressure-sensitive adhesive layer. Of these, the amount of MQ resin blended in the first pressure-sensitive adhesive layer applied to wallpaper is preferably about 30% by mass or more, about 40% by mass or more, about 45% by mass or more, or about 50% by mass or more, and is preferably about 70% by mass or less, about 60% by mass or less, about 55% by mass or less, or about 50% by mass or less, from the viewpoints of applicability to wallpaper and peelability therefrom. The amount of MQ resin contained in the second pressure-sensitive adhesive layer applied to components such as hooks is preferably about 30% by weight or more, about 40% by weight or more, about 45% by weight or more, or about 50% by weight or more, from the viewpoint of the retention of such components, and is preferably about 70% by weight or less, about 60% by weight or less, about 55% by weight or less, or about 50% by weight or less.

[0076] From the viewpoints of applicability to wallpaper, peelability from wallpaper, and balance of component retention, it is preferable that the modified silicone contains at least one selected from the group consisting of silicone polyurea block copolymers, silicone polyoxamide block copolymers, and silicone polyoxamide-hydrazide block copolymers.

[0077] In embodiments, the silicone polyurea block copolymer contains the reaction product of a polydiorganosiloxane diamine (sometimes referred to as a "silicone diamine"), a polyisocyanate, and, optionally, an organic polyamine. The silicone polyurea block copolymer may be used alone or in combination of two or more thereof.

[0078] Suitable silicone polyurea block copolymers include repeating units of Formula I: [ka] It is represented by:

[0079] In formula I, R is preferably, each independently, an alkyl moiety having from about 1 to 12 carbon atoms, or preferably, a group represented by the formula R 2 (CH2) a CH=CH2 (wherein, R 2 Ha-(CH2) b - or (CH2) cR is a higher alkenyl group represented by the formula (CH=CH-, a is 1, 2, or 3, b is 0, 3, or 6, and c is 3, 4, or 5), a cycloalkyl moiety having about 6 to 12 carbon atoms, an alkyl group, a fluoroalkyl group, and an optionally substituted vinyl group, or an aryl moiety having preferably about 6 to 20 carbon atoms, such as an alkyl group, a cycloalkyl group, a fluoroalkyl group, and an optionally substituted vinyl group, or R is a perfluoro group as described in U.S. Pat. No. 5,028,679. No. 5,236,997, or perfluoropolyether-containing groups as described in U.S. Pat. No. 4,900,474 and U.S. Pat. No. 5,118,775; preferably, at least 50% of the R moieties are methyl groups, with the remainder being monovalent alkyl or substituted alkyl groups, alkenyl groups, phenyl groups, or substituted phenyl groups having 1 to 20 carbon atoms; each Z is a polyvalent group, preferably an arylene or aralkylene group having about 6 to 20 carbon atoms. Preferably, Z is an alkylene or cycloalkylene group having about 6 to 20 carbon atoms, and preferably Z is 2,6-toluylene, 4,4'-methylenediphenylene, 3,3'-dimethoxy-4,4'-biphenylene, tetramethyl-m-xylylene, 4,4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclamate xylene, 1,6-hexamethylene, 1,4-cyclohexylene, 2,2,4-trimethylenehexylene, and mixtures thereof; each Y is independently 1 to 10 carbon atoms. D is an alkylene group, preferably an aralkylene group or an arylene group having 6 to 20 carbon atoms; D is independently selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, phenyl, and a group which completes a ring structure with B or Y to form a heterocycle; in formula I, B is a polyvalent group selected from the group consisting of alkylene, aralkylene, cycloalkylene, polyalkylene oxides such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide, and copolymers and mixtures thereof;m is a number from 0 to about 1000, n is a number of at least 1, and p is a number of at least 10, preferably a number from about 15 to about 2000, and more preferably a number from 30 to 1500;

[0080] Useful silicone polyurea block copolymers are disclosed, for example, in U.S. Pat. No. 5,512,650, U.S. Pat. No. 5,214,119, U.S. Pat. No. 5,461,134, WO 96 / 17726A, WO 96 / 34028A, WO 96 / 34030A, and WO 97 / 40103A.

[0081] Examples of useful silicone diamines for use in the synthesis of silicone polyurea block copolymers include those represented by the following formula (II): [ka] Preferably, the polydiorganosiloxane diamine has a number average molecular weight of about 700 g / mol or more.

[0082] In formula II, R, Y, D, and p are each defined as above.

[0083] Useful polydiorganosiloxane diamines include any of the polydiorganosiloxane diamines within the scope of formula II. Among these, from the viewpoint of balance between applicability to wallpaper, peelability therefrom, and component retention, polydiorganosiloxane diamines having a number average molecular weight of about 700 g / mol or more, about 1000 g / mol or more, about 3000 g / mol or more, about 5000 g / mol or more, about 10000 g / mol or more, about 15000 g / mol or more, about 20000 g / mol or more, or about 25000 g / mol or more, and about 150000 g / mol or less, about 100000 g / mol or less, about 80000 g / mol or less, about 60000 g / mol or less, about 50000 g / mol or less, or about 40000 g / mol or less can be preferably used.

[0084] Suitable methods for synthesizing polydiorganosiloxane diamines and polydiorganosiloxane diamines are disclosed, for example, in U.S. Pat. No. 3,890,269, U.S. Pat. No. 4,661,577, U.S. Pat. No. 5,026,890, U.S. Pat. No. 5,276,122, WO 95 / 03354A, and WO 96 / 35458A.

[0085] Examples of useful polydiorganosiloxane diamines include polydimethylsiloxane diamine, polydiphenylsiloxane diamine, polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine, polyvinylmethylsiloxane diamine, poly(5-hexenyl)methylsiloxane diamine, and combinations or copolymers thereof.

[0086] Suitable polydiorganosiloxane diamines are commercially available, for example, from Shin-Etsu Silicones of America Inc. (Torrance, California) and Hules America, Inc. The polydiorganosiloxane diamines are preferably substantially pure and can be synthesized by methods such as those disclosed in U.S. Pat. No. 5,214,119. Such high purity polydiorganosiloxane diamines can be synthesized by a two-step reaction of cyclic organosilanes with bis(aminoalkyl)disiloxanes using anhydrous aminoalkyl functional silanolate catalysts, such as tetramethylammonium-3 aminopropyldimethylsilanolate, preferably in an amount of less than 1.15 wt.% based on the total amount of cyclic organosilanes. Particularly preferably, the polydiorganosiloxane diamines are synthesized using cesium and rubidium catalysts, such synthesis methods being disclosed, for example, in U.S. Pat. No. 5,512,650.

[0087] The polydiorganosiloxane diamine component can provide a means for adjusting the modulus of the synthesized silicone polyurea block copolymer. In general, high molecular weight polydiorganosiloxane diamines can result in low modulus copolymers, while low molecular weight polydiorganosiloxane polyamines can result in high modulus copolymers.

[0088] Examples of useful polyamines include those available from HUNTSMAN (Houston, Texas) under the trade names: JEFFAMINE® D-230 (i.e., a polyoxypropylene diamine having a number average molecular weight of 230 g / mol), JEFFAMINE® D-400 (i.e., a polyoxypropylene diamine having a number average molecular weight of 400 g / mol), JEFFAMINE® D-2000 (i.e., a polyoxypropylene diamine having a number average molecular weight of 2,000 g / mol), JEFFAMINE® D-4000, and JEFFAMINE® ED polyoxyalkylene diamines, including polyoxyalkylene diamines available under the trade names T-2001, and JEFFAMINE® EDR-148 (i.e., triethylene glycol diamine); polyoxyalkylene triamines, including polyoxyalkylene triamines, available under the trade names T-403, T-3000, and T-5000 from HUNTSMAN; and alkylene diamines, including ethylene diamine and polyalkylenes, available under the trade names Dytek® A and Dytek® EP from DuPont, Wilmington, Delaware.

[0089] The optional polyamine may provide a means to adjust the modulus of the copolymer. By adjusting the concentration, type, and molecular weight of the organic polyamine, the modulus of the silicone polyurea block copolymer can be adjusted.

[0090] In embodiments, the silicone polyurea block copolymer preferably contains about 3 mol or less, more preferably about 0.25 mol to about 2 mol. Preferably, the polyamine has a number average molecular weight of about 300 g / mol or less.

[0091] The polyisocyanate is not particularly limited, and for example, diisocyanates, triisocyanates, etc. can be used.

[0092] Examples of suitable diisocyanates include aromatic diisocyanates such as 2,6-toluene diisocyanate, 2,5-toluene diisocyanate, 2,4-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, methylene bis(o-chlorophenyl diisocyanate), methylene diphenylene-4,4'-diisocyanate, polycarbonate diimide modified methylene diphenylene diisocyanate, (4,4'-diisocyanato-3,3',5,5'-tetraethyl)diphenylmethane, 4,4'-diisocyanato-3,3'-dimethoxybiphenyl (o-dianisidine diisocyanate), 5-chloro-2,4-toluene diisocyanate, and 1-chloromethyl-2,4-diisocyanate benzene, aromatic-aliphatic diisocyanates such as m-xylene diisocyanate and tetramethyl-m-xylene diisocyanate, aliphatic diisocyanates such as 1,4-diisocyanate butane, 1,6-diisocyanate hexane, 1,12-diisocyanate dodecane, and 2-methyl-1,5-diisocyanate pentane, and alicyclic diisocyanates such as methylenedicyclohexylene-4,4'-diisocyanate, and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), cyclohexylene-1,4-diisocyanate.

[0093] Any triisocyanate that can react with polyamines, especially polydiorganosiloxane diamines, is suitable. Examples of such triisocyanates include the polyfunctional isocyanates produced from biurets, isocyanurates, and adducts. Examples of commercially available polyisocyanates include some of the series of polyisocyanates available from Bayer AG under the trade names DESMODUR (trade name) and MONDUR (trade name), from Asahi Kasei Corporation under the trade name Duranate (trade name), and from Dow Plastics Co. under the trade name PAPI (trade name).

[0094] The polyisocyanate is preferably present in a stoichiometric amount based on the amount of polydiorganosiloxane diamine and any optional polyamine.

[0095] Silicone polyurea block copolymers can be synthesized, for example, by solvent-based reactions, solvent-free reactions, or a combination thereof. Effective solvent-based processes are described, for example, by Tyagi et al., "Segmented Organosiloxane Copolymers: 2. Thermal and Mechanical Properties of Siloxane-Urea Copolymers," Polymer, Vol. 25, December 1984, and U.S. Patent No. 5,214,119 (Leir et al.). Useful methods for preparing silicone polyurea block copolymers are also described, for example, in U.S. Patent No. 5,512,650, U.S. Patent No. 5,214,119, U.S. Patent No. 5,461,134, WO 96 / 35458A, WO 98 / 17726A, WO 96 / 34028A, and WO 97 / 40103A.

[0096] Pressure sensitive adhesive compositions containing the silicone polyurea block copolymers can be prepared, for example, using a solvent-based reaction, a solventless reaction, or a combination thereof.

[0097] In solvent-based reactions, the MQ resin can be incorporated before, during, or after the polyamine and polyisocyanate are introduced into the reaction mixture. The reaction of the polyamine and polyisocyanate can be carried out in a single solvent or a mixture of solvents. Preferably, the solvent does not react with the polyamine or polyisocyanate. It is preferred that the starting materials and the final product are thoroughly miscible in the solvent during and after the polymerization reaction is complete. These reactions can be carried out at room temperature or below the boiling point of the reaction solvent. The reaction is preferably carried out at ambient temperature, preferably up to about 50°C.

[0098] In a substantially solvent-free reaction, a polyamine and a polyisocyanate are mixed with an MQ resin in a reaction vessel and reacted with the polyamine and polyisocyanate to form a silicone polyurea block copolymer, which can be reacted with the MQ resin to form a pressure sensitive adhesive composition.

[0099] One useful method, including solvent-based and solventless reactions, is carried out by preparing the silicone polyurea block copolymer using a solventless reaction and then mixing the silicone polyurea block copolymer with a solution of the MQ resin in a solvent.Preferably, the silicone polyurea block copolymer-based pressure sensitive adhesive composition can be synthesized by the combination method described above, which produces a mixture of the silicone polyurea block copolymer and the MQ resin.

[0100] In embodiments, the silicone polyoxamide block copolymers and silicone polyoxamide-hydrazide copolymers include repeating units of Formula A: [ka] Contains at least two of the following:

[0101] In formula A, each R 1is independently an alkyl, haloalkyl, aralkyl, alkenyl, or aryl, or an aryl substituted with an alkyl, alkoxy, or halo; each Y is independently an alkylene, aralkylene, or combinations thereof; each G is independently a bond or a group of the formula R 3 HN-G-NHR 3 of diamine to two NHR 3 is a divalent residue equivalent to the residue except for the R 3 is independently hydrogen or alkyl, or each R 3 G and R 3 and G together with the nitrogen to which they are attached form a heterocyclic group, each n is independently an integer from 0 to 1500, each p is independently an integer from 1 to 10, and each q is independently an integer greater than or equal to 1. At least 50% of the q's are the integer 2.

[0102] R in formula A 1 Suitable alkyl groups for typically have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, and isobutyl. In many cases, R 1 Suitable haloalkyl groups for R are those in which only a portion of the hydrogen atoms of the corresponding alkyl group are replaced with halogen. Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groups having 1 to 3 halo atoms and 3 to 10 carbon atoms. 1 Alkenyl groups suitable for R often have 2 to 10 carbon atoms. Exemplary alkenyl groups often have 2 to 8, 2 to 6, or 2 to 4 carbon atoms, such as ethenyl, n-propenyl, and n-butenyl. 1Suitable aryl groups for often have 6 to 12 carbon atoms. Phenyl is an exemplary aryl group. The aryl group can be unsubstituted or substituted with alkyl (e.g., alkyl having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), alkoxy (e.g., alkoxy having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro). 1 Suitable aralkyl groups typically have an alkylene group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms. In some exemplary aralkyl groups, the aryl group is phenyl and the alkylene group has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms (i.e., the aralkyl structure is alkylene-phenyl, where the alkylene is bonded to a phenyl group).

[0103] In an embodiment, R in some repeat units of formula A 1 At least 40 percent, preferably at least 50 percent, of the groups are methyl. For example, R 1 At least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, or at least 99% of the groups may be methyl. 1 The groups may be selected from alkyls having at least 2 carbon atoms, haloalkyls, aralkyls, alkenyls, and aryls, as well as alkyl, alkoxy, and aryls substituted with halo.

[0104] Each Y in formula A is independently an alkylene, an aralkylene, or a combination thereof. Suitable alkylene groups typically have up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms. Exemplary alkylene groups include methylene, ethylene, propylene, and butylene. Suitable aralkylene groups typically have an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. In some of the exemplary aralkylene groups, the arylene moiety is phenylene. That is, the divalent aralkylene group is a phenylene-alkylene, where the phenylene is bonded to an alkylene having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used herein, with respect to the Y group, "combinations thereof" refers to a combination of two or more groups selected from alkylene groups and aralkylene groups. For example, the combination can be a single aralkylene bonded to a single alkylene (e.g., alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylene combination, the arylene is phenylene and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

[0105] Each G in formula A is independently a bond or a group represented by formula R 3 HN-G-NHR 3 From the diamine compound, two amino groups (i.e., -NHR 3 When G is a bond, the copolymer is a silicone polyoxamide-hydrazide. In an embodiment, G is a bond and each R 3 is hydrogen.

[0106] When G is a residue unit, the copolymer is a silicone polyoxamide. The diamine may have primary or secondary amino groups. 3 The group is hydrogen or alkyl (e.g., 1 to 10, 1 to 6, or 1 to 4 carbon atoms), or R 3 G and R3 Both G and G together with the nitrogen to which they are attached form a heterocyclic group (e.g., R 3 HN-G-NHR 3 is piperazine. In most embodiments, R 3 is hydrogen or alkyl. In many embodiments, both amino groups in the diamine are primary amino groups (i.e., both R 3 The groups are hydrogen), and the diamine has the formula H2N-G-NH2.

[0107] In embodiments, G is an alkylene, heteroalkylene, arylene, aralkylene, or combinations thereof. Suitable alkylenes often have 2 to 10, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkylene groups include ethylene, propylene, butylene, and the like. Suitable heteroalkylenes often are polyoxyalkylenes, such as polyoxyethylenes having at least two ethylene units, polyoxypropylenes having at least two propylene units, or copolymers thereof. Suitable aralkylene groups typically contain an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. Some exemplary aralkylene groups are phenylene-alkylenes, where the phenylene is bonded to an alkylene having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. As used herein, with respect to the G group, "combinations thereof" refers to combinations of two or more groups selected from alkylene, heteroalkylene, polydiorganosiloxane, arylene, and aralkylene. For example, the combination can be an aralkylene bonded to an alkylene (e.g., alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylene combination, the arylene is phenylene, and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

[0108] Each subscript n in formula A is independently an integer from 0 to 1,500. For example, subscript n may be an integer of up to 1000, up to 500, up to 400, up to 300, up to 200, up to 100, up to 80, up to 60, up to 40, up to 20, or up to 10. The value of n is often at least 1, at least 2, at least 3, at least 5, at least 10, at least 20, or at least 40. For example, subscript n may be in the range of 40 to 1500, 0 to 1000, 40 to 1000, 0 to 500, 1 to 500, 40 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to 100, 1 to 80, 1 to 40, or 1 to 20.

[0109] Each subscript p is independently an integer from 1 to 10. For example, the value of p is often an integer that is at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, or at most 2. The value of p can range from 1 to 8, 1 to 6, or 1 to 4.

[0110] Each subscript q is independently an integer greater than or equal to 1, and at least 50% of the q's are the integer 2. In embodiments, at least 75%, at least 90%, at least 99%, or all of the q's are the integer 2.

[0111] In one embodiment, the silicone polyoxamide block copolymers and silicone polyoxamide-hydrazide block copolymers have the formula: -R a -(CO)-NH-(wherein, R a is alkylene). Every carbonylamino group along the backbone of the copolymer material is part of an oxalylamino group (e.g., a-(CO)-(CO)-NH- group). That is, every carbonyl group along the backbone of the copolymer material is bonded to another carbonyl group and is part of an oxalyl group. More specifically, the copolymer contains multiple amino oxalylamino groups.

[0112] Silicone polyoxamide block copolymers and silicone polyoxamide-hydrazide block copolymers are linear block copolymers (i.e., containing hard and soft blocks) and may be elastomeric. They tend to have better solvent resistance than known polydiorganosiloxane polyoxamides. Some of the copolymers are insoluble, for example, in toluene or even tetrahydrofuran. Here, the following method can determine whether a copolymer is "insoluble" in a particular solvent. Approximately 1 g of sample copolymer was placed in a jar, about 100 g of the desired solvent was added, the jar was sealed, and placed on a roller at ambient temperature for about 4 hours. If 90% or more of the original mass is retained after the sample copolymer is dried to constant weight, the copolymer sample is considered to be insoluble.

[0113] Silicone polyoxamide block copolymers and silicone polyoxamide-hydrazide block copolymers can be prepared, for example, according to the methods of the present disclosure by reacting at least two repeat units of formula B: [ka] Copolymer materials can be prepared which contain:

[0114] In formula B, each R 1 is independently an alkyl, haloalkyl, aralkyl, alkenyl, or aryl, or an aryl substituted with an alkyl, alkoxy, or halo; each Y is independently an alkylene, aralkylene, or combinations thereof; each G is independently a bond or a group of the formula R 3 HN-G-NHR 3 From the diamine, two -NHR 3 is a divalent residue equivalent to the residue except for the R 3 are independently hydrogen or alkyl, or R 3 G and R 3 and G together with the nitrogen to which they are attached form a heterocyclic group, and each n is independently an integer from 0 to 1500.

[0115] R 1 , Y, G, and R 3 Suitable examples of are the same as those described above for formula A.

[0116] The first step of the method of the present disclosure is to provide a compound of formula C: [ka] The method may involve the use of a compound of the formula:

[0117] In formula C, p is an integer of 1 to 10.

[0118] The compound of formula C contains at least one polydiorganosiloxane segment and at least two oxalylamino groups. 1 The R groups, Y groups, and subscript n are the same as described for formula B, and p is an integer from 1 to 10. 2 The groups are independently alkyl, haloalkyl, or aryl, or aryl substituted with alkyl, alkoxy, halo, or alkoxycarbonyl, or have the formula D: [ka] It is.

[0119] In formula D, each R 4 are independently hydrogen, alkyl, or aryl, or R 4 together form a ring.

[0120] R in formula C 2Suitable alkyl and haloalkyl groups for often have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Tertiary alkyl groups (e.g., t-butyl) and haloalkyl groups can be used, but often a primary or secondary carbon atom is directly attached to the adjacent oxy group. Exemplary alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, and iso-butyl. Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groups, in which some, but not all, of the hydrogen atoms on the corresponding alkyl group are replaced with halo atoms. For example, the chloroalkyl or fluoroalkyl group can be chloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl, 4-chlorobutyl, fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 4-fluorobutyl, and the like. R 2 Suitable aryl groups for include those having 6 to 12 carbon atoms, such as phenyl. The aryl group may be unsubstituted or substituted with alkyl (e.g., alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, or n-propyl), alkoxy (e.g., alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, or propoxy), halo (e.g., chloro, bromo, or fluoro), or alkoxycarbonyl (e.g., alkoxycarbonyl having 2 to 5 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, or propoxycarbonyl).

[0121] The compound of formula C can include a single compound (i.e., all of the compounds have the same values ​​for p and n) or can include multiple compounds (i.e., the compounds have different values ​​for p, different values ​​for n, or different values ​​for both p and n). Compounds with different n values ​​have siloxane chains of different lengths. Compounds with a p value of at least 2 are chain extended.

[0122] In an embodiment, the mixture is a first compound of formula C, where the subscript p is equal to 1, and a second compound of formula C, where the subscript p is equal to at least 2. The first compound can include a plurality of different compounds having different n values. The second compound can include a plurality of compounds having different p values, different n values, or different values ​​for both p and n. The mixture can contain at least 50% by weight of the first compound of formula C (i.e., p is equal to 1) and 50% or less by weight of the second compound of formula C (i.e., p is equal to at least 2), based on the total weight of the first and second compounds in the mixture. In some of the mixtures, the first compound is present in an amount of at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 98% by weight, based on the total amount of the compounds of formula C. The mixture often contains up to 50%, up to 45%, up to 40%, up to 35%, up to 30%, up to 25%, up to 20%, up to 15%, up to 10%, up to 5%, or up to 2% by weight of the second compound.

[0123] Different amounts of the chain extending compound of formula C in the mixture can affect the final properties of the elastomeric material of formula B. That is, the amount of the second compound of formula C (i.e., p is at least equal to 2) can be advantageously varied to provide elastomeric materials with different properties. For example, increasing the amount of the second compound of formula C can tailor the melt rheology (e.g., make the elastomeric material flow more easily when present as a melt), tailor the flexibility of the elastomeric material, decrease the modulus of the elastomeric material, or a combination thereof.

[0124] In the first step of the disclosed method, a compound of formula C and a molar excess of a compound of formula E: [ka] are combined under reactive conditions.

[0125] R in formula E 3 and the G group is as described for formula B.

[0126] The diamine of formula E may be optionally classified as an organic diamine or as a polydiorganosiloxane diamine with an organic diamine, such as, for example, one selected from alkylenediamines, heteroalkylenediamines, arylenediamines, aralkylenediamines, or alkylene-aralkylenediamines. Since the diamines have only two amino groups, the resulting polydiorganosiloxane polyoxamides and polyoxamide-hydrazides are linear block copolymers that are often elastomeric, melt at high temperatures, and are soluble in some common organic solvents. The diamines do not have polyamines with more than two primary or secondary amino groups. There may be tertiary amines that do not react with the compound of formula C.

[0127] Exemplary polyoxyalkylene diamines (i.e., G is a heteroalkylene where the heteroatom is oxygen) include, but are not limited to, those commercially available under the trade names JEFFAMINE™ D-230, JEFFAMINE™ D-400, JEFFAMINE™ D-2000, and JEFFAMINE™ EDR-148 from HUNTSMAN (Woodlands, TX), listed above, as well as JEFFAMINE™ HK-511 (i.e., a polyether diamine having both oxyethylene and oxypropylene groups and having a number average molecular weight of 220 g / mol), and JEFFAMINE™ ED-2003 (i.e., a polyethylene glycol having a number average molecular weight of 2000 g / mol).

[0128] Exemplary alkylenediamines (i.e., G is alkylene) include, but are not limited to, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, 2-methylpentamethylene-1,5-diamine (i.e., available from Dupont, Wilmington, Del. under the trade name DYTEK™ A), 1,3-pentanediamine (available from Dupont under the trade name DYTEK™ EP), 1,4-cyclohexanediamine, 1,2-cyclohexanediamine (available from Dupont under the trade name DHC-99), 4,4′-bis(aminocyclohexyl)methane, and 3-aminomethyl-3,5,5-trimethylcyclohexylamine.

[0129] Exemplary arylene diamines (i.e., G is an arylene, such as phenylene) include, but are not limited to, m-phenylene diamine, o-phenylene diamine, and p-phenylene diamine. Exemplary aralkylene diamines (i.e., G is an aralkylene, such as alkylene-phenyl) include, but are not limited to, 4-aminomethyl-phenylamine, 3-aminomethyl-phenylamine, and 2-aminomethyl-phenylamine. Exemplary alkylene-aralkylene diamines (i.e., G is an alkylene-aralkylene, such as alkylene-phenylene-alkylene) include, but are not limited to, 4-aminomethyl-benzylamine, 3-aminomethyl-benzylamine, and 2-aminomethyl-benzylamine.

[0130] Exemplary hydrazines (ie, G is a bond) include, but are not limited to, hydrazine and N,N'-diaminopiperazine.

[0131] In some preferred embodiments, the diamine of formula E is selected from the group consisting of hydrazine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-pentanediamine, 1,6-diaminohexane, and m-xylylenediamine.

[0132] Reaction of a compound of formula C with a molar excess of a diamine of formula E provides a compound of formula F: [ka] This results in an amine-terminated polymer of

[0133] The reaction can be carried out using multiple compounds of formula C, multiple diamines, or combinations thereof. Multiple compounds of formula C with different number average molecular weights can be mixed with a single diamine or multiple diamines under reaction conditions. For example, the compound of formula C can include a mixture of materials with different values ​​of n, different values ​​of p, or different values ​​for both n and p. Multiple diamines can include, for example, a first diamine that is an organic diamine and a second diamine that is a polydiorganosiloxane diamine. Similarly, a single compound of formula C can be combined with multiple diamines under reaction conditions.

[0134] The condensation reaction of the compound of formula C with the diamine is often carried out at room temperature or at an elevated temperature (e.g., a temperature of up to about 250°C). For example, the reaction can often be carried out at room temperature or at a temperature of up to about 100°C. In other examples, the reaction can be carried out at a temperature of at least about 100°C, at least about 120°C, or at least about 150°C. For example, the reaction temperature is often in the range of about 100°C to about 220°C, about 120°C to about 220°C, or about 150°C to about 200°C. The condensation reaction is often complete in less than about 1 hour, less than about 2 hours, less than about 4 hours, less than about 8 hours, or less than about 12 hours.

[0135] The reaction can occur in the presence or absence of a solvent. A suitable solvent typically does not react with the reactants or products involved in the reaction. Furthermore, a suitable solvent typically can keep all reactants and all products in solution throughout the process. Exemplary solvents include, but are not limited to, toluene, tetrahydrofuran, dichloromethane, aliphatic hydrocarbons (e.g., alkanes such as hexane), and mixtures thereof.

[0136] After the reaction is complete, the excess diamine and solvent, if any, are removed. The excess diamine can be removed, for example, by vacuum distillation.

[0137] The resulting amine-terminated polymer of formula F is then treated with an oxalate ester to utilize the amine end groups to form repeat units of formula F. Useful oxalate esters are of formula G: [ka] has.

[0138] The oxalate of formula G can be, for example, a compound of formula R 5 It can be prepared by reacting an alcohol of -OH with oxalyl dichloride. Commercially available oxalates of formula G (e.g., from Sigma-Aldrich (Milwaukee, WI) and VWR International (Bristol, CT)) include, but are not limited to, dimethyl oxalate, diethyl oxalate, di-n-butyl oxalate, di-tert-butyl-oxalate, bis(phenyl)oxalate, bis(pentafluorophenyl)oxalate, 1-(2,6-difluorophenyl)-2-(2,3,4,5,6-pentachlorophenyl)oxalate, and bis(2,4,6-trichlorophenyl)oxalate.

[0139] Particularly useful oxalates of formula G include, for example, the oxalates of phenol, ethanol, butanol, methyl ethyl ketone oxime, acetone oxime, and trifluoroethanol.

[0140] Any suitable reactor (e.g., glass vessel or general vessel equipped with a stirrer) or process can be used to prepare the silicone polyoxamide block copolymers and silicone polyoxamide-hydrazide block copolymers according to the methods of the present disclosure. The reaction can be carried out using a batch process, a semi-batch process, or a continuous process.

[0141] Any solvent present can be removed from the resulting polydiorganosiloxane polyoxamide or polyoxamide-hydrazide at the end of the reaction. This removal process is often carried out at a temperature of at least about 100° C., at least about 125° C., or at least about 150° C. This removal process is typically carried out at a temperature of less than about 300° C., less than about 250° C., or less than about 225° C.

[0142] It may be desirable to carry out the reaction in the absence of a solvent: in a solvent that is not compatible with both the reactants and the product, the reaction will be incomplete and the degree of polymerization will be low.

[0143] The pressure-sensitive adhesive layer of the present disclosure can contain, as optional components, for example, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, fillers, pigments, and dyes, provided that the effects of the present disclosure are not impaired.

[0144] The wallpaper laminate of the present disclosure has a nonwoven fabric layer or a foam layer as a core layer, where the "core layer" is a layer disposed between the first and second pressure-sensitive adhesive layers of the wallpaper laminate, as shown in FIG.

[0145] The nonwoven fabric layer of the present disclosure has a thickness of about 12 g / m from the viewpoint of a balance between applicability to wallpaper, peelability from the wallpaper, and component retention. 2 In one embodiment, the nonwoven layer has a basis weight of about 15 g / m 2 More than about 20g / m 2 Above, about 25g / m 2 Above, about 30g / m 2 Above, about 35g / m 2 More than about 40g / m 2 Above, about 50g / m 2 Above, about 55g / m 2 More than about 60g / m 2 or more, or about 70 g / m 2 Above 260g / m 2 Below, about 230g / m 2 Below, about 200g / m 2 Below, about 150g / m 2 or less than 130 g / m 2 Basis weight is calculated from the weight of a 10cm x 10cm sample.

[0146] In some embodiments, the nonwoven layer comprises a nonwoven substrate. The nonwoven substrate can be a nonwoven fabric or web made by any of the commonly known processes for making nonwoven fabrics or webs. In this disclosure, "nonwoven" refers to a fabric having a structure of individual fibers or filaments, randomly and / or unidirectionally assembled in a mat form, but without the identifiable properties of knitted fabrics.

[0147] Nonwoven fabrics or webs can be formed by various processes, such as meltblown, spunbond, spunlace, bonded carded web, airlaying, and wetlaying processes. In some embodiments, the nonwoven layer contains a multi-layer nonwoven material, for example, having at least one layer of meltblown nonwoven and at least one layer of spunbond nonwoven, or any other suitable combination of nonwoven materials. For example, the nonwoven layer may be a multi-layer material of spunbond-meltbond-spunbond, spunbond-spunbond, or spunbond-spunbond-spunbond. In embodiments, long fiber-based nylon spunbond nonwoven, polyester-based spunbond nonwoven, and polyolefin-based spunbond nonwoven are preferred.

[0148] In this disclosure, "meltblown" refers to a method for forming a nonwoven fibrous web by extruding molten fiber-forming material through multiple orifices in a die, contacting the fibers with air or other damping fluid while forming the fibers to attenuate the fibers into fine fibers, and then collecting the fine fibers. An exemplary meltblown process is taught, for example, in U.S. Patent No. 6,607,624 (Berrigan et al.). "Meltblown fiber" refers to a meltblowing process or a fiber produced by a meltblowing process.

[0149] In this disclosure, "spunbonding" and "spunbond process" refer to a method for forming a nonwoven fibrous web by extruding molten fiber-forming material as continuous or semi-continuous fibers from a plurality of fine capillaries of a spinneret and then collecting the attenuated fibers. An exemplary spunbond process is disclosed, for example, in U.S. Pat. No. 3,802,817 (Matsuki et al.). "Spunbond fibers" and "spunbonded fibers" refer to fibers produced using a spunbond or spunbond process. Such fibers are generally continuous and are sufficiently entangled or point bonded to form a coherent nonwoven fibrous web. Thus, it is generally not possible to extract one complete spunbond fiber from a mass of such fibers. The fibers may have shapes as described in U.S. Pat. No. 5,277,976 (Hogle et al.), which describes fibers having unknown shapes.

[0150] In this disclosure, "carding" and "carding process" refer to a method of forming a nonwoven fibrous web by treating staple fibers in a combing or carding unit, where the staple fibers are separated or broken and aligned lengthwise to form a generally longitudinally oriented fibrous nonwoven web. Exemplary carding processes and carding machines are taught, for example, in U.S. Pat. No. 5,114,787 (Chaplin et al.) and U.S. Pat. No. 5,643,397.

[0151] In this disclosure, "bonded carded web" refers to a nonwoven fibrous web formed by a carding process, in which at least a portion of the fibers are bonded together by methods including, for example, thermal point bonding, autogenous bonding, hot air bonding, ultrasonic bonding, needle punching, calendaring, application of spray adhesives, etc. Further details regarding the manufacture and properties of nonwoven webs and laminates including nonwoven webs can be found, for example, in U.S. Pat. No. 9,469,091 (Henke et al.), which is incorporated herein by reference in its entirety.

[0152] In this disclosure, "air laying" refers to a process in which bundles of small fibers having a typical length of about 3 millimeters to about 52 millimeters (mm) are separated and entrained in an air supply, and then typically deposited on a forming screen with the aid of a vacuum supply. The randomly oriented fibers may then be bonded to one another using, for example, thermal point bonding, autogenous bonding, hot air bonding, needle punching, calendaring, spray adhesives, and the like. An exemplary air laying process is taught, for example, in U.S. Patent No. 4,640,810 (Laursen et al.).

[0153] "Wet laying" in this disclosure refers to a process in which bundles of small fibers having a typical length of about 3 millimeters to about 52 millimeters (mm) are separated and entrained in a feed liquid, and then typically deposited on a forming screen with the aid of a vacuum feed. Water is typically the preferred liquid. The randomly deposited fibers may be further entangled (e.g., hydroentangled) or bonded to one another using, for example, thermal point bonding, autogenous bonding, hot air bonding, ultrasonic bonding, needle punching, calendaring, application of spray adhesives, and the like. Exemplary wet laying and bonding processes are taught, for example, in U.S. Pat. No. 5,167,765 (Nielsen et al.). Exemplary bonding processes are also disclosed, for example, in U.S. Pat. No. 9,139,940 (Berrigan et al.).

[0154] Fibrous materials which provide useful nonwoven layers can be made from natural fibers (eg, wood or cotton fibers), synthetic fibers (eg, thermoplastic fibers), or combinations of natural and synthetic fibers.

[0155] Exemplary materials for forming the thermoplastic fibers include polyolefins (eg, polyethylene, polypropylene, polybutylene, ethylene copolymers, propylene copolymers, butylene copolymers, and copolymers and blends of these polymers), polyesters, and polyamides.

[0156] The nonwoven substrate that makes up the nonwoven layer can be formed from fibers or filaments made of any suitable thermoplastic polymeric material, including, but not limited to, polyolefins, polyisoprene, polybutadiene, fluorinated polymers, chlorinated polymers, polyamides, polyimides, polyethers, polyethersulfones, polysulfones, copolymers of polyvinyl acetate and vinyl acetate (e.g., polyethylene-co-polyvinyl alcohol), polyphosphazenes, polyvinyl esters, polyvinyl ethers, polyvinyl alcohol, and polycarbonates.

[0157] Suitable polyolefins include, but are not limited to, polyethylene, polypropylene, poly 1-butene, copolymers of ethylene and propylene, alpha-olefin copolymers (e.g., copolymers of ethylene or propylene with 1-butene, 1-hexene, 1-octene, and 1-decene), polyethylene-co-1-butene, and poly(ethylene-co-1-butene-co-1-hexene).

[0158] Suitable fluorinated polymers include, but are not limited to, polyvinyl fluoride, polyvinylidene fluoride, copolymers of vinylidene fluoride (e.g., polyvinylidene fluoride-co-hexafluoropropylene), and copolymers of chlorotrifluoroethylene (e.g., poly(ethylene-co-chlorotrifluoroethylene).

[0159] Suitable polyamides include, but are not limited to, polyiminoadipoyliminohexamethylene, polyiminoadipoyliminodecamethylene, and polycaprolactam.Suitable polyimides include polypyromellitimide.

[0160] Suitable polyethersulfones include, but are not limited to, polydiphenylethersulfone and polydiphenylsulfone-co-diphenyleneoxidesulfone.

[0161] Suitable copolymers of vinyl acetate include, but are not limited to, polyethylene-co-vinyl acetate and copolymers in which at least some of the acetate groups are hydrolyzed to produce various polyvinyl alcohols, such as polyethylene-co-vinyl alcohol.

[0162] The fibers may also be multicomponent fibers, for example having a core of one thermoplastic material and a sheath of another thermoplastic material. The sheath may melt at a lower temperature than the core, providing partially random bonds between the fibers when the mat of fibers is exposed to the sheath melt. A combination of monocomponent fibers with different melting points may also be useful for this purpose.

[0163] In some embodiments, the nonwoven fabric or nonwoven web useful for the nonwoven layer according to the present disclosure is at least partially elastic. Examples of polymers for making elastic fibers include thermoplastic elastomers such as ABA block copolymers, polyurethane elastomers, polyolefin elastomers (e.g., metallocene polyolefin elastomers), olefin block copolymers, polyamide elastomers, ethylene vinyl acetate elastomers, and polyester elastomers. ABA block copolymer elastomers are generally elastomers in which the A block is polystyrenic and the B block is prepared from a conjugated diene (e.g., a lower alkylene diene). The A block is generally formed primarily from substituted (e.g., alkylated) or unsubstituted styrenic moieties (e.g., polystyrene, poly(alpha methyl styrene), or poly(t-butyl styrene)) and has a number average molecular weight of about 4,000 grams to 50,000 grams per mole. The B block is generally formed primarily from conjugated dienes (e.g., isoprene, 1,3-butadiene, or ethylene-butylene monomers) that may be substituted or unsubstituted, and has a number average molecular weight of about 5,000 grams to 500,000 grams per mole. The A and B blocks may be configured, for example, in a linear, radial, or star configuration. ABA block copolymers may contain multiple A and / or B blocks, which may be made from the same or different monomers. Typical block copolymers are linear ABA block copolymers, where the A blocks may be the same or different, or block copolymers with four or more blocks that terminate primarily in A blocks. Multiblock copolymers may contain a certain percentage of AB diblock copolymers, which tend to form, for example, more pressure-sensitive adhesive elastomeric film segments. Other elastomeric polymers may be blended with the block copolymer elastomer, and various elastomeric polymers may be blended to provide various degrees of elastomeric properties.Numerous types of thermoplastic elastomers are commercially available, including, for example, those sold under the trade name "STYROFLEX™" by BASF (Florham Park, NJ), those sold under the trade name "KRATON™" by Kraton™ Polymers (Houston, Tex.), those sold under the trade names "PELLETHANE™", "INFUSE™", "VERSIFY™", and "NORDEL™" by Dow Chemical (Midland, Mich.), those sold under the trade name "ARNITEL™" by DSM (Heerlen, Netherlands), those sold under the trade name "HYTREL™" by EI DuPont de Nemours and Company, and those sold under the trade name "VISTAMAXX™" by ExxonMobil (Irving, Tex.).

[0164] For example, the nonwoven webs can be made by carding, air laying, wet laying, spunlacing, spunbonding, electrospinning, or meltblowing processes such as meltspun or meltblowing, or combinations thereof. Any of the nonwoven webs may be made from a single type of fiber or two or more types of fibers differing in thermoplastic polymer type, shape, and / or thickness, and at least one of the single fiber type or fiber types may each be a multicomponent fiber as described above.

[0165] Staple fibers may also be present in the web. The presence of staple fibers generally results in a web with higher loft (bulk) and lower density than a web formed solely from meltblown microfibers. A higher loft web may have lower cohesion at the interface of the nonwoven layer or the bulk of the nonwoven layer itself, making it easier to separate from one or more pressure-sensitive adhesive layers.

[0166] The nonwoven layer may optionally further comprise one or more layers of scrim. For example, either or both major surfaces of the nonwoven layer may optionally further comprise a scrim layer. Scrims are typically reinforcements for woven or nonwoven fabrics made from fibers and are included in nonwoven articles to provide strength. Suitable scrim materials include, but are not limited to, nylon, polyester, fiberglass, polyethylene, polypropylene, and the like. The average thickness of the scrim may vary. The layer of scrim may optionally be bonded to the nonwoven base. Various adhesives can be used to bond the scrim to the nonwoven base. Alternatively, the scrim may be thermally bonded to the nonwoven.

[0167] The nonwoven web of the nonwoven layer may also be treated / finished with various techniques to improve properties such as static control, polarizability, coloration, flame retardancy, UV stability, absorbency, and other properties apparent to those skilled in the art.

[0168] Useful nonwoven layers can have any suitable effective fiber diameter (EFD) desired for a particular application. In this disclosure, "effective fiber diameter" is the apparent diameter of the fibers in a fibrous web based on air permeability testing, in which air at 1 atmosphere and room temperature is passed through a web sample at a specified thickness and a specified face velocity (5.3 cm / sec) and the corresponding pressure drop is measured. Based on the measured pressure drop, the effective fiber diameter is calculated, such as by the method described in Davies, CN, The Separation of Airborne Dust and Particulates, Institution of Mechanical Engineers, London Proceedings, 1B (1952). In some embodiments, the fibers of the nonwoven base may be about 0.1 micrometer or more, about 1 micrometer or more, about 2 micrometers or more, or about 4 micrometers or more, and about 125 micrometers or less, about 75 micrometers or less, about 50 micrometers or less, about 35 micrometers or less, about 25 micrometers or less, about 20 micrometers or less, about 15 micrometers or less, about 10 micrometers or less, about 8 micrometers or less, or about 6 micrometers. For example, a spunbond nonwoven layer typically has an effective fiber diameter of about 35 micrometers or less, while an airlaid nonwoven layer may have a larger effective fiber diameter of about 100 micrometers.

[0169] The loft (bulk) of a nonwoven layer can be evaluated by its solidity. Solidity is determined by dividing the measured bulk density of a nonwoven fibrous web by the density of the material that makes up the solid portion of the web. The bulk density of a web can be determined by first weighing a portion of the web (e.g., a 10 cm x 10 cm section). The measured weight of the web is then divided by the area of ​​the web to determine the basis weight of the web, which is expressed in g / m 2The thickness of a web can be measured by removing (e.g., by die cutting) a disk of the web having a diameter of 135 mm and measuring the web thickness with a 230 g weight having a diameter of 100 mm centered on the web. The bulk density of a web is determined by dividing the basis weight of the web by the thickness of the web and is expressed in g / m 3 The solidity is then determined by dividing the bulk density of the nonwoven fibrous web by the density of the material (e.g., polymer) that contains the solid filaments of the web. The bulk density of the polymer can be measured by standard means if the supplier does not specify the material density.

[0170] Loft is reported as 100% minus solidity (e.g., 7% solidity equals 93% loft). Higher loft is particularly advantageous for pattern embossed nonwoven layers, as the pressure sensitive adhesive can penetrate and flow relatively easily throughout the void volume during application of thermal energy and / or pressure. In some embodiments, high loft nonwoven layers can be combined in an embossing patterning process to create the required array of recesses.

[0171] The solidity of the nonwoven layer can be between about 2.0% and less than 12.0% (i.e., the loft is between about 98.0% and greater than 88.0%). In some embodiments, the solidity of the nonwoven layer can be at most about 7.5%, at most about 7.0%, or at most about 6.5%, and can be at least about 5.0%, at least about 5.5%, or at least about 6.0%.

[0172] The foam layer of the present disclosure may be in the form of a foam having any suitable thickness, composition, and opacity or transparency. The foam layer can be a single layer foam or a multi-layer foam.

[0173] In some embodiments, the foam layer has a pull tab that extends beyond the first and second pressure-sensitive adhesive layers and serves as a handle when the wallpaper laminate is stretched and peeled off the wallpaper. The shape, size, thickness, and transparency of the pull tab can be appropriately set in consideration of design, ease of handling, and the like.

[0174] In some embodiments, the foam layer may be a composite in which a film layer is applied to the foam. For example, a composite including a film layer bonded to a foam can be formed using any suitable technique, including, for example, co-extrusion of the film and foam, co-molding, extrusion coating, bonding with a binder, pressure bonding, heat bonding, and combinations thereof. If only one member of the composite, the film or foam, is stretched to achieve peeling from the wallpaper, the member should exhibit sufficient physical properties and be of sufficient thickness to achieve that purpose.

[0175] The foam layer is typically selected to have mechanical properties suitable for use in wallpaper laminates. For example, the foam layer is selected to be able to stretch (elongate) at least 50 percent in a first direction (e.g., longitudinal) without breaking. That is, the foam layer can be stretched at least about 50 percent without breaking, thereby increasing at least one dimension, such as the length of the foam layer. In some embodiments, the foam layer can be stretched at least 100 percent, at least 150 percent, at least 200 percent, at least 300 percent, at least 400 percent, or at least 500 percent without breaking. The foam layer can often be stretched up to 1200 percent, up to 1000 percent, up to 800 percent, up to 750 percent, or up to 700 percent without breaking. These relatively large stretch values ​​can facilitate stretch peeling of the wallpaper laminate after it is applied to the wallpaper.

[0176] The Young's modulus of the foam layer can be an indicator of the resistance of the foam layer to stretching. In some embodiments, the Young's modulus of the foam layer can be about 520 MPa or less, about 345 MPa or less, about 170 MPa or less, about 70 MPa or less, about 20 MPa or less, about 7 MPa or less, or about 3.4 MPa or less. The lower limit of the Young's modulus of the foam layer is not particularly limited, and can be, for example, about 0.1 MPa or more, about 0.5 MPa or more, about 1.0 MPa or more, about 1.5 MPa or more, or about 2.0 MPa or more. The Young's modulus can be measured using the method of ASTM D790-07 or ASTM D882-02.

[0177] The foam layer may be prepared from, for example, polyolefins (e.g., polyethylenes such as high density polyethylene, low density polyethylene, linear low density polyethylene, and linear very low density polyethylene, polypropylene, and polybutylene), vinyl copolymers (e.g., polyvinyl chloride and polyvinyl acetate), olefin copolymers (e.g., ethylene / methyl acrylate copolymers, ethylene / vinyl acetate copolymers, and ethylene / propylene copolymers), acrylonitrile-butadiene-styrene copolymers, (meth)acrylic polymers and copolymers, polyurethanes, and combinations or blends thereof. Exemplary blends may include, for example, polypropylene / polyethylene blends, polyurethane / polyolefin blends, polyurethane / polycarbonate blends, and polyurethane / polyester blends. Other suitable blends may include, for example, blends of thermoplastic polymers, elastomeric polymers, and combinations thereof. Suitable compounds may include, for example, styrene-butadiene copolymers, polychloroprene (i.e., neoprene), nitrile rubber, butyl rubber, polysulfide rubber, cis-1,4-polyisoprene, ethylene-propylene terpolymers (e.g., EPDM rubber), silicone rubber, silicone polyurea block copolymers, polyurethane rubber, natural rubber, (meth)acrylate rubber, thermoplastic rubbers (e.g., styrene-butadiene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene / butylene-styrene block copolymers, and styrene-ethylene / propylene-styrene block copolymers), thermoplastic polyolefin rubber materials, and combinations thereof.

[0178] Useful foam layers are typically flexible, e.g., to increase the degree of surface contact between a first pressure-sensitive adhesive layer disposed on the foam layer and the wallpaper surface. The foam layer can achieve an elongation of about 50 percent to about 600 percent (i.e., the foam layer is extensible at least about 50 percent to about 600 percent). The elongation at break of the foam layer is preferably high enough to maintain the foam layer intact when the wallpaper laminate is peeled from the wallpaper to which it is attached.

[0179] The foam layer is often selected to optimize properties such as flexibility and resilience. Flexible and resilient polymer foams are suitable for the intended use where the wallpaper laminate is applied to wallpaper having recesses and protrusions.

[0180] From the viewpoint of the balance between applicability to wallpaper, peelability from the wallpaper, and component retention, the foam layer preferably has an expansion ratio of about 5 times or more, about 10 times or more, or about 15 times or more, and about 50 times or less, about 40 times or less, or about 35 times or less. The expansion ratio of the foam layer was determined by measuring the apparent density by a method in accordance with JIS K7222, and calculating the reciprocal of the apparent density as the expansion ratio.

[0181] The foam layer can have any suitable thickness. Suitable foam layers often have a thickness of at least 100 micrometers, at least 200 micrometers, at least 300 micrometers, at least 400 micrometers, at least 500 micrometers, at least 600 micrometers, or at least 700 micrometers. The thickness may be up to 5.0 mm, up to 4.0 mm, up to 3.0 mm, or up to 2.0 mm. In some embodiments, the foam layer may be a multi-layered construction, with each layer of the foam layer contributing different properties such as density, elongation, tensile strength, and combinations thereof.

[0182] Useful polyethylene vinyl acetate copolymer foams are available from Voltek, Division of Sekisui America Corporation, Lawrence, Massachusetts, under the trade name VOLEXTRA™ and VOLARA™ series.

[0183] When the foam layer is in the form of a composite in which a film layer is applied to the foam, the foam layer can be in a variety of forms including, for example, single or multi-layer films, porous films, and combinations thereof. The film layer can include one or more fillers (e.g., calcium carbonate). The film layer can be a continuous layer or a discontinuous layer. The multi-layer films are preferably integrally bonded to each other in the form of composite films, laminated films, and combinations thereof. The multi-layer films can be prepared using any suitable method including, for example, co-molding, co-extrusion, extrusion coating, bonding with a binder, pressure bonding, heat bonding, and combinations thereof.

[0184] In embodiments in which the foam layer comprises at least one foam layer and at least one film layer, the film layer may contain a poly(alkylene) copolymer derived from at least two different alkene monomers. The poly(alkylene) copolymer may be the reaction product of an alkene mixture containing 1) a first alkene selected from ethene, propene, or a mixture thereof, and 2) a second alkene monomer selected from 1,2-alkenes having 4 to 8 carbon atoms. For example, the second alkene monomer often has 4, 6, or 8 carbon atoms. That is, the alkene mixture contains 1) ethene, propene, or a mixture thereof, and 2) butene, hexane, octane, or a mixture thereof. These copolymers may be prepared using metallocene catalysts. Mixtures or combinations of these copolymers may also be used.

[0185] The wallpaper laminate of the present disclosure, which includes the above-mentioned nonwoven fabric layer as a core layer, has an embossed pattern as shown in Figures 2 to 4. The embossed pattern may be on only one side of the wallpaper laminate, or on both sides. From the viewpoint of the balance between applicability to wallpaper, peelability from the wallpaper, and component retention, it is preferable that the embossed pattern be on both sides. When the embossed pattern is formed on both sides, the same pattern may be formed on both sides as shown in Figure 2, or different patterns may be used.

[0186] Wallpapers usually have projections and recesses to impart a design, are made of brittle foam, and are made from various materials (e.g., plasticizer-containing polyvinyl chloride resin, polyolefin resin). The wallpaper laminate according to the present disclosure includes a nonwoven fabric layer and has an embossed pattern, and thus can exert good retention on such wallpapers, and can provide a structure with an excellent balance between adhesion and removability, which can be peeled off from the wallpaper without leaving any pressure-sensitive adhesive residue while reducing or suppressing damage such as tearing when peeled off from the wallpaper.

[0187] Among the embossed patterns, from the viewpoint of the balance between applicability to wallpaper, peelability from the wallpaper, and component retention, an embossed pattern having a sea-island structure in which the embossed portion is a sea portion and the non-embossed portion is an island portion, as shown in Figures 2 to 4, is preferred.

[0188] The island portion as the non-embossed portion may be formed discontinuously as shown in Fig. 3, or may be formed continuously in one direction (for example, the x direction in Fig. 4) as shown in Fig. 4. In some embodiments, the embossed portion may be formed discontinuously in the island portion as the non-embossed portion.

[0189] As shown in Figure 3, when the island portions as non-embossed portions are formed discontinuously, for example, as shown in Figure 3, an array of island portions in the y direction and an array of adjacent island portions in the y direction may be arranged asymmetrically or symmetrically.

[0190] The shape of the island portion when the wallpaper laminate is viewed from above may be a substantially circular shape as shown in FIG. 3 or a substantially wavy shape as shown in FIG. 4, or may be a substantially polygonal shape (for example, a substantially triangular shape, a substantially square shape, a substantially rectangular shape, a substantially regular pentagonal shape, a substantially hexagonal shape, a substantially regular octagonal shape, a substantially trapezoidal shape, a substantially diamond shape, a substantially star shape, or a substantially lattice shape), a substantially elliptical shape, a substantially linear shape (a substantially striped shape), or a combination of these shapes.

[0191] Fig. 2 is a schematic cross-sectional view of a wallpaper laminate according to an embodiment of the present disclosure having an embossed pattern with the release liner removed. The wallpaper laminate 200 in Fig. 2 includes a first pressure-sensitive adhesive layer 203, a nonwoven fabric layer 205 as a core layer, and a second pressure-sensitive adhesive layer 207, in that order. In the embossed portion and its periphery, the nonwoven fabric layer and the pressure-sensitive adhesive layer are thermally fused by heat embossing.

[0192] The minimum pitch interval b between an island portion and an adjacent island portion and the length a of the embossed top at a position corresponding to this pitch interval b may be the same or different. From the viewpoint of peelability of the embossing roll, it is preferable that a and b satisfy the formula A>b. Here, in this disclosure, "pitch interval" means the distance from the bottom of an island portion to the bottom of an adjacent island portion.

[0193] The shape of the top of the island portion may be approximately flat as shown in FIG. 2, or may be approximately convex or approximately concave.

[0194] The pitch interval b may be the same or different over the entire region. As shown in Fig. 2, the pitch interval b on both the upper and lower surfaces of the laminate may be the same or different. From the viewpoint of the balance between applicability to wallpaper, peelability from the wallpaper, and component retention, the pitch interval b is preferably about 0.01 mm or more, about 0.05 mm or more, or about 0.1 mm or more, and is preferably about 3.0 mm or less, about 2.0 mm or less, or about 1.0 mm or less.

[0195] The embossing depth h may be the same or different throughout the thickness direction of the laminate. As shown in FIG. 2, the embossing depth h on both the upper and lower surfaces of the laminate may be the same or different. The embossing depth h may be, for example, preferably about 0.01 mm or more, about 0.05 mm or more, or about 0.1 mm or more, and may be about 3.0 mm or less, about 2.0 mm or less, or about 1.0 mm or less, from the viewpoint of the balance between applicability to wallpaper, peelability from the wallpaper, and component retention. Here, the embossing depth h refers to the distance from the bottom of the embossed portion to the top of the non-embossed portion.

[0196] In the wallpaper laminate of the present invention, other layers such as a printing layer, a decorative layer, a masking layer, etc. may be disposed between the layers (for example, between the pressure-sensitive adhesive layer and the core layer) as necessary, as long as the effects of the present invention are not impaired. The other layers may be applied to the entire surface or to a part of the surface.

[0197] An example of a method for producing the wallpaper laminate of the present disclosure is shown below, but the production method is not limited to this method. The release liner, pressure-sensitive adhesive layer, and core layer (nonwoven fabric layer or foam layer) used in this method can be the same as those described above.

[0198] The pressure-sensitive adhesive can be disposed on the core layer by any known method. For example, the core layer can be directly coated with the pressure-sensitive adhesive, or, for example, a release liner can be coated with the pressure-sensitive adhesive to form a separate layer, which can then be laminated to the core layer. The latter method is preferred in view of the resistance of the pressure-sensitive adhesive to penetration into the nonwoven or foam.

[0199] The method of applying the pressure-sensitive adhesive to the core layer or release layer is not particularly limited, and methods that can be used include solvent coating methods such as notch bar coating, knife coating, roll coating, reverse roll coating, gravure coating, wire wound rod coating, slot orifice coating, slot die coating, and extrusion coating, water-based coating methods, or hot melt coating methods. After the pressure-sensitive adhesive is applied to the core layer or release liner, optional steps such as drying and curing may be applied as necessary.

[0200] Examples of the method of applying a pressure-sensitive adhesive to a release liner to form another layer include a method of applying a pressure-sensitive adhesive to the release layer of a release liner to form a pressure-sensitive adhesive layer, and then bonding another release liner via the release layer to obtain an intermediate member 900 including a release liner 901, a pressure-sensitive adhesive layer 903, and a release liner 904 in this order, as shown in Figure 9, and a method of applying a pressure-sensitive adhesive to one release layer of a release liner having release layers on both sides to form a pressure-sensitive adhesive layer and winding it up into a roll to obtain a roll body 1000, as shown in Figure 10. The former intermediate member can be suitably used in a discontinuous batch-type manufacturing method, and the latter roll body can be suitably used in a continuous manufacturing method.

[0201] Both the intermediate member and the roll body can constitute a part of the final wallpaper laminate, i.e., either one of the two release liners of the intermediate member can constitute the first release liner or the second release liner, and the pressure-sensitive adhesive layer can constitute the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer, and the release liner of the roll body can constitute the first release liner or the second release liner, and the pressure-sensitive adhesive layer can constitute the first pressure-sensitive adhesive layer or the second pressure-sensitive adhesive layer.

[0202] Here, the two release liners (the first release liner and the second release liner) included in the intermediate member may be the same type of release liner or different types of release liners. In an embodiment, the first release liner and the second release liner are both release liners having a fluorine-based release layer, or the first release liner and the second release liner are both release liners having a non-fluorine-based release layer and a non-silicone-based release layer. Alternatively, the first release liner and the second release liner may be a release liner having a fluorine-based release layer and a release liner having a non-fluorine-based and non-silicone-based release layer, respectively, or a release liner having a non-fluorine-based and non-silicone-based release layer and a release liner having a fluorine-based release layer, respectively. In addition, release liners having different fluorine-based release layers (or release liners having different non-fluorine-based and non-silicone-based release layers) can be used as the first release liner and the second release liner.

[0203] When the core layer is coated with a pressure-sensitive adhesive, a release liner can be applied to the pressure-sensitive adhesive layers applied to both sides of the core layer, and embossing, cutting, or the like can be performed as necessary to obtain a wallpaper laminate.

[0204] The thickness of the silicone pressure-sensitive adhesive layer can be about 1 μm or more, about 5 μm or more, or about 10 μm or more, and about 100 μm or less, about 80 μm or less, or about 50 μm or less. Here, the thickness of the pressure-sensitive adhesive layer is the average value of the thickness at any position of at least five points in the pressure-sensitive adhesive layer having the laminate structure, measured by scanning electron microscope in the thickness direction of the cross section of the laminate structure. Such a thickness measurement method can be similarly used for each layer (for example, base and release layer) constituting the above-mentioned laminate.

[0205] When using an intermediate member having a configuration as shown in Figure 9, one of the release liners 904 is removed, and a pressure-sensitive adhesive layer 903 and a release liner 901 are applied to both sides of the core layer via the pressure-sensitive adhesive layer 903, and embossing or the like is performed as necessary to obtain a wallpaper laminate.

[0206] When using a roll having the configuration shown in FIG. 10, the release liner 1001 and the pressure-sensitive adhesive layer 1003 are unwound from the roll 1000, and applied to both sides of the core layer via the pressure-sensitive adhesive layer 1003, and embossed or cut as necessary to obtain a wallpaper laminate.

[0207] The embossing is not particularly limited, and may be performed, for example, by passing the wallpaper laminate through at least one patterned (e.g., engraved) embossing roll having a concave-convex area corresponding to the array of desired embossed parts, or by pressing the wallpaper laminate placed on at least one patterned (e.g., engraved) embossing mold having a concave-convex area corresponding to the array of desired embossed parts. The former embossing method is sometimes called the rotary embossing method, and the latter embossing method is sometimes called the heat press embossing method. In particular, the rotary embossing method is preferred from the viewpoint of productivity. When using the rotary embossing method, it is preferable to use the above-mentioned non-fluorine-based and non-silicone-based release layer as the release layer of the intermediate member or roll body. Such a release layer can reduce or suppress post-manufacturing defects such as unintended peeling and warping of the release liner in the wallpaper laminate formed using the rotary embossing method, compared to a fluorine-based release layer.

[0208] The temperature and pressure of the embossing process can be appropriately set depending on the type and thickness of the release liner, pressure-sensitive adhesive layer, and core layer, the size and shape of the required embossed pattern, etc. For example, the embossing temperature may be about 70° C. or more, about 80° C. or more, about 90° C. or more, or about 100° C. or more, and may be about 220° C. or less, about 200° C. or less, about 180° C. or less, or about 150° C. or less. The embossing pressure is about 50 N / cm 2 Above, about 100N / cm 2 Above, about 150N / cm 2 Above, about 200N / cm 2 or more, or about 250N / cm 2or more, and may be about 1 kN / cm 2 Below, about 800N / cm 2 Below, about 600N / cm 2 Less than or equal to 500N / cm 2 The wallpaper laminate of the present disclosure can exhibit various favorable performance properties even when such an embossing process is performed.

[0209] The obtained wallpaper laminate may be cut as necessary. The cutting method is not particularly limited, and known cutting methods such as laser cutting, die cutting, stamping, crimping, or a combination thereof can be used.

[0210] For example, the wallpaper laminate of the present disclosure can be used in a variety of ways. In some embodiments, the wallpaper laminate is applied, attached, or pressed onto a substrate (e.g., wallpaper and components that make up the article to which the wallpaper is applied). This method brings the wallpaper laminate into contact with the substrate. If a release liner is present, the release liner is removed before the wallpaper laminate is applied, attached, or pressed onto the substrate. In some embodiments, at least a portion of the substrate may be wiped with isopropyl alcohol before the wallpaper laminate is applied, attached, or pressed onto the substrate.

[0211] To peel the wallpaper laminate from the substrate, at least a portion of the wallpaper laminate may be peeled off from the substrate (e.g., peeled off at 90 degrees to the substrate), or at least a portion of the wallpaper laminate may be stretched (e.g., stretched parallel to the substrate) to peel off from the substrate. In an embodiment in which a pull tab is present, a user can grasp the pull tab and use it to stretch the wallpaper laminate to peel or remove it from the wallpaper. In some embodiments, the pull tab is typically stretched at an angle of 35° or less relative to the wallpaper. The wallpaper laminate of the present disclosure uses a pressure-sensitive adhesive layer containing modified silicone, so that the wallpaper laminate can be peeled off from the wallpaper even at an angle of more than 35° and not more than 90°.

[0212] Fig. 5 is a schematic diagram showing a hook member as an article to which a wallpaper laminate according to an embodiment of the present disclosure is applied, and showing a state in which the hook member has been separated from the wallpaper. According to Fig. 5, for example, when an attempt is made to peel the hook member from the wallpaper by gripping the curved hook portion of the hook member, the pressure-sensitive adhesive layer applied to the non-embossed portion can be peeled off from the non-embossed portion and stretched while being sequentially peeled off from the wallpaper, and the hook member can be removed from the wallpaper.

[0213] In some embodiments, the wallpaper laminate of the present disclosure is used in a state where it is attached via the second pressure-sensitive adhesive layer to a base surface having at least one recess located on the back side of the article with the base after removing the second release liner. The back side of the article to be used by attaching to a wall surface or the like usually has a substantially flat shape in order to improve adhesion with the pressure-sensitive adhesive layer. When the back side of the article has a substantially flat shape, the pressure-sensitive adhesive layer attached to the back side is attached to the wallpaper in a state where it is supported by the entire back side of the article, so that the entire surface of the supported pressure-sensitive adhesive layer can be attached to the wallpaper. As a result, the pressure-sensitive adhesive layer adheres well to both the wallpaper and the article, and therefore it may be difficult to remove the wallpaper laminate from the wallpaper or the article.

[0214] On the other hand, the article of the present disclosure has a recess 612 on the base surface of the article that is adhered to the pressure-sensitive adhesive layer, as shown in FIG. 6(e). For example, when a wallpaper laminate is attached via a pressure-sensitive adhesive layer so as to cover the recess 612 shown in FIG. 6(e), the pressure-sensitive adhesive layer is supported on the base surface 610 except for the recess 612. Since the pressure-sensitive adhesive layer in this state is supported on a part of the base surface, the pressure-sensitive adhesive force between the article and the pressure-sensitive adhesive layer is weaker than that of a pressure-sensitive adhesive layer supported on the entire surface of the base surface. As a result, as shown in FIG. 8, the article attached to the wallpaper via the wallpaper laminate can be easily removed in two stages. The wallpaper laminate of the present disclosure can be suitably used for an article having such a base surface. In particular, the wallpaper laminate of the present disclosure, which includes a nonwoven fabric layer as a core layer and has an embossed pattern, is more suitably used because it has excellent article retention and can more easily perform two-stage peeling of the article.

[0215] The wallpaper laminate of the present disclosure may be applied to the entire base surface of an article, or to a portion of the base surface.

[0216] In some embodiments, the configuration of the article having a base surface with at least one recess includes a configuration in which a protrusion (e.g., a hook portion) sized to function as a tab for peeling is not disposed on the surface of the article opposite the wallpaper side, as shown in Figure 5. Articles having such a configuration can include, for example, clips, whiteboards, frames, picture panels, and mirrors, as shown in Figures 6 and 7.

[0217] Here, the shape of the protrusion is not particularly limited, and examples thereof include an angular shape and a round shape. In an embodiment, from the viewpoint of retention, the dimension of the angular protrusion having a hook portion may be about 15 mm or more, about 20 mm or more, or about 25 mm or more. The upper limit of the dimension is not particularly limited, but may be about 70 mm or less, about 60 mm or less, or about 55 mm or less. Also, from the viewpoint of retention, the diameter of the round protrusion having a hook portion may be about 20 mm or more, about 30 mm or more, or about 40 mm or more, and the upper limit may be about 70 mm or less, about 60 mm or less, or about 50 mm or less. The height (length in the thickness direction) of these angular protrusions and round protrusions varies depending on the shape of the hook portion, but generally can be in the range of about 5 mm or more, about 7 mm or more, or about 10 mm or more at the highest point to about 30 mm or less, about 20 mm or less, or about 15 mm or less.

[0218] 6 shows a generally circular clip 600 with no protrusions on its surface as an article to which the wallpaper laminate of the present disclosure can be applied. Clip 600 has a base portion 601 and a clamp portion 603 attached via a support member 605. The clip may include a member such as a spring formed integrally with or separately from the support member.

[0219] In the case of a round clip as shown in Figures 6 and 7, the diameter may be about 20 mm or more, about 30 mm or more, or about 40 mm or more and about 70 mm or less, about 60 mm or less, or about 50 mm or less. The height (length in the thickness direction) varies depending on the shape of the clip, but generally can be in the range of about 5 mm or more, about 6 mm or more, or about 7 mm or more to about 20 mm or less, about 15 mm or less, or about 10 mm or less.

[0220] When removing a clip with this structure from wallpaper, it is usually removed by pinching the sides of the clip with the thumb and index finger. Since a recess 612 is formed in the base surface 601 of clip 600, even clip 600 that is difficult to clamp can be easily removed from wallpaper. Here, the "recess" in the base surface of the present invention does not include recesses formed for other purposes, such as a recess in joint 607 provided to join base 601 and clamp portion 603 of the clip, as shown in FIG. 6.

[0221] The shape, size, number and depth of the recesses can be appropriately set depending on the application, taking into consideration the ability of the article to be held to the wallpaper and the ability to be peeled off from the wallpaper.

[0222] Examples of the shape of the recess include a substantially polygonal shape (e.g., a substantially triangular shape, a substantially square shape, a substantially rectangular shape, a substantially regular pentagonal shape, a substantially hexagonal shape, a substantially regular octagonal shape, a substantially trapezoidal shape, a substantially rhombus shape, a substantially star shape, etc.), a substantially circular shape, a substantially elliptical shape, a substantially semicircular shape, a substantially semielliptical shape, etc. These shapes may be used alone or in combination of two or more of them. When the shape of the recess is a substantially polygonal shape, the corners may have a curved shape.

[0223] The size of the recess can be changed depending on the size of the article. The size of the recess can be, for example, the ratio of the total area of ​​the recess 612 to the total area of ​​the base surface 610 including the recess 612 when viewed from the base surface 610 side as shown in Fig. 6(e). The ratio of the total area can be, for example, about 10% or more, about 20% or more, about 30% or more, about 40% or more, or about 50% or more, and about 95% or less, about 90% or less, about 80% or less, about 70% or less, or about 60% or less.

[0224] The number of recesses may be, for example, 1 or more, 2 or more, 4 or more, or 6 or more. The upper limit of the number of recesses is not particularly limited, and can be, for example, 1000 or less, 700 or less, 500 or less, 300 or less, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, 30 or less, or 20 or less.

[0225] The depth of the recess can be, for example, about 0.5 mm or more, about 1 mm or more, about 2 mm or more, about 3 mm or more, about 4 mm or more, or about 5 mm or more. The upper limit of the depth is not particularly limited, but can be, for example, about 1 cm or less, about 9 mm or less, about 8 mm or less, about 7 mm or less, about 6 mm or less, or about 5 mm or less. Here, the "depth of the recess" means the distance from the bottom of the recess to the base surface.

[0226] 7 shows another embodiment of a generally circular clip 700 that does not have any protrusions on its surface. The clip 700 has an integrated base portion 701 and clamp portion 703. The clip has a hook portion 707 between the base portion 701 and the clamp portion 703 to assist in clamping an object.

[0227] The base surface 710 on the back side of the clip in Figure 7 has a first recess 712 and a second recess 714. If, for example, a wallpaper laminate is applied to cover only these recesses, the other recesses are not included in the "recesses" in the base surface. However, if the wallpaper laminate is applied, for example, to cover the entire base surface 710, the other recesses are treated as a third recess 722, a fourth recess 724, a fifth recess 726, and a sixth recess 728.

[0228] The method for forming the recesses is not particularly limited, and examples thereof include injection molding, cutting, and 3D printing.

[0229] The wallpaper laminate of the present disclosure and the article including this laminate are attached to wallpaper via a first pressure-sensitive adhesive layer. Since such a pressure-sensitive adhesive layer contains the above-mentioned modified silicone, it can be applied to and removed from various wallpapers.

[0230] The material of the wallpaper is not particularly limited, and examples thereof include polyvinyl chloride resin, polyolefin resin, silicone resin, and (meth)acrylate resin. These materials may contain a plasticizer. These wallpaper materials may be used alone or in combination of two or more. For example, a stain-resistant layer such as silicone resin or a protective layer such as polyolefin resin or (meth)acrylate resin may be provided on a polyvinyl chloride resin foam.

[0231] The polyolefin resin is, for example, at least one of a homogeneous resin such as polyethylene (low density polyethylene (LDPE), high density polyethylene (HDPE)), polypropylene, polybutene, polybutadiene, or polyisoprene, a copolymer of an alpha-olefin having four or more carbon atoms (linear low density polyethylene (LLDPE)); an ethylene (meth)acrylic acid-based copolymer such as an ethylene-acrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, or an ethylene-methacrylic acid copolymer; an ethylene-vinyl acetate copolymer (EVA), a saponified ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, or an ionomer.

[0232] The wallpaper may be foamed or non-foamed. The surface of the wallpaper may be provided with an uneven pattern by embossing or the like. Since the pressure-sensitive adhesive layer of the wallpaper laminate of the present invention contains the above-mentioned modified silicone, even wallpaper that is fragile such as foamed wallpaper or wallpaper with an uneven pattern that makes the pressure-sensitive adhesive easily peelable can be peeled off by applying the pressure-sensitive adhesive layer.

[0233] The wallpaper laminate of the present invention, which has a nonwoven fabric layer as the core layer, is constructed by using a nonwoven fabric layer having an embossed pattern and a specific basis weight, a specific pressure-sensitive adhesive layer, and a specific release liner, and can be peeled off from the wallpaper without tearing it when pulled in a direction of about 90 degrees to the wallpaper surface, for example, and can be applied to the wallpaper as an adherend and peeled off. Also, the wallpaper laminate of the present invention, which has a foam layer as the core layer, is constructed by using a specific pressure-sensitive adhesive layer and a specific release liner, and can be peeled off from the wallpaper without tearing it when stretched in a direction parallel to the wallpaper surface, for example, and can be applied to the wallpaper as an adherend and peeled off.

[0234] In some embodiments, the wallpaper laminate of the present disclosure exhibits a retention of about 7000 minutes or more, about 8000 minutes or more, about 9000 minutes or more, or about 10000 minutes or more in the retention test described below. The upper limit of the retention is not particularly limited, and may be, for example, about 50000 minutes or less, about 30000 minutes or less, or about 20000 minutes or less.

[0235] In some embodiments, the adhesive strength of the wallpaper laminate of the present disclosure to wallpaper is about 1.0 N / 25 mm or more, about 1.3 N / 25 mm or more, or about 1.5 N / 25 mm or more, and about 10 N / 25 mm or less, about 9.5 N / 25 mm or less, about 9.0 N / 25 mm or less, or about 8.0 N / 25 mm or less, in the 90 degree peel strength test described below. EXAMPLES

[0236] Specific embodiments of the present disclosure are illustrated in the following examples, but the present invention is not limited to these embodiments. All parts and percentages are by weight unless otherwise stated. The numerical values ​​inherently contain errors due to the measurement principle and the measuring device. The numerical values ​​are expressed to significant digits with normal rounding.

[0237] Experimental Example 1 In Experimental Example 1, wallpaper laminates made using the same release liner as the first and second release liners were examined. The differences in embossing patterns are further examined in Table 3, and the differences in nonwoven fabrics are further examined in Tables 4 to 6. The various materials used in Experimental Example 1 are shown in Table 1. Here, "Mw" in the table refers to the weight average molecular weight, "Ra" refers to the surface roughness, "Sdr" refers to the "developed area ratio," "DEHP" refers to di-2-ethylhexyl phthalate, and "DINP" refers to the plasticizer dinonyl phthalate.

[0238] [Table 1-1]

[0239] [Table 1-2]

[0240] The prepared samples were evaluated as follows.

[0241] Holding power test: Holding power against wallpaper After cleaning the wallpaper and stainless steel panel with isopropyl alcohol, retention tests were performed as follows: (1) Double-sided tape (ST-416, available from 3M, St. Paul, Minnesota) was attached to one side of a 50 mm x 100 mm x 1.0 mm stainless steel (SUS304BA) panel. After removing the release paper from the double-sided tape, the wallpaper was attached to the double-sided tape while pressing firmly with fingers to avoid wrinkling the wallpaper. (2) The evaluation laminate was cut to 25 mm x 30 mm, and one release liner in the evaluation laminate was removed. Next, this laminate was attached to a 30 mm x 50 mm x 1.0 mm stainless steel (SUS304BA) panel and pressed firmly with a finger. Here, a hole of φ5 mm was made in the vicinity of the center of one end in the longitudinal direction (long side direction) of the stainless steel panel. (3) The other release liner of the laminate was peeled off, and the laminate was attached to the wallpaper attached to the stainless steel panel in (1) above, with the end with the φ5 mm hole at the bottom. (4) The laminate was pressed with a static load of about 15 kg for 5 seconds to obtain a test panel. All test panels were cured for 24 hours at room temperature (23±1° C., relative humidity 50±5%). (5) After 24 hours, a 200 g weight was hung in the hole located at the bottom of the test panel at room temperature (23±1°C, relative humidity 50±5%), and the retention time for each test panel was recorded.

[0242] In the table, for example, ">10080" means that the retention is longer than 10080 minutes, and "<720" means that the retention is shorter than 720 minutes.

[0243] 90 degree peel strength test: Adhesion to wallpaper After cleaning the wallpaper and stainless steel panel with isopropyl alcohol, a 90 degree peel strength test was performed as follows: (1) Double-sided tape (ST-416, available from 3M) was attached to one side of a 50 mm x 100 mm x 1.0 mm stainless steel (SUS304BA) panel. After removing the release paper from the double-sided tape, wallpaper was attached to the double-sided tape, pressed firmly with fingers to avoid wrinkling, and a 7 kg steel roller was rolled back and forth once over the wallpaper at a speed of 300 mm / min to obtain a test base. (2) At room temperature (23±1°C, relative humidity 50±5%), one release liner was peeled off from the 25 mm x 40 mm evaluation laminate, and the laminate was then attached to the wallpaper surface of the test base and pressed down using a 7 kg steel roller, moving it back and forth once at a speed of 300 mm / min. (3) After peeling off the other release liner of the evaluation laminate, one side of the test sample (the pressure-sensitive adhesive layer side of the evaluation laminate) was laminated with 30 mm × 100 mm × 0.21 mm fine paper (180 gsm, MCSPA1R4, available from Epson Corporation) as a backing material (lining material), and the surface was rolled back and forth once at a speed of 300 mm / min using a 7 kg steel roller to obtain a test sample. (4) The test samples were cured at room temperature (23±1°C, relative humidity 50±5%) for 2 days. (5) Using a universal material testing machine (TENSILON available from A&D Company, Limited, Toshima-ku, Tokyo, Japan), the adhesive strength was measured when the test sample was peeled off while pulling the wood-free paper as a backing material in a 90-degree direction at a speed of 300 mm / min.

[0244] Damage-free peel test: Check for damage to wallpaper and residual pressure-sensitive adhesive After cleaning the wallpaper and stainless steel panel with isopropyl alcohol, a damage-free peel test was performed as follows: (1) Double-sided tape (ST-416, obtained from 3M) was attached to one side of a 50 mm x 100 mm x 1.0 mm stainless steel (SUS304BA) panel. After removing the release paper from the double-sided tape, wallpaper was attached to the double-sided tape. The wallpaper was pressed firmly with a finger to avoid wrinkles. (2) The evaluation laminate was cut to a size of 25 mm x 30 mm, one release liner of the evaluation laminate was peeled off, and the laminate was then attached to a small hook and pressed firmly with a finger. (3) The other release liner of the laminate was peeled off and a small hook was attached to the wallpaper that was attached to the stainless steel panel in (1) above. (4) The small hook attached to the wallpaper was pressed with a static load of about 15 kg for 5 seconds to obtain a test panel. All test panels were cured at room temperature (23±1°C, relative humidity 50±5%) for one week. (5) After curing, the hook was peeled off the wallpaper by hand, and the damage to the wallpaper, the residual pressure-sensitive adhesive on the wallpaper, and the degree of dirt were visually observed and evaluated based on each of the criteria shown below. Here, a score of 0 to 1 can be evaluated as a pass level, and a score of 2 to 3 can be evaluated as a fail level.

[0245] Degree of damage to wallpaper 0: The wallpaper was not damaged. 1: The wallpaper is slightly damaged (less than 10%). 2: Wallpaper is extensively damaged (10%-50%). 3: Wallpaper is more extensively damaged (>50% - 100%). Degree of pressure sensitive adhesive residue 0: No pressure sensitive adhesive was left on the wallpaper. 1: There was a small amount of pressure-sensitive adhesive remaining on the wallpaper (less than 10%). 2: Extensive pressure-sensitive adhesive residue remained on the wallpaper (10%-50%). 3: The wallpaper had a larger area of ​​pressure sensitive adhesive remaining (>50% - 100%). Dirt level 0: No staining was observed. 1: Slight staining was observed in limited areas. 2: Slight staining was observed in all areas. 3: Stains were clearly observed.

[0246] Wettability Test: Wetting of Pressure Sensitive Adhesives on Wallpaper After cleaning the wallpaper with isopropyl alcohol, a wettability test was performed as follows: (1) The laminate for evaluation was cut to a size of 25 mm x 30 mm, attached to wallpaper (EB7112), and pressed with a static load of approximately 15 kg for 5 seconds. (2) The test samples were conditioned on dry ice for 30 minutes and then immediately slit with a razor and the cross-sectional area at the interface between the pressure-sensitive adhesive layer and the wallpaper was observed. (3) The cross-sectional field of view in this cross-sectional region was observed using a digital microscope VHX-1000 (Keyence Corporation, Osaka-shi, Osaka, Japan), and a digital image of the interface between the pressure-sensitive adhesive layer and the wallpaper was taken. (4) The wettability (surface contact rate) of the pressure-sensitive adhesive of the evaluation laminate to the wallpaper surface was calculated based on the following formula X.

number

[0247] Here, the surface length of the wallpaper refers to the length of the wallpaper surface that forms the interface between the pressure-sensitive adhesive layer and the wallpaper in the cross-sectional field of the observed test sample. The contact length of the pressure-sensitive adhesive is the length of the wallpaper surface where the pressure-sensitive adhesive layer is not in contact with the wallpaper at the interface between the pressure-sensitive adhesive layer and the wallpaper, measured in the same cross-sectional field of the observed test sample, and the measured lengths are added together, and the total length of the non-contact area of ​​the pressure-sensitive adhesive layer with respect to the wallpaper is subtracted from the surface length of the wallpaper. The measurement was repeated four times, and the average of the measured values ​​is shown in the table.

[0248] Wallpaper Analysis The surface roughness (Ra) and developed area ratio (Sdr) of each wallpaper shown in Table 1 were analyzed in accordance with ISO 25178 using a wide-area three-dimensional measuring device (VR-5200, obtained from Keyence Corporation, Osaka-shi, Osaka, Japan). In the analysis, the wallpaper was attached to the stage of the device, and an area of ​​24 mm × 19 mm was observed.

[0249] The surface components of the wallpaper were analyzed using an FT-IR measurement device (Nicolet 6700, obtained from Thermo), and the concentration of plasticizers in the wallpaper was analyzed using a GC-MS measurement device (7890A+5975C, obtained from Agilent Technologies).

[0250] Example 1 The MQ resin and modified silicone were added to a 225 mL glass bottle in the amounts shown in Table 2, and the mixture was placed in a hybrid mixer (ARE-250, available from Thinky Corporation, Chiyoda-ku, Tokyo, Japan) and shaken at 2000 rpm for 5 minutes, and then shaken with a roller set at approximately 25 rpm for 12 hours or more to obtain a pressure-sensitive adhesive composition.

[0251] Release liner FD-75 was coated with the pressure-sensitive adhesive composition using a wet gap of 0.25 to 0.26 mm to prepare a pressure-sensitive adhesive layer having a thickness of about 0.050 to about 0.065 mm. The coated pressure-sensitive adhesive sample was dried in an oven at 70 °C for 10 minutes.

[0252] A laminate sample was obtained by placing a pressure-sensitive adhesive sample on both sides of the nonwoven layer, with the pressure-sensitive adhesive layer facing the nonwoven layer. The laminate sample was subjected to a pressure of about 0.3 kN / cm 2 The laminate was passed through a heat press equipped with an embossing mold with a roughly hexagonal pattern at a pressure of 1000 psi and 115°C for 1 second, and then punched out to a size of 25 x 30 mm to obtain a laminate for evaluation. The embossing pattern of the obtained laminate was a roughly hexagonal sea-island structure (the embossed part was the sea part, and the non-embossed part was the island part). The pitch interval (pitch interval b in Figure 2) of the non-embossed parts (island parts) was about 0.6 to about 0.7 mm, and the embossing depth (embossing depth h in Figure 2) was about 0.1 mm.

[0253] Examples 2, 4, and 12-14 Laminates for evaluation of Examples 2, 4, and 12 to 14 were obtained in the same manner as in Example 1, except that a release liner 1 prepared using precursor polymer 1 described below was used and the formulation was changed to the formulation in Table 2.

[0254] Precursor polymer 1 STA, ISA, and AEBP were mixed so that the blend ratios of these monomers were 50.0 parts by mass, 50.0 parts by mass, and 0.2 parts by mass, respectively. The monomer mixture was diluted with a mixed solvent of ethyl acetate / n-heptane (50% by mass / 50% by mass) until the monomer concentration was 50% by mass. Furthermore, V-601 was added as an initiator at a ratio of 0.20 parts by mass based on the alkyl (meth)acrylate monomer component, and the system was purged with nitrogen for 2 minutes. Thereafter, the reaction was allowed to proceed for 48 hours in a thermostatic bath at 65°C, and a viscous solution-like precursor polymer 1 was obtained.

[0255] Release Liner 1 Precursor polymer 1 was diluted to 1% by weight with a toluene / MEK mixed solvent (50% by weight / 50% by weight). The diluted solution was coated onto a polyester film (EMBLET® S-50) using a bar coater (#04). The solvent was then evaporated to form a release precursor layer having a thickness of about 0.1 micrometers.

[0256] Using an ultraviolet irradiation device (F300, medium pressure mercury lamp (H bulb), Heraeus (Hanau, Hessen, Germany)), the polyester film having the release precursor layer was irradiated with ultraviolet light in one pass at a line speed of 20 m / min in a nitrogen gas atmosphere to cure the release precursor layer, thereby producing a release liner 1. During irradiation, the amount of ultraviolet light per pass measured with an actinometer UV POWER PUCK (trade name) II (available from EIT) was 350 mJ / cm. 2 (UVA 168mJ / cm 2 , UVB 158mJ / cm 2 , and UVC 24mJ / cm 2 ) In this table, the release liners are abbreviated as "Liner 1," for example, for Release Liner 1. Also, "NSNF" in the table means non-fluorine-based and non-silicone-based.

[0257] Examples 3, 5-7, and 9-11 Laminates for evaluation of Examples 3, 5 to 7, and 9 to 11 were obtained in the same manner as in Example 1, except that the formulation was changed to that shown in Table 2. Note that in Example 11 as well, the nonwoven fabric was changed to S0703WDO.

[0258] Example 8 Aerosil® R812 and MQ resin were placed in a 225 mL glass bottle and mixed for 5 minutes at 2000 rpm using a hybrid mixer (ARE-250, available from Thinky Corporation, Chiyoda-ku, Tokyo, Japan). The modified silicone was then added and the mixture was subjected to a hybrid mixer and shaken at 2000 rpm for 5 minutes, then shaken with a roller set at about 25 rpm for at least 12 hours to obtain a pressure-sensitive adhesive composition.

[0259] A laminate for evaluation of Example 8 was obtained in the same manner as in Example 1, except that this pressure-sensitive adhesive composition was used.

[0260] Comparative Example 1 Dowsil® 4584 was added to a 225 mL glass bottle, and toluene and Dowsil® NC-25 were added to it. The mixture was placed in a hybrid mixer (ARE-250, available from Thinky Corporation, Chiyoda-ku, Tokyo, Japan) and shaken at 2000 rpm for 5 minutes, and then shaken with a roller set at about 25 rpm for 12 hours or more to obtain a pressure-sensitive adhesive composition.

[0261] A laminate for evaluation of Comparative Example 1 was obtained in the same manner as in Example 1, except that this pressure-sensitive adhesive composition was used and the nonwoven fabric was changed to T0703WDO.

[0262] The laminates for evaluation of Examples 1 to 14 and Comparative Example 1 were subjected to the above-mentioned evaluations, and the results are shown in Table 2.

[0263] [Table 2-1]

[0264] [Table 2-2]

[0265] Examples 15 to 20 Laminates for evaluation of Examples 15 to 20 were obtained in the same manner as in Example 2, except that an embossing pattern with a composition and a sea-island structure (the embossed portion is the sea portion, and the non-embossed portion is the island portion) shown in Table 3 was used. In the embossing pattern shown in Table 3, the pitch interval of the non-embossed portions (island portions) corresponds to the pitch interval b in FIG. 2, and the embossing depth corresponds to the embossing depth h in FIG. 2.

[0266] The laminates for evaluation of Examples 15 to 20 were subjected to the above-mentioned evaluations, and the results are shown in Table 3.

[0267] [Table 3]

[0268] Examples 21 to 24 Except for changing the nonwoven fabric to the nonwoven fabric shown in Table 4, the same procedure as in Example 17 was carried out to obtain laminates for evaluation of Examples 21 to 24.

[0269] The laminates for evaluation of Examples 21 to 24 were subjected to the above-mentioned evaluations, and the results are shown in Table 4.

[0270] [Table 4]

[0271] Examples 25 to 29 Except for changing the nonwoven fabric to the nonwoven fabric shown in Table 5, the same procedure as in Example 17 was carried out to obtain laminates for evaluation of Examples 25 to 29.

[0272] The laminates for evaluation of Examples 25 to 29 were subjected to the above-mentioned evaluations, and the results are shown in Table 5.

[0273] [Table 5]

[0274] Examples 30 to 34 Except for changing the nonwoven fabric to the nonwoven fabric shown in Table 6, the same procedure as in Example 17 was carried out to obtain laminates for evaluation of Examples 30 to 34.

[0275] The laminates for evaluation of Examples 30 to 34 were subjected to the above-mentioned evaluations, and the results are shown in Table 6.

[0276] [Table 6]

[0277] Experimental Example 2 In Experimental Example 2, a release liner having a non-fluorine-based, non-silicone-based release layer (sometimes referred to as an "NSNF release liner") that is applicable to a pressure-sensitive adhesive layer containing modified silicone was investigated.

[0278] Various materials used in Example 2 are shown in Table 7. Here, for HCA-32, HCA-32 (2-tetradecyl octadecyl acrylate) was synthesized from the esterification reaction of 2-tetradecyl-1-octadecanol (iso-C32 alcohol) and acryloyl chloride using the reaction conditions and purification method disclosed in Method 2 on pages 8-9 (column 14, line 63 to column 15, line 8) of U.S. Patent No. 8,137,807.

[0279] [Table 7]

[0280] Precursor polymers 2-9 Precursor polymers 2 to 9 were obtained in the same manner as the above-mentioned precursor polymer 1, except that the formulation was changed to the formulation shown in Table 8.

[0281] [Table 8]

[0282] Release Liner 2~9 Release liners 2 to 9 were obtained in the same manner as the release liner 1 described above, except that precursor polymers 2 to 9 shown in Table 8 were used for release liners 2 to 9, respectively. Here, for precursor polymers 8 and 9, these precursor polymers were diluted to 1.06% by mass with a mixed solvent of toluene / MEK / n-heptane (34% by mass / 33% by mass / 33% by mass).

[0283] Preparation of pressure-sensitive adhesive tape using the produced release liner The tape samples evaluated were prepared in two ways.

[0284] (1) Applying the pressure sensitive adhesive solution onto the prepared release liner (direct application) 50 parts by weight of SPU33K and 50 parts by weight of XR37-B1795 were mixed to prepare a pressure-sensitive adhesive solution. The prepared release liner was coated with the pressure-sensitive adhesive solution and dried at 105°C for 10 minutes. The dried pressure-sensitive adhesive layer had a thickness of about 50 micrometers. A release liner FD-75 was applied onto the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.

[0285] (2) Applying the prepared release liner to the pressure sensitive adhesive layer (dry lamination) The release liner FD-75 was coated with the above pressure-sensitive adhesive solution and dried at 105° C. for 10 minutes. The dried pressure-sensitive adhesive layer had a thickness of about 50 micrometers. The prepared release liner was applied onto the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.

[0286] The adhesive tapes produced were subjected to the following evaluations, and the results are shown in Tables 9 to 12.

[0287] Peel strength test: Peel strength of the pressure-sensitive adhesive layer to the release layer of the prepared release liner The release liner FD-75 was peeled off from the pressure-sensitive adhesive tape, and a polyester film (COSMOSHINE (trademark) A4100) was attached to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape. The polyester film was then attached to a SUS panel via a double-sided tape. The peel strength of the prepared release liner (NSNF release liner) was measured at a peel speed of 300 mm / min in a 180 degree direction using a precision universal testing machine (Shimadzu Corporation (Kyoto-shi, Kyoto, Japan)). Table 9 shows the test results of the adhesive tape prepared by direct application. Table 10 shows the test results of the adhesive tape prepared by direct application when it was aged in an environment of 50°C and 80% RH for several weeks. Table 11 shows the test results of the adhesive tape prepared by direct application and the adhesive tape prepared by dry lamination.

[0288] Residual Adhesion Test After the peel strength test, the polyester film with the pressure-sensitive adhesive layer remaining on the SUS panel was peeled off from the double-sided tape, and the pressure-sensitive adhesive layer exposed on the polyester film was attached to a SUS304 (BA) panel. After leaving it at room temperature for 30 minutes, the adhesive strength when the polyester film was peeled off in a 180° direction at a peeling speed of 300 mm / min was measured as the residual adhesive strength using a precision universal testing machine Autograph AG-X (Shimadzu Corporation (Kyoto-shi, Kyoto, Japan)). In addition, Table 12 shows the residual adhesive strength of the adhesive tape manufactured by the above-mentioned direct use method (1) using two fluorine-based release liners (FD-75) as Reference Example 1.

[0289] [Table 9]

[0290] The results in Table 9 confirm that, for example, a light release type release liner (peel strength less than 0.3 N / 25 mm) and a heavy release type release liner with a peel strength of 0.3 N / 25 mm can be produced separately.

[0291] [Table 10]

[0292] [Table 11]

[0293] [Table 12]

[0294] From the results in Table 12, it was confirmed that the residual adhesive strength of the pressure-sensitive adhesive layer in the NSNF release liner was equivalent to that of the fluorine-based release liner of Reference Example 1.

[0295] Experimental Example 3 In Experimental Example 3, wallpaper laminates prepared using a release liner having a non-fluorine-based and non-silicone-based release layer and a release liner having a fluorine-based release layer were investigated.

[0296] The various materials used in Experimental Example 3 are shown in Table 13.

[0297] [Table 13]

[0298] Example 59 The MQ resin and modified silicone were added to a 225 mL glass bottle in the prescribed amounts shown in Table 14, and the mixture was placed in a hybrid mixer (ARE-250, available from Thinky Corporation, Chiyoda-ku, Tokyo, Japan) and shaken at 2000 rpm for 5 minutes, and then shaken with a roller set at approximately 25 rpm for 12 hours or more to obtain a pressure-sensitive adhesive composition.

[0299] A fluororesin release liner FD-75 was coated with the pressure-sensitive adhesive composition using a wet gap of 0.25 to 0.26 mm to prepare a pressure-sensitive adhesive layer having a thickness of about 0.050 to about 0.065 mm. The coated pressure-sensitive adhesive sample 1 was dried in a 70°C oven for 10 minutes.

[0300] Similarly, Liner 1, the NSNF release liner described above, was coated with a pressure-sensitive adhesive composition using a wet gap of 0.25 to 0.26 mm to prepare a pressure-sensitive adhesive layer having a thickness of about 0.050 to about 0.065 mm. The coated pressure-sensitive adhesive sample 2 was dried in a 70° C. oven for 10 minutes.

[0301] Pressure-sensitive adhesive sample 1 was placed on one side of the nonwoven fabric layer, and pressure-sensitive adhesive sample 2 was placed on the other side of the nonwoven fabric layer, with the pressure-sensitive adhesive layer facing the nonwoven fabric layer, to obtain a laminate sample. This laminate sample was subjected to a pressure of about 0.3 kN / cm 2The laminate was passed through a heat press equipped with an embossing mold with a roughly hexagonal pattern at 115°C for 1 second under a pressure of 1000 psig, and then punched out to a size of 50 x 100 mm to obtain a laminate for evaluation. The embossing pattern of the obtained laminate had a roughly hexagonal sea-island structure, with a pitch interval of about 0.6 to about 0.7 mm between the non-embossed portions (island portions), and the embossing depth was about 0.1 mm.

[0302] The evaluation laminate of Example 59 was subjected to a holding power test, a damage-free peel test, and the following tests, and the results are shown in Table 14.

[0303] Peel strength test: Peel strength before and after embossing The release strength of the NSNF release liner (Liner 1) of the evaluation laminate before and after embossing was evaluated as follows. (1) Test pieces measuring 25 mm in width and 100 mm in length were taken from the laminate for evaluation before and after embossing. (2) The fluorine-based release liner FD-75 was peeled off. (3) After a stainless steel (SUS304BA) panel was washed with isopropyl alcohol, the pressure-sensitive adhesive layer of the test piece was attached to the stainless steel panel surface. (4) Using a universal material testing machine (TENSILON, available from A&D Company, Limited, Toshima-ku, Tokyo, Japan), the peel strength was measured when the NSNF release liner (Liner 1) of the test piece was peeled off in a 180 degree direction at a speed of 300 mm / min.

[0304] [Table 14]

[0305] Experimental Example 4 In Experimental Example 4, a wallpaper laminate produced using a rotary embossing method was investigated.

[0306] The various materials used in Experimental Example 4 are shown in Table 15.

[0307] [Table 15]

[0308] Release liner 10 was manufactured in the same manner as release liner 9, except that the base of release liner 9 was changed to EMBLET (trademark) SD-75, and release liner 11 was manufactured in the same manner as release liner 9, except that the base of release liner 9 was changed to EMBLET (trademark) SD-100 instead of the fluorine-based release liner FD-75.

[0309] Example 60 The MQ resin and modified silicone were added to a 225 mL glass bottle in the amounts shown in Table 16, and the mixture was placed in a hybrid mixer (ARE-250, available from Thinky Corporation, Chiyoda-ku, Tokyo, Japan) and shaken at 2000 rpm for 5 minutes, and then shaken with a roller set at approximately 25 rpm for 12 hours or more to obtain pressure-sensitive adhesive composition a.

[0310] A pressure-sensitive adhesive layer was prepared by coating pressure-sensitive adhesive composition a on a release liner 10 in the coating amount shown in Table 16. The coated pressure-sensitive adhesive sample was dried in an oven at 70° C. for 10 minutes.

[0311] A laminate sample was obtained by placing a pressure-sensitive adhesive sample on both sides of the nonwoven fabric layer so that the pressure-sensitive adhesive layer faced the nonwoven fabric layer. The laminate sample was passed through a heat press equipped with an embossing die patterned into a substantially hexagonal shape under the embossing conditions shown in Table 17 to obtain a laminate for evaluation. The embossing pattern of the obtained laminate had a substantially hexagonal sea-island structure, with a pitch interval of about 0.6 to about 0.7 mm between the non-embossed portions (island portions), and an embossing depth of about 0.1 mm.

[0312] Examples 61 to 64 In Example 61, the embossing conditions using the rotary embossing method were changed, and in Examples 62 to 64, release liner 10 was changed to release liner 11, and the embossing conditions shown in Table 17 were adopted. Except for this, evaluation laminates for Examples 61 to 64 were obtained in the same manner as in Example 60.

[0313] Examples 65 to 67 The evaluation laminates of Examples 65 to 67 were obtained in the same manner as in Example 60, except that the pressure-sensitive adhesive composition a and the coating amount were changed to the pressure-sensitive adhesive composition b and the coating amount shown in Table 16, the release liner was changed to FD-75, and the embossing conditions were changed to those shown in Table 17.

[0314] [Table 16]

[0315] Immediately after producing the evaluation laminates of Examples 60 to 67 by the rotary embossing method and when cutting, defects such as peeling of the release liner were visually observed and evaluated according to the following criteria, and the results are shown in Table 17. In Table 17, the pressure-sensitive adhesive layer located on the upper surface of the laminate is referred to as the "first pressure-sensitive adhesive layer," and the pressure-sensitive adhesive layer located on the lower surface is referred to as the "second pressure-sensitive adhesive layer." Here, the "upper surface" of the laminate refers to the surface located on the top roll side of the rotary embossing device, and the "lower surface" refers to the surface located on the bottom roll side of the rotary embossing device.

[0316] When embossing: A: No lifting or peeling of the release film was observed. B: Part of the release film was peeled off or lifted. C: Most of the release film was lifted or peeled off. D: The release film has been completely peeled off.

[0317] On disconnect: A: No lifting or peeling of the release film was observed. B: Part of the release film was peeled off or lifted. C: Most of the release film was lifted or peeled off. D: The release film has been completely peeled off.

[0318] [Table 17]

[0319] Experimental Example 5 In Experimental Example 5, the peelability of an article having a recess on the base surface to which the wallpaper laminate was attached was examined.

[0320] Example 68 A clip made of ABS resin and having the structure shown in Fig. 6 was prepared. The diameter of the circular part of this clip shown in Fig. 6(b) is about 3.8 cm, and the area of ​​the circular part is about 11 cm. 2 The height in the longitudinal direction in FIG. 6(c) was approximately 1.1 cm.

[0321] A laminate having the embossed pattern of Example 11 using SPU33K as the modified silicone, or a laminate having the embossed pattern of Example 10 using SPO20K as the modified silicone was produced. One release liner of this laminate was peeled off, and the laminate was attached to the base surface 610 of a clip via a pressure-sensitive adhesive layer so as to cover the eight recesses 612 in FIG. 6(e) but not to cover the joints 607.

[0322] Wallpaper (No. SP9924 in the catalog "SP2015-2017", Sangetsu Corporation, Nagoya-shi, Aichi, Japan) was cleaned with isopropyl alcohol. Next, the other release liner of the laminate was removed, and the laminate was attached to the wallpaper. Then, the clip was pressed with 10 kg for 5 seconds, and then left for 1 hour.

[0323] In all laminates, when the attached clip was picked up with the fingers and peeled off, only the clip could be peeled off, as shown in Figure 8. Next, the laminate could be removed from the wallpaper.

[0324] Reference example 2 In the configuration shown in FIG. 6, a clip made of ABS resin and having a substantially flat base surface excluding the joint portion was prepared.

[0325] The laminate of Example 10 or Example 11 was attached to this clip in the same manner as in Example 68, and the same operation as in Example 68 was carried out.

[0326] For both laminates, when the clip was pinched with the fingers to remove the attached clip, more effort was required as the clip was more difficult to remove than Example 68. Once the clip was successfully removed, the laminate was integrally attached to the backside of the clip.

[0327] Example 69 A clip made of ABS resin and having the structure shown in Fig. 7 was prepared. The diameter of the circular part on the front side of this clip was about 3.8 cm, and the area of ​​the circular part was about 11 cm. 2 The width in FIG. 7(a) was approximately 0.7 cm.

[0328] A laminate having the embossed pattern of Example 11 using SPU33K as the modified silicone, or a laminate having the embossed pattern of Example 10 using SPO20K as the modified silicone was produced. One release liner of this laminate was peeled off, and the laminate was attached to the base surface 710 of the clip via a pressure-sensitive adhesive layer so as to cover the second recess 714, the fifth recess 726, and the sixth recess 728 in FIG.

[0329] Wallpaper (No. SP9924 in the catalog "SP2015-2017", Sangetsu Corporation, Nagoya-shi, Aichi, Japan) was cleaned with isopropyl alcohol. Next, the other release liner of the laminate was removed, and the laminate was attached to the wallpaper. Then, the clip was pressed with 10 kg for 5 seconds, and then left for 1 hour.

[0330] In all laminates, when the attached clip was picked up with the fingers and peeled off, only the clip could be peeled off, as shown in Figure 8. Next, the laminate could be removed from the wallpaper.

[0331] Reference example 3 A clip made of ABS resin and having the same configuration as that shown in FIG. 7 was prepared, except that the portions of second recess 714, fifth recess 726, and sixth recess 728 in FIG. 7 were substantially flat.

[0332] The laminate of Example 10 or Example 11 was attached to this clip in the same manner as in Example 69, and the same operation as in Example 69 was carried out.

[0333] For both laminates, when the clip was pinched with the fingers to remove the attached clip, more effort was required as the clip was more difficult to remove than Example 69. Once the clip was successfully removed, the laminate was integrally attached to the backside of the clip.

[0334] It will be apparent to those skilled in the art that various modifications can be made to the above-described embodiments and examples without departing from the basic principles of the present invention. In addition, it will be apparent to those skilled in the art that various improvements and modifications can be made without departing from the spirit and scope of the present invention.

[0335] Explanation of symbols 100: Wallpaper laminate 101: First release liner 103: First pressure sensitive adhesive layer 105: Core layer (nonwoven fabric layer or foam layer) 107: Second pressure sensitive adhesive layer 109: Second release liner 200: Wallpaper laminate with release liner removed 203: First pressure sensitive adhesive layer 205: Core layer (nonwoven fabric layer) 207: Second pressure sensitive adhesive layer 600: Clip 601: Base 603: Clamp section 605: Support member 607: Joint 610: Base surface 612: Recess 700: Clip (integral) 701: Base 703: Clamp section 707: Hook part 710: Base surface 712: First recess 714: Second recess 722: Third recess 724: 4th recess 726: Fifth recess 728: 6th recess 801:Wallpaper 803: Wallpaper laminate 805: Goods 900: Intermediate parts 901: Release liner (first or second release liner) 903: Pressure-sensitive adhesive layer (first or second pressure-sensitive adhesive layer) 904: Release liner 1000: Roll body 1001: Release liner (first or second release liner) 1003: Pressure-sensitive adhesive layer (first or second pressure-sensitive adhesive layer) a: embossed top length b: Pitch interval h: embossing depth

Claims

1. A wallpaper laminate comprising: a first release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer; a first pressure-sensitive adhesive layer comprising a modified silicone; 12 g / m ２ a nonwoven fabric layer having a basis weight of at least a second pressure sensitive adhesive layer, The wallpaper laminate has an embossed pattern, A wallpaper laminate, wherein the first pressure sensitive adhesive layer is applicable and peelable from wallpaper.

2. 1. An article including a base, The wallpaper laminate according to claim 1 is attached to the back base surface of the article via a second pressure-sensitive adhesive layer; The article, wherein the base surface has at least one recess.

3. A wallpaper laminate comprising: a first release liner having a fluorine-based release layer or a non-fluorine-based and non-silicone-based release layer; a first pressure-sensitive adhesive layer comprising a modified silicone; A foam layer; a second pressure sensitive adhesive layer, A wallpaper laminate, wherein the first pressure sensitive adhesive layer is applicable and peelable from wallpaper.

4. The laminate of claim 1 , wherein the second pressure sensitive adhesive layer comprises a modified silicone.

5. The laminate of claim 1 , wherein at least one of the first and second pressure sensitive adhesive layers comprises 30 to 70 weight percent MQ resin.

6. 5. The laminate according to claim 4, wherein the modified silicone comprises at least one selected from the group consisting of silicone polyurea block copolymers, silicone polyoxamide block copolymers, and silicone polyoxamide-hydrazide block copolymers.

7. the modified silicone comprises at least one selected from the group consisting of a silicone polyoxamide block copolymer and a silicone polyoxamide-hydrazide block copolymer; The silicone polyoxamide block copolymers and silicone polyoxamide-hydrazide block copolymers comprise repeating units of Formula A: 【Chemistry 1】 (In formula A, Each R １ is independently alkyl, haloalkyl, aralkyl, alkenyl, or aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently an alkylene, an aralkylene, or a combination thereof; Each G is independently a bond or a group of formula R ３ HN-G-NHR ３ From the diamine, two -NHR ３ is a divalent residue equivalent to the group excluding Each R ３ is independently hydrogen or alkyl, or each R ３ is G and R ３ and G together with the nitrogen to which they are attached form a heterocyclic group; each n is independently an integer from 0 to 1500; each p is independently an integer from 1 to 10; Each q is independently an integer greater than or equal to 1, and at least 50% of the q's are the integer 2. The laminate of claim 4 comprising a copolymer comprising at least two of:

8. The first pressure-sensitive adhesive layer has an elastic modulus of 2×10 at −20° C. ５ Pa or more and 7×10 ７ The laminate according to claim 1, wherein the modulus is 0.1 Pa or less.

9. 2. The laminate of claim 1, wherein the wallpaper laminate comprises a second release liner, and the peel strength of the first pressure-sensitive adhesive layer to the release layer of the first release liner differs from the peel strength of the second pressure-sensitive adhesive layer to the release layer of the second release liner by a factor of 2.0 or more.

10. 10. The laminate of claim 9, wherein the release layers of the first release liner and the second release liner are non-fluorine-based and non-silicone-based release layers.

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