Building laminate and decorative film

Abstract

To provide an architectural laminate which can maintain a decorative appearance by exhibiting good weather resistance even when exposed to sunlight.SOLUTION: The architectural laminate comprises a transparent substrate layer 12, an adhesive layer 14, and a colored resin layer 16 in this order. The adhesive layer contains an acrylic adhesive polymer and an acrylic polymer additive. The glass-transition temperature of the acrylic adhesive polymer is from -70°C to -20°C. The glass-transition temperature of the acrylic polymer additive is from 20°C to 120°C. The content of the acrylic polymer additive in the adhesive layer is from 11 pts.mass to 40 pts.mass based on 100 pts.mass of the acrylic adhesive polymer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a building laminate and a decorative film.

Background Art

[0002] In vehicles, buildings, traffic signs, billboards, packaging materials, etc., decorative films or sheets in which an adhesive layer is provided on a film base material are widely used. For example, a transparent decorative film is useful as a painting alternative means in outdoor and indoor marking applications, such as glass decoration, backlight billboards, plastic coloring, etc. As an adhesive for decorative films, those having excellent adhesive properties in a wide temperature range from winter to summer are desired. As such an adhesive, an acrylic pressure-sensitive adhesive polymer having excellent weather resistance is widely used.

[0003] Patent Document 1 (Japanese Patent Laid-Open No. 10-310754) describes "a resin composition (1) having a weight average molecular weight of 800,000 or more, which is mainly composed of an alkyl (meth)acrylate having 1 to 12 carbon atoms in the alkyl group, contains a carboxyl group, and copolymerizes 0.5 to 10% by weight of a copolymerizable unsaturated monomer; and a resin composition (2) having a glass transition temperature (Tg) of 40°C or higher and a weight average molecular weight of 100,000 or less, which is mainly composed of one or more monomers selected from methacrylic acid alkyl esters or methacrylic acid cycloalkyl esters having 1 to 20 carbon atoms in the alkyl group, benzyl methacrylate, or styrene, contains an amino group, and copolymerizes 0.5 to 10% by weight of a copolymerizable unsaturated monomer. The adhesive composition contains the resin composition (2) in an amount of 1 to 40% by weight with respect to 100 parts by weight of the resin composition (1)".

[0004] Patent Document 2 (Japanese Patent Application Laid-Open No. 2012-021142) describes an acrylic resin solution containing an acrylic resin (A) obtained by polymerizing a monomer component (a) containing a (meth)acrylic acid alkyl ester monomer as a main component in the presence of an organic solvent (b) having a chain transfer constant of 250 or more to vinyl acetate in an organic solvent at 60°C, wherein the acrylic resin (A) has a weight average molecular weight of 50,000 to 300,000 and the solid content concentration of the resin solution is 60% or more.

[0005] Patent Document 3 (Japanese Patent Application Laid-Open No. 2014-108968) describes an adhesive composition containing (A) an acrylic copolymer, (B) a tackifier resin, and (C) an isocyanate crosslinking agent, wherein the acrylic copolymer (A) is an acrylic copolymer having a weight average molecular weight (Mw) of less than 300,000 with a content of a polymer having a molecular weight of 30,000 or less of less than 30% by weight, and the acrylic copolymer is a copolymer of monomers containing (a-1) an alkyl (meth)acrylate: 50 to 95.9% by weight, (a-2) a hydroxyl group-containing (meth)acrylate: 0.1 to 5% by weight, and the tackifier resin (B) consists of (b-1) a polymerized rosin ester and (b-2) a petroleum resin, and the reactivity of the polymer having a molecular weight of 30,000 or less separated from the acrylic copolymer (A) with the isocyanate crosslinking agent (C) is greater than the reactivity of the polymer having a molecular weight of 150,000 or more separated by GPC with the isocyanate crosslinking agent (C).

[0006] Patent Document 4 (Japanese Patent Application Laid-Open No. 2014-196442) describes an adhesive composition comprising at least an acrylic adhesive and an isocyanate compound as a crosslinking agent, wherein the acrylic adhesive is composed of an acrylic resin having a mass average molecular weight in the range of 50,000 to 300,000, and the isocyanate compound is contained in a solid ratio of 0.3 to 0.8 parts by weight with respect to 100 parts by weight of the acrylic adhesive.

[0007] Patent Document 5 (Japanese Patent Application Laid-Open No. 2013-010837) describes "a pressure-sensitive adhesive composition containing a first (meth)acrylic acid ester polymer (A) having a weight average molecular weight of 500,000 to 3,000,000, a second (meth)acrylic acid ester polymer (B) having a weight average molecular weight of 8,000 to 300,000, and a crosslinking agent (C), wherein the first (meth)acrylic acid ester polymer (A) and the second (meth)acrylic acid ester polymer (B) each substantially contain no acidic group and contain a hydroxyl group-containing monomer as a monomer unit constituting the polymer, the hydroxyl group-containing monomer contained in the first (meth)acrylic acid ester polymer (A) and the hydroxyl group-containing monomer contained in the second (meth)acrylic acid ester polymer (B) are of the same type, and the molar ratio of the hydroxyl group contained in the second (meth)acrylic acid ester polymer (B) to the hydroxyl group contained in the first (meth)acrylic acid ester polymer (A) is 1.0 to 40."

[0008] Patent Document 6 (Japanese Patent Application Laid-Open No. 2009-035602) describes "a pressure-sensitive adhesive composition containing a carboxyl group-containing (meth)acrylic pressure-sensitive adhesive polymer (1) having a weight average molecular weight of less than 800,000 and a glass transition temperature of -100°C to -30°C, and an amino group-containing (meth)acrylic non-pressure-sensitive adhesive polymer (2) having a weight average molecular weight of 30,000 to 100,000 and a glass transition temperature of 20°C to 90°C, and containing 1 part by mass or more and less than 20 parts by mass of the polymer (2) with respect to 100 parts by mass of the polymer (1)."

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

[0010] When a transparent decorative film is applied (internally pasted) to the indoor side of a glass substrate such as a window of a building, the adhesive contained in the transparent decorative film may deteriorate. The deterioration of the adhesive is specifically the decomposition of the pressure-sensitive polymer that is the main component of the adhesive, for example, an acrylic pressure-sensitive polymer, and is considered to be mainly caused by exposure to sunlight passing through the glass substrate (especially exposure to ultraviolet rays) and the continuous high-temperature environment created by the heat accumulated in the relatively thick glass substrate. It is generally known to improve the weather resistance of the transparent decorative film by including an ultraviolet absorber in the film substrate of the transparent decorative film. However, in the case of internal pasting, since the film substrate is located behind the adhesive layer with respect to sunlight, the ultraviolet absorber contained in the film substrate does not directly contribute to reducing the amount of ultraviolet rays incident on the adhesive layer. Thus, the deterioration of the adhesive in the transparent decorative film becomes a problem rather in internal pasting than in external pasting (applying the transparent decorative film to the outdoor side of the glass substrate). When the adhesive deteriorates, the cohesive force of the adhesive decreases, and the internal stress of the film substrate generated during construction overcomes the cohesive force of the adhesive, causing the transparent decorative film to shrink, or bubbles may occur between the transparent decorative film and the glass substrate. Therefore, it is desired to improve the weather resistance of the transparent decorative film including the adhesive layer.

[0011] The present disclosure provides a building laminate that can exhibit good weather resistance and maintain a decorative appearance even when exposed to sunlight. The present disclosure also provides a decorative film that can be used for such a building laminate. [Means for Solving the Problems]

[0012] The inventor has found that by adding a large amount of an acrylic polymer having a glass transition temperature within a specific range to an adhesive, the decrease in the cohesive force of the adhesive when exposed to sunlight is suppressed, and the weather resistance of the decorative film is improved.

[0013] According to one embodiment, there is provided a building laminate including a transparent base material layer, an adhesive layer, and a colored resin layer in this order, wherein the adhesive layer includes an acrylic pressure-sensitive adhesive polymer and an acrylic polymer additive, the glass transition temperature of the acrylic pressure-sensitive adhesive polymer is -70°C to -20°C, the glass transition temperature of the acrylic polymer additive is 20°C to 120°C, and the content of the acrylic polymer additive in the adhesive layer is 11 parts by mass to 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer.

[0014] According to another embodiment, there is provided a decorative film for a building laminate including an adhesive layer and a colored resin layer, wherein the adhesive layer includes an acrylic pressure-sensitive adhesive polymer and an acrylic polymer additive, the glass transition temperature of the acrylic pressure-sensitive adhesive polymer is -70°C to -20°C, the glass transition temperature of the acrylic polymer additive is 20°C to 120°C, and the content of the acrylic polymer additive in the adhesive layer is 11 parts by mass to 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer.

Effects of the Invention

[0015] According to the present disclosure, there are provided a building laminate that can exhibit good weather resistance and maintain a decorative appearance even when exposed to sunlight, and a decorative film that can be used for such a building laminate.

[0016] It should be noted that the above description should not be regarded as disclosing all embodiments of the present invention and all advantages related to the present invention.

Brief Description of the Drawings

[0017] [Fig. 1]It is a schematic cross-sectional view of a building laminate according to an embodiment. [Fig. 2] It is a photograph showing the results of weather resistance test 2 of Examples 1 to 4 and Comparative Examples 1 to 4.

Mode for Carrying Out the Invention

[0018] Hereinafter, for the purpose of exemplifying typical embodiments of the present invention, a more detailed description will be given with reference to the drawings, but the present invention is not limited to these embodiments.

[0019] In the present disclosure, “(meth)acrylic” means acrylic or methacrylic, and “(meth)acrylate” means acrylate or methacrylate.

[0020] In the present disclosure, the “film” includes an article called “sheet”.

[0021] In the present disclosure, “pressure-sensitive adhesion (property)” means the property of a material or composition that adheres to various surfaces with only a slight pressure applied for a short time within the use temperature range, for example, in the range of 0°C or higher and 50°C or lower, and does not exhibit a phase change (from liquid to solid). In the present disclosure, “adhesion (property)” is used interchangeably with “pressure-sensitive adhesion (property)”.

[0022] In the present disclosure, “disposed on top” includes not only the case of being directly disposed on top but also the case of being indirectly disposed on top, that is, via other materials or layers.

[0023] A building laminate according to an embodiment includes a transparent base material layer, an adhesive layer, and a colored resin layer in this order. A laminate including the adhesive layer and the colored resin layer, which is a part of the building laminate, can be regarded as a decorative film.

[0024] Examples of the transparent substrate layer include inorganic materials such as glass, quartz, and silica, organic materials such as polycarbonate, polyethylene terephthalate, acrylic resin, polyolefin, polyvinyl chloride, and polyurethane, or those containing a combination thereof. In one embodiment, the transparent substrate layer contains an inorganic material, preferably glass.

[0025] The thickness of the transparent substrate layer can vary. For example, it can be about 10 μm or more, about 50 μm or more, or about 100 μm or more, and about 20 mm or less, about 15 mm or less, or about 10 mm or less.

[0026] In one embodiment, the visible light transmittance of the transparent substrate layer is 50 - 100%, 70 - 100%, or 90 - 100%. In the present disclosure, the "visible light transmittance" means the average visible light transmittance at wavelengths of 380 nm to 780 nm measured in accordance with JIS A 5759:2008.

[0027] The adhesive layer contains an acrylic pressure - sensitive adhesive polymer and an acrylic polymer additive. Since the acrylic pressure - sensitive adhesive polymer has a glass transition temperature of - 70°C to - 20°C, which is lower than room temperature, pressure - sensitive adhesiveness is imparted to the adhesive layer at the use temperature (e.g., 5°C to 35°C). The acrylic pressure - sensitive adhesive polymer is generally a (meth)acrylate polymer or copolymer containing structural units derived from alkyl (meth)acrylates. When such a pressure - sensitive adhesive polymer is exposed to sunlight, the main chain of the pressure - sensitive adhesive polymer decomposes (depolymerizes), and its cohesive force decreases. Exposure to sunlight causes hydrolysis of the ester moiety of the side chain of the pressure - sensitive adhesive polymer, and the resulting alcohol acts as a plasticizer, which may also cause a decrease in the cohesive force of the pressure - sensitive adhesive polymer. Without being bound by any theory, it is considered that by adding a relatively large amount of an acrylic polymer additive having a high glass transition temperature of 20°C to 120°C to the acrylic pressure - sensitive adhesive polymer, the decrease in the cohesive force of the acrylic pressure - sensitive adhesive polymer caused by exposure to sunlight can be suppressed, and the adhesive force can be maintained at a desired level.

[0028] An acrylic pressure-sensitive adhesive polymer can be obtained by polymerizing or copolymerizing a polymerizable composition containing a (meth)acrylic monomer and, if necessary, a monomer having other monoethylenically unsaturated groups. In the present disclosure, the (meth)acrylic monomer and the monomer having other monoethylenically unsaturated groups are collectively referred to as polymerizable components. The (meth)acrylic monomer and the monomer having other monoethylenically unsaturated groups may each be used alone or in combination of two or more.

[0029] (Meth)acrylic monomers generally include alkyl (meth)acrylates. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate may be 1 to 12. Examples of the alkyl (meth)acrylate include linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-methylbutyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate; and alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate. The alkyl (meth)acrylate preferably includes n-butyl acrylate, 2-methylbutyl (meth)acrylate, 2-ethylhexyl acrylate, or a combination thereof.

[0030] Alkyl (meth)acrylate constitutes the main component of the acrylic pressure-sensitive polymer. In one embodiment, the acrylic pressure-sensitive polymer is obtained by copolymerizing a polymerizable composition containing alkyl (meth)acrylate in an amount of about 50% by mass or more, about 70% by mass or more, or about 80% by mass or more, about 99.5% by mass or less, about 99% by mass or less, or about 98% by mass or less based on the mass of the polymerizable components, and contains structural units derived from alkyl (meth)acrylate in the above mass ratio.

[0031] (Meth)acrylic monomers may include aromatic (meth)acrylates such as phenyl (meth)acrylate and p-tolyl (meth)acrylate; phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as methoxypropyl (meth)acrylate and 2-methoxybutyl (meth)acrylate; or cyclic ether-containing (meth)acrylates such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate.

[0032] (Meth)acrylic monomers or other monomers having a monoethylenically unsaturated group may include polar monomers copolymerizable with alkyl (meth)acrylates. Examples of the polar monomers include carboxy group-containing monomers such as (meth)acrylic acid, mono-hydroxyethyl phthalate (meth)acrylate, β-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, maleic acid; aminoalkyl (meth)acrylates such as aminoethyl (meth)acrylate, monoalkylaminoalkyl (meth)acrylates such as butylaminoethyl (meth)acrylate, dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA), N,N-dimethylaminoethyl methacrylate (DMAEMA), dialkylaminoalkyl (meth)acrylamides such as N,N-dimethylaminopropyl acrylamide (DMAPAA), N,N-dimethylaminopropyl methacrylamide, dialkylaminoalkyl vinyl ethers such as N,N-dimethylaminoethyl vinyl ether, N,N-diethylaminoethyl vinyl ether and other amino group-containing monomers; amide group-containing monomers such as (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; and unsaturated nitriles such as (meth)acrylonitrile. These polar monomers can enhance the cohesive force of the adhesive layer and improve the adhesive strength.

[0033] Examples of other monomers having a monoethylenically unsaturated group include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene; and vinyl esters such as vinyl acetate.

[0034] The acrylic pressure-sensitive polymer is preferably a carboxy group-containing (meth)acrylic polymer. The carboxy group-containing (meth)acrylic polymer can be obtained by copolymerizing a polymerizable composition containing a carboxy group-containing monomer as a polymerizable component. The carboxy group-containing (meth)acrylic polymer can enhance the cohesive force due to the presence of the carboxy group and improve the adhesive force. The carboxy group-containing (meth)acrylic polymer may also be able to enhance the adhesion between the transparent base material layer and / or the colored resin layer and the adhesive layer. As the carboxy group-containing monomer, (meth)acrylic acid is preferred.

[0035] In one embodiment, the carboxy group-containing (meth)acrylic polymer is obtained by copolymerizing a polymerizable composition containing a carboxy group-containing monomer in an amount of about 0.5% by mass or more, about 1% by mass or more, or about 2% by mass or more, and about 15% by mass or less, about 10% by mass or less, or about 8% by mass or less based on the mass of the polymerizable components, and contains structural units derived from the carboxy group-containing monomer in the above mass ratio.

[0036] The polymerization or copolymerization of the acrylic pressure-sensitive polymer can be carried out by radical polymerization. As the radical polymerization, known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used. It is advantageous to use solution polymerization which can easily synthesize high molecular weight polymers. As the polymerization initiator, for example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate; or azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionic acid) dimethyl, azobis(2,4-dimethylvaleronitrile) (AVN) can be used. The amount of the polymerization initiator used is generally about 0.01 part by mass or more, or about 0.05 part by mass or more, and about 5 parts by mass or less, or about 3 parts by mass or less based on 100 parts by mass of the polymerizable components.

[0037] The glass transition temperature (Tg) of the acrylic pressure-sensitive polymer is from about -70°C to about -20°C. In one embodiment, the glass transition temperature of the acrylic pressure-sensitive polymer is about -65°C or higher, or about -60°C or higher, about -25°C or lower, or about -30°C or lower. By setting the glass transition temperature of the acrylic pressure-sensitive polymer to about -70°C or higher, adhesive strength and holding power can be imparted to the adhesive layer. By setting the glass transition temperature of the acrylic pressure-sensitive polymer to about -20°C or lower, initial adhesiveness (tack) can be imparted to the adhesive layer when combined with an acrylic polymer additive.

[0038] The glass transition temperature (Tg) of the acrylic pressure-sensitive polymer can be determined as the calculated glass transition temperature using the following FOX equation (Fox, T. G., Bull. Am. Phys. Soc., 1 (1956), p. 123) assuming that each polymer is copolymerized from n types of monomers.

Equation

Equation

[0039] In one embodiment, the weight average molecular weight (Mw) of the acrylic pressure-sensitive polymer is about 150,000 or higher, about 200,000 or higher, or about 250,000 or higher, about 2,000,000 or lower, about 1,500,000 or lower, or about 1,000,000 or lower. In the present disclosure, the "weight average molecular weight" means the molecular weight converted by standard polystyrene by gel permeation chromatography (GPC) method.

[0040] As described above, the acrylic polymer additive is a component that suppresses the decrease in the cohesive force of the acrylic pressure-sensitive adhesive polymer due to exposure to sunlight and maintains the adhesive strength of the adhesive layer, and its glass transition temperature (Tg) is about 20°C to about 120°C. In one embodiment, the glass transition temperature of the acrylic polymer additive is about 30°C or higher, or about 45°C or higher, about 100°C or lower, or about 80°C or lower. By setting the glass transition temperature of the acrylic polymer additive to about 20°C or higher, the cohesiveness of the adhesive layer in a high-temperature environment such as in summer can be ensured. By setting the glass transition temperature of the acrylic polymer additive to about 100°C or lower, the adhesiveness in the normal temperature range can be ensured. The glass transition temperature of the acrylic polymer additive can be determined using the FOX equation in the same manner as the acrylic pressure-sensitive adhesive polymer.

[0041] The content of the acrylic polymer additive in the adhesive layer is about 11 parts by mass to about 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer. In one embodiment, the content of the acrylic polymer additive is about 12 parts by mass or higher, or about 15 parts by mass or higher, about 30 parts by mass or lower, or about 25 parts by mass or lower based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer. By setting the content of the acrylic polymer additive to about 11 parts by mass or higher based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, the decrease in the cohesive force of the acrylic pressure-sensitive adhesive polymer due to exposure to sunlight can be suppressed and the adhesive strength of the adhesive layer can be maintained. By setting the content of the acrylic polymer additive to about 40 parts by mass or lower based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, the low-temperature adhesiveness can be ensured.

[0042] In one embodiment, the content of the acrylic polymer additive in the pressure-sensitive adhesive layer is about 9% by mass or more, about 10% by mass or more, or about 11% by mass or more, and about 29% by mass or less, about 25% by mass or less, or about 20% by mass or less based on the mass of the pressure-sensitive adhesive layer. By setting the content of the acrylic polymer additive to about 9% by mass or more based on the mass of the pressure-sensitive adhesive layer, it is possible to suppress the decrease in the cohesive force of the acrylic pressure-sensitive adhesive polymer due to exposure to sunlight and maintain the adhesive strength of the pressure-sensitive adhesive layer. By setting the content of the acrylic polymer additive to about 29% by mass or less based on the mass of the pressure-sensitive adhesive layer, low-temperature adhesiveness can be ensured.

[0043] The acrylic polymer additive can be obtained by polymerizing or copolymerizing a polymerizable composition containing (meth)acrylic monomers and, if necessary, monomers having other monoethylenically unsaturated groups, in the same manner as the acrylic pressure-sensitive adhesive polymer. The types and contents of the monomers contained in the polymerizable composition can be determined using the above FOX formula so that the glass transition temperature of the acrylic polymer additive is about 20°C to about 120°C.

[0044] In one embodiment, the weight-average molecular weight (Mw) of the acrylic polymer additive is about 1,000 or more, about 5,000 or more, or about 10,000 or more, and about 200,000 or less, about 100,000 or less, or about 80,000 or less.

[0045] The acrylic polymer additive is preferably an amino group-containing (meth)acrylic polymer. The amino group-containing (meth)acrylic polymer can be obtained by copolymerizing a polymerizable composition containing an amino group-containing monomer as a polymerizable component. The amino group-containing (meth)acrylic polymer can capture trace metal ions contained in the inorganic material, such as iron ions, with amino groups when the transparent base material layer contains an inorganic material such as glass. Thereby, the depolymerization reaction of the acrylic pressure-sensitive adhesive polymer that can be catalyzed by metal ions activated by ultraviolet rays contained in sunlight under a high-temperature environment can be suppressed. As the amino group-containing monomer, dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA) and N,N-dimethylaminoethyl methacrylate (DMAEMA) are preferable.

[0046] When the acrylic pressure-sensitive adhesive polymer is a carboxy group-containing (meth)acrylic polymer, the acrylic polymer additive is preferably an amino group-containing (meth)acrylic polymer, and more preferably an amino group-containing (meth)acrylic polymer that does not contain monomer units derived from aromatic vinyl monomers (hereinafter also referred to as "amino group-containing non-aromatic (meth)acrylic polymer" in the present disclosure). The amino group-containing (meth)acrylic polymer can enhance the cohesive force of the adhesive layer and improve the adhesion characteristics of the adhesive layer by interacting with the carboxy group-containing (meth)acrylic polymer. Since the amino group-containing non-aromatic (meth)acrylic polymer has excellent compatibility with the carboxy group-containing (meth)acrylic polymer, the above interaction with the carboxy group-containing (meth)acrylic polymer can be made more effective.

[0047] The amino group-containing non-aromatic (meth)acrylic polymer does not contain a structural unit derived from an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene, vinylanthraquinone, (meth)acrylamide of aromatic amine, and (meth)acrylate of a hydroxyl group-containing aromatic compound. Examples of the aromatic amine include aniline, benzylamine, naphthylamine, aminoanthracene, aminoanthraquinone, and derivatives thereof. Examples of the hydroxyl group-containing aromatic compound include a hydroxyl group-containing compound corresponding to the above aromatic amine.

[0048] In one embodiment, the amino group-containing (meth)acrylic polymer is obtained by copolymerizing a polymerizable composition containing an amino group-containing monomer in an amount of about 0.5% by mass or more, about 1% by mass or more, or about 3% by mass or more, and about 20% by mass or less, about 15% by mass or less, or about 10% by mass or less based on the mass of the polymerizable components, and contains a structural unit derived from the amino group-containing monomer in the above mass ratio.

[0049] The pressure-sensitive adhesive layer can be formed on a colored resin layer, a transparent base material layer, or a liner using a pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive polymer, an acrylic polymer additive, and, if necessary, a crosslinking agent, a solvent, and / or other additives.

[0050] The crosslinking agent is not particularly limited as long as it can form a crosslink between the polymer chains of the acrylic pressure-sensitive adhesive polymer. For example, when the acrylic pressure-sensitive adhesive polymer is a carboxy group-containing (meth)acrylic polymer, an epoxy-based crosslinking agent, a bisamide-based crosslinking agent, an aziridine-based crosslinking agent, a carbodiimide-based crosslinking agent, an isocyanate-based crosslinking agent, etc. can be used as the crosslinking agent.

[0051] Examples of epoxy crosslinking agents include, for example, N,N,N’,N’-tetraglycidyl-1,3-benzenedimethanamine (trade names: TETRAD-X (Mitsubishi Gas Chemical Company, Inc., Chiyoda-ku, Tokyo, Japan), E-AX and E-5XM (both from Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)), and N,N’-(cyclohexane-1,3-diylbis(methylene))bis(diglycidylamine) (trade names: TETRAD-C (Mitsubishi Gas Chemical Company, Inc., Chiyoda-ku, Tokyo, Japan), and E-5C (Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)).

[0052] Examples of bisamide crosslinking agents include, for example, 1,1’-(1,3-phenylenedicarbonyl)bis(2-methylaziridine), 1,4-bis(ethyleneiminocarbonylamino)benzene, 4,4’-bis(ethyleneiminocarbonylamino)diphenylmethane, and 1,8-bis(ethyleneiminocarbonylamino)octane.

[0053] Examples of aziridine crosslinking agents include, for example, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] (trade names: Chemitec (registered trademark) PZ-33 (Nippon Shokubai Co., Ltd., Osaka, Japan), and Crosslinker CX-100 (DSM Coating Resins B.V., Zwolle, the Netherlands)).

[0054] Examples of carbodiimide crosslinking agents include, for example, Carbodilite V-03, V-05, and V-07 (all from Nisshinbo Chemical Inc., Chuo-ku, Tokyo, Japan).

[0055] Examples of isocyanate crosslinking agents include, for example, Coronate L and Coronate HK (both from Tosoh Corporation, Minato-ku, Tokyo, Japan).

[0056] The crosslinking agent can be used in an amount of about 0.01 parts by mass or more, about 0.02 parts by mass or more, or about 0.05 parts by mass or more, and about 0.5 parts by mass or less, about 0.4 parts by mass or less, or about 0.3 parts by mass or less, based on 100 parts by mass of the acrylic adhesive polymer.

[0057] Examples of the solvent include methanol, ethanol, hexane, heptane, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, etc., or a mixed solvent thereof.

[0058] Examples of other additives include a UV absorber, an antioxidant, a heat stabilizer, a filler, a tackifier, etc.

[0059] The thickness of the adhesive layer may vary, and for example, it can be about 5 μm or more, about 10 μm or more, or about 20 μm or more, and about 200 μm or less, about 100 μm or less, or about 50 μm or less.

[0060] In one embodiment, the visible light transmittance of the adhesive layer is about 50% to about 100%, about 70% to about 100%, or about 90% to about 100%.

[0061] The colored resin layer may be a transparent material or an opaque material. As the colored resin layer, for example, a film containing polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate, acrylic resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polystyrene, or polyamide can be used. The colored resin layer may be colored with a colorant such as a pigment or a dye. The colored resin layer may have a printed layer thereon.

[0062] In one embodiment, the colored resin layer contains polyvinyl chloride and a colorant. The colored resin layer containing polyvinyl chloride has excellent weather resistance.

[0063] The thickness of the colored resin layer may vary, for example, it can be about 5 μm or more, about 10 μm or more, or about 20 μm or more, and about 500 μm or less, about 300 μm or less, or about 200 μm or less.

[0064] In one embodiment, the visible light transmittance of the colored resin layer is about 10% or more, about 30% or more, or about 50% or more, and about 99% or less, about 97% or less, or about 95% or less.

[0065] The building laminate can be manufactured by attaching a decorative film including an adhesive layer and a colored resin layer onto a transparent base material layer. A decorative film of one embodiment includes a colored resin layer and an adhesive layer disposed on the colored resin layer, and the adhesive layer includes a solid content of an adhesive composition or a solid content of a reaction product of the adhesive composition.

[0066] FIG. 1 shows a schematic cross-sectional view of a building laminate of one embodiment. The building laminate 10 includes a transparent base material layer 12, an adhesive layer 14, and a colored resin layer 16 in this order. The building laminate 10 is manufactured by attaching a decorative film 20 including the adhesive layer 14 and the colored resin layer 16 onto the transparent base material layer 12. The building laminate 10 may be used such that the colored resin layer 16 and the adhesive layer 14 are located outdoors, that is, the decorative film 20 may be attached to the outdoor surface of the transparent base material layer 12. The building laminate 10 may be used such that the colored resin layer 16 and the adhesive layer 14 are located indoors, that is, the decorative film 20 may be attached to the indoor surface of the transparent base material layer 12.

[0067] The decorative film can be manufactured by known methods. For example, an adhesive composition is applied onto a liner by knife coating, bar coating, etc. and dried to form an adhesive layer. The adhesive layer may be heated using hot air, an oven, etc. during drying in order to react a crosslinking agent of an optional component. A colored resin layer can be laminated onto the obtained adhesive layer by a method such as dry lamination to manufacture a decorative film. A decorative film can also be manufactured by directly applying an adhesive composition onto the colored resin layer and drying it.

[0068] The colored resin layer and the adhesive layer may be in direct contact with each other, or other layers, such as a printing layer, a metal layer, a primer layer, etc., may be interposed between these layers. Another layer, such as a printing layer, a metal layer, a surface protection layer, a clear layer, etc., may be laminated on the surface of the colored resin layer on the side opposite to the adhesive layer. The surface of the colored resin layer in contact with the adhesive layer may be subjected to surface treatment such as corona treatment or plasma treatment.

[0069] The decorative film may have a liner on the surface of the adhesive layer on the side opposite to the colored resin layer. Examples of the liner, which is an optional component, include plastic materials such as polyethylene, polypropylene, polyester, and cellulose acetate, paper, and laminated paper of the plastic materials. These liners may have a surface subjected to a release treatment with silicone or the like. The thickness of the liner can usually be about 10 μm or more, or about 25 μm or more, about 500 μm or less, or about 200 μm or less.

[0070] The adhesive layer may be solid, porous, or foamed. The adhesive surface of the adhesive layer may be flat or may have irregularities. On the uneven adhesive surface, a convex portion containing the solid content of the adhesive composition or the solid content of the reaction product and a concave portion surrounding the convex portion are formed on the adhesive surface of the adhesive layer, and an adhesive surface including a communication passage formed to communicate with the outside defined by the concave portion between the surface of the transparent base material layer and the adhesive surface in a state of being adhered to the transparent base material layer is included. An example of a method for forming the uneven adhesive surface will be described below.

[0071] Prepare a liner having a release surface with a predetermined uneven structure. Apply an adhesive composition to the release surface of this liner and heat it if necessary to form an adhesive layer. Thereby, the uneven structure (negative structure) of the liner is transferred to the surface of the adhesive layer in contact with the liner (which becomes the adhesive surface in the decorative film), and an uneven adhesive surface having a predetermined structure (positive structure) is formed on the adhesive surface. The unevenness of the adhesive surface is designed in advance to include grooves capable of forming a communication passage when the convex portion is adhered to the transparent base material layer as described above.

[0072] The grooves in the adhesive layer may form grooves in a regular pattern by arranging grooves of a certain shape along a regular pattern on the adhesion surface, or may form grooves in an irregular pattern by arranging irregular grooves. When a plurality of grooves are formed to be arranged substantially parallel to each other, the arrangement interval of the grooves is preferably about 10 μm or more, or about 100 μm or more, about 2000 μm or less, or about 1000 μm or less. The depth of the groove (the distance from the adhesion surface to the bottom of the groove measured in the direction toward the colored resin layer) is usually about 10 μm or more and about 100 μm or less. The shape of the groove is not particularly limited as long as the effects of the present invention are not impaired. For example, the shape of the groove can be substantially rectangular (including trapezoidal), substantially semicircular, or substantially semi-elliptical in the cross section of the groove in the direction perpendicular to the adhesion surface.

[0073] In one embodiment, the visible light transmittance of the decorative film excluding the liner is about 10% or more, about 30% or more, or about 50% or more, about 99% or less, about 97% or less, or about 95% or less.

[0074] The building laminate can also be manufactured by forming an adhesive layer on a transparent base material layer instead of the colored resin layer and laminating the colored resin layer on the adhesive layer.

[0075] In a building laminate according to one embodiment, the transparent base material layer constitutes at least a part of a wall or a window of a building, has a first surface and a second surface opposite to the first surface, the adhesive layer is disposed on the second surface of the transparent base material layer, and the colored resin layer is visually recognized through the first surface of the transparent base material layer. The building laminate of this embodiment can be manufactured by disposing (inner pasting) the decorative film on the indoor side when viewed from the transparent base material layer.

[0076] In one embodiment, the visible light transmittance of the building laminate is about 10% or more, about 30% or more, or about 50% or more, about 99% or less, about 97% or less, or about 95% or less.

[0077] The building laminate and the decorative film of the present disclosure can be used for the purpose of decorating walls and windows of buildings, and are particularly suitable for inner pasting applications.

Examples

[0078] In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited thereto. All parts and percentages are by mass unless otherwise specified.

[0079] Table 1 shows the materials used for producing the decorative film and the building laminate.

[0080] [Table 1]

[0081] Example 1 An adhesive composition containing an adhesive polymer 1 (ADH1), an amino group-containing acrylic polymer (AAP1), and a crosslinking agent 1 (CL1) was prepared. The mass ratio of ADH1, AAP1, and CL1 was 100:15:0.15 based on the non-volatile content. The adhesive composition was applied onto Film 1 (FL1) using a knife coater. The adhesive layer was dried at 95°C for 5 minutes. After drying, an adhesive layer with a thickness of 30 μm was obtained. The adhesive layer and a release liner 1 (RL1) were laminated to obtain the decorative film of Example 1.

[0082] Examples 2 to 18, Comparative Examples 1 to 10 Decorative films were obtained in the same procedure as in Example 1 except that the type of the adhesive polymer, the blending amount of AAP1, the type and blending amount of the crosslinking agent, or the type of the film were changed as shown in Table 2.

[0083] Thermal shrinkage The decorative film was cut into test pieces with a width of 50 mm and a length of 100 mm. The test pieces were attached onto an aluminum panel with a roller in an environment at 23°C and left for 24 hours in the environment at 23°C. Cross cuts were made on the test pieces with a cutter. Then, the test pieces were heated at 65°C for 48 hours. After heat aging, the shrinkage amount (mm) of the film was measured with a microscope, and the maximum value was recorded.

[0084] Weather resistance test 1 The decorative film was cut into a 65 mm square to prepare test pieces. The test pieces were attached to a 3 mm thick float glass panel (AGC Inc., Chiyoda-ku, Tokyo, Japan) at room temperature using a squeegee to prepare a laminate. The laminate was exposed to xenon light using a xenon weather resistance test apparatus Ci5000 Weather-Ometer (Tokyo Seiki Seisakusho Co., Ltd., Kita-ku, Tokyo, Japan). The test conditions conformed to JIS K 5600-7-7:2008. The xenon light was irradiated from the glass panel side for 500 hours. When no shrinkage or bubbles were observed in the test piece, it was evaluated as "A". When shrinkage of the test piece was observed but no bubbles were observed, it was evaluated as "B". When both shrinkage and bubbles of the test piece were observed, it was evaluated as "C".

[0085] Weather Resistance Test 2 The decorative film was cut into a 65 mm square to prepare test pieces. The test pieces were attached to a float glass panel (AGC Inc., Chiyoda-ku, Tokyo, Japan) at room temperature using a squeegee to prepare a laminate. The laminate was exposed to xenon light using a xenon weather resistance test apparatus Ci5000 Weather-Ometer (Tokyo Seiki Seisakusho Co., Ltd., Kita-ku, Tokyo, Japan). The test conditions conformed to JIS K 5600-7-7:2008. The xenon light was irradiated from the glass panel side for 2500 hours. When no shrinkage or bubbles were observed in the test piece, it was evaluated as "A". When shrinkage and bubbles of the test piece were observed but no bubbles were observed, it was evaluated as "B". When both shrinkage and bubbles of the test piece were observed, it was evaluated as "C".

[0086] The evaluation results of the decorative films of Examples 1 to 18 and Comparative Examples 1 to 10 are shown in Table 2.

[0087]

Table 2

[0088] The results of Weather Resistance Test 2 for Examples 1 to 4 and Comparative Examples 1 to 4 are shown in a photograph in Figure 2. In Figure 2, from the upper left in order are Example 1, Example 2, Example 3, and Example 4, and from the lower left in order are Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4.

[0089] It is obvious to those skilled in the art that the above embodiments and examples can be variously modified without departing from the basic principles of the present invention. It is also obvious to those skilled in the art that various improvements and modifications of the present invention can be implemented without departing from the spirit and scope of the present invention. A part of an embodiment of the present invention will be described below. [Aspect 1] A building laminate including a transparent base material layer, an adhesive layer, and a colored resin layer in this order, wherein the adhesive layer contains an acrylic pressure-sensitive adhesive polymer and an acrylic polymer additive, the glass transition temperature of the acrylic pressure-sensitive adhesive polymer is -70°C to -20°C, the glass transition temperature of the acrylic polymer additive is 20°C to 120°C, and the content of the acrylic polymer additive in the adhesive layer is 11 parts by mass to 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer. The building laminate. [Aspect 2] The building laminate according to Aspect 1, wherein the acrylic pressure-sensitive adhesive polymer is a carboxy group-containing (meth)acrylic polymer. [Aspect 3] The building laminate according to any one of Aspects 1 or 2, wherein the acrylic polymer additive is an amino group-containing (meth)acrylic polymer. [Aspect 4] The building laminate according to any one of Aspects 1 to 3, wherein the content of the acrylic polymer additive in the adhesive layer is 9% by mass to 29% by mass based on the mass of the adhesive layer. [Aspect 5] The building laminate according to any one of Aspects 1 to 4, wherein the visible light transmittance of the transparent base material layer is 50 to 100%. [Aspect 6] The building laminate according to any one of Aspects 1 to 5, wherein the transparent base material layer contains an inorganic material. [Aspect 7] The building laminate according to Aspect 6, wherein the transparent base material layer is glass. [Aspect 8] The building laminate according to any one of Aspects 1 to 7, wherein the visible light transmittance of the adhesive layer is 50 to 100%. [Aspect 9] The transparent base material layer constitutes at least a part of a wall or a window of a building, has a first surface and a second surface opposite to the first surface, the adhesive layer is disposed on the second surface of the transparent base material layer, and the colored resin layer is visually recognized through the first surface of the transparent base material layer. The building laminate according to any one of Aspects 1 to 8. [Aspect 10] The building laminate according to any one of Aspects 1 to 9, wherein the colored resin layer contains polyvinyl chloride and a coloring agent. [Aspect 11] A decorative film for a building laminate, including an adhesive layer and a colored resin layer, wherein the adhesive layer contains an acrylic pressure-sensitive adhesive polymer and an acrylic polymer additive, the glass transition temperature of the acrylic pressure-sensitive adhesive polymer is -70°C to -20°C, the glass transition temperature of the acrylic polymer additive is 20°C to 120°C, A decorative film in which the content of the acrylic polymer additive in the adhesive layer is 11 parts by mass to 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer.

Description of Symbols

[0090] 10 Building laminate 12 Transparent base material layer 14 Adhesive layer 16 Colored resin layer 20 Decorative film

Claims

1. An architectural laminate comprising a transparent base material layer, an adhesive layer, and a colored resin layer in this order, wherein the adhesive layer contains an acrylic pressure-sensitive adhesive polymer and an acrylic polymer additive, the glass transition temperature of the acrylic pressure-sensitive adhesive polymer is -70°C to -20°C, the glass transition temperature of the acrylic polymer additive is 20°C to 120°C, the content of the acrylic polymer additive in the adhesive layer is 11 parts by mass to 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, and the architectural laminate, wherein the transparent base material layer constitutes at least a part of a wall or window of a building and has a first surface and a second surface opposite to the first surface, the adhesive layer is disposed on the second surface of the transparent base material layer, the colored resin layer is visible through the first surface of the transparent base material layer, and the adhesive layer and the colored resin layer are located on the indoor side of the building. An architectural laminate.

2. The architectural laminate according to claim 1, wherein the acrylic pressure-sensitive adhesive polymer is a carboxy group-containing (meth)acrylic polymer.

3. The architectural laminate according to any one of claims 1 or 2, wherein the acrylic polymer additive is an amino group-containing (meth)acrylic polymer.

4. The architectural laminate according to any one of claims 1 to 3, wherein the content of the acrylic polymer additive in the adhesive layer is 9% by mass to 29% by mass based on the mass of the adhesive layer.

5. The architectural laminate according to any one of claims 1 to 4, wherein the visible light transmittance of the transparent base material layer is 50 to 100%.

6. The architectural laminate according to any one of claims 1 to 5, wherein the transparent base material layer contains an inorganic material.

7. The architectural laminate according to any one of claims 1 to 6, wherein the visible light transmittance of the adhesive layer is 50 to 100%.

8. The architectural laminate according to any one of claims 1 to 7, wherein the colored resin layer contains polyvinyl chloride and a coloring agent.

9. A decorative film for an architectural laminate, comprising an adhesive layer and a colored resin layer, wherein the adhesive layer contains an acrylic pressure-sensitive adhesive polymer and an acrylic polymer additive, the glass transition temperature of the acrylic pressure-sensitive adhesive polymer is -70°C to -20°C, the glass transition temperature of the acrylic polymer additive is 20°C to 120°C, A decorative film, wherein the content of the acrylic polymer additive in the pressure-sensitive adhesive layer is 11 parts by mass to 40 parts by mass based on 100 parts by mass of the acrylic pressure-sensitive adhesive polymer. The building laminate includes a transparent base material layer that constitutes at least a part of a wall or a window of a building and has a first surface and a second surface opposite to the first surface. When the decorative film is applied to the building laminate, the pressure-sensitive adhesive layer is disposed on the second surface of the transparent base material layer, the colored resin layer is visually recognized through the first surface of the transparent base material layer, and the pressure-sensitive adhesive layer and the colored resin layer are located on the indoor side of the building.

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