JP6395519B2 - Adhesive for glass-attached decorative sheet and decorative sheet using the same - Google Patents

Description

The present invention relates to an adhesive. More specifically, the present invention relates to a pressure-sensitive adhesive that is excellent in adhesive strength with glass, moisture and heat resistance, heat resistance, transparency, and hardness, and that is suitable for forming a pressure-sensitive adhesive layer of a decorative sheet used by being attached to glass.

In recent years, glass has opened and closed the front panel of the door body and the opening of the main body plane of articles such as refrigerators, washing machines, cupboards, and clothes racks due to its transparent design. It attracts attention as a member constituting the flat panel of the lid. However, glass has a problem that it has low impact resistance and is easily broken. Therefore, it has been proposed to attach a resin sheet (decorative sheet) with a design to the back side of the front panel made of glass and also to provide a scattering prevention function (for example, Patent Documents 1 and 2). However, these technologies have a problem that the adhesive strength is reduced and peels off in a high-temperature and high-humidity environment; when a decorative sheet is struck from the back side in the production process of the door body, the door body, etc. From the front side of the glass, and the problem that it is observed as a dent, which deteriorates the designability; and the front panel made of glass, the support frame, and the back in the production process of the refrigerator door body There is a problem that the glass and the decorative sheet are peeled off in the step of filling the space formed by the panel with the foamed heat insulating material, and an adhesive that can solve these problems is demanded.

As a technique for solving the problem of the pressure-sensitive adhesive in a high temperature and high humidity environment, for example, “(meth) acrylic acid ester, carboxyl group-containing monomer and hydroxyl group-containing monomer copolymerizable with the (meth) acrylic acid ester” An acrylic pressure-sensitive adhesive composition containing an acrylic copolymer (A) having a weight average molecular weight of 500,000 to 2,000,000, copolymerized with a monomer mixture (a) containing a crosslinking agent (B), With respect to 100 parts by mass of the acrylic copolymer (A), 0.05 to 1.6 parts by mass of a metal chelate crosslinking agent as the crosslinking agent (B) and 0.05 to 0.2 crosslinking agent having an epoxy group. An acrylic pressure-sensitive adhesive composition characterized in that it is blended with parts by mass "has been proposed (Patent Document 3). However, as a result of testing by the present inventor, it was not possible to solve the peeling problem and the dent problem in the foam insulation filling process.

JP 2014-062709 A JP 2010-060190 A JP 2011-032350 A

The object of the present invention is excellent in adhesive strength with glass, heat and humidity resistance, heat resistance, transparency, and hardness, and solves problems such as peeling in the foam insulation filling process, peeling in a high temperature and high humidity environment, and dents. Another object of the present invention is to provide a pressure-sensitive adhesive suitable for forming a pressure-sensitive adhesive layer of a decorative sheet used by being attached to glass. A further object of the present invention is to provide a decorative sheet suitable for application to glass.

As a result of intensive studies, the present inventor has found that the above-mentioned problems can be achieved by a pressure-sensitive adhesive having a specific composition.

That is, the present invention comprises (A) an acrylic polymer having a glass transition temperature of −50 to −25 ° C. 100 parts by mass; (B) a silane coupling agent having an epoxy group 0.01 to 3 parts by mass; (C) 1 A pressure-sensitive adhesive for a glass-attached decorative sheet, comprising: 0.01 to 0.5 parts by mass of a compound having two or more epoxy groups in the molecule; and (D) 0.01 to 0.5 parts by mass of an organic polyvalent metal compound. is there.

A second invention is a decorative sheet having a layer made of the pressure-sensitive adhesive described in the first invention.

A third invention is the decorative sheet according to the second invention, wherein the adhesion strength with glass is 5 N / 25 mm or more after heat treatment at a temperature of 60 ° C. for 10 minutes.

The fourth invention is a treatment in which an adhesive strength residual ratio with glass is exposed to an environment having a temperature of −30 ° C. and a relative humidity of 90% for 6 hours and then exposed to an environment of a temperature of 60 ° C. and a relative humidity of 90% for 6 hours Is a decorative sheet according to the second or third invention, which is 70% or more after a heat cycle treatment in which a total of 3 cycles is taken as one cycle.

According to a fifth aspect of the present invention, the residual strength of adhesion to glass is 70% or more after immersion in a sodium hydroxide aqueous solution having a concentration of 5% by mass and a temperature of 25 ° C. for 24 hours. It is a decorative sheet of any one of -4 invention.

6th invention has the layer of the transparent resin sheet, the adhesive bond layer, and the layer of the colored resin sheet in this order, The said adhesive bond layer is (p1) 100 mass parts of transparent adhesives; and (p2) average particle | grains And an adhesive comprising 0.01 to 9 parts by mass of glass particles coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. The decorative sheet according to any one of the second to fifth inventions.

A seventh invention is an article comprising the pressure-sensitive adhesive described in the first invention.

An eighth invention is an article comprising the decorative sheet according to any one of the second to sixth inventions.

The pressure-sensitive adhesive of the present invention is excellent in adhesive strength with glass, moisture and heat resistance, heat resistance, transparency, and hardness, and has problems such as peeling in the foam insulation filling process, peeling in a high temperature and high humidity environment, and dents. It has been resolved. Therefore, the pressure-sensitive adhesive of the present invention can be suitably used to form a pressure-sensitive adhesive layer of a decorative sheet that is used by being attached to glass. Moreover, the decorative sheet of the present invention can be suitably used for application to glass.

1. Adhesive The adhesive for a glass adhesive decorative sheet of the present invention comprises: (A) 100 parts by mass of an acrylic polymer having a glass transition temperature of −50 to −25 ° C .; (B) a silane coupling agent having an epoxy group 0.01 to 3 parts by mass; (C) a compound having two or more epoxy groups in one molecule 0.01 to 0.5 parts by mass; and (D) an organic polyvalent metal compound 0.01 to 0.5 parts by mass Part;

(A) Acrylic polymer having a glass transition temperature of -50 to -25 [deg.] C. The component A, as a main component of the pressure-sensitive adhesive, exhibits adhesiveness, and the components B to D and other optional components. It works to include.

The glass transition temperature of the component A is −50 ° C. or higher, preferably −40 ° C. or higher from the viewpoint of solving the problem of dents. On the other hand, it is −25 ° C. or less, preferably −30 ° C. or less from the viewpoint of improving the tackiness (initial adhesion).

In the present specification, the glass transition temperature of the component A is a calculated value obtained by a conventional method, that is, a value obtained from the following formula (Fox formula).
1 / (Tg + 273) = W ₁ / (Tg ₁ +273) + W ₂ / (Tg ₂ +273) + W ₃ / (Tg ₃ +273) +... + W _n / (Tg _n +273)
In the formula, Tg is a glass transition temperature (° C.) of a polymer composed of n types of monomers, and W ₁ , W ₂ , W ₃ ... W _n are each unit in the monomer composition. is the mass% of the _{dimer, Tg 1, Tg 2, Tg} 3 ··· Tg n is the glass transition temperature of the homopolymer of each monomer (° C.). As the Tg of each homopolymer, for example, those described in the polymer handbook can be used.

The component A is not limited except that the glass transition temperature is −50 to −25 ° C., and any acrylic polymer can be used. Examples of the acrylic polymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic acid. Hexyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester monomers such as palmitic acid and stearyl (meth) acrylate; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, and β-carboxyethyl (meth) acrylate; (meth) acrylic acid Glycidyl and 4-hydroxybutyl (me ) Epoxy group-containing monomers such as acrylate glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate A polymer comprising one or a mixture of two or more hydroxyl group-containing (meth) acrylic acid ester monomers such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; A copolymer can be mentioned. (Meth) acrylic acid means acrylic acid or methacrylic acid. (Meth) acrylate means acrylate or methacrylate. Commercial examples include “Acrybase LKG-1010 (trade name)” by Fujikura Kasei Co., Ltd., glass transition temperature of −34 ° C .; “Acrybase LKG-1012 (trade name)”, glass transition temperature of −35 ° C .; Acrybase LKG-1007 (trade name) ”, glass transition temperature −44 ° C., and the like. As said component A, these 1 type, or 2 or more types of mixtures can be used.

(B) Silane coupling agent having an epoxy group A silane coupling agent is a hydrolyzable group (e.g., an alkoxy group such as a methoxy group or an ethoxy group; an acyloxy group such as an acetoxy group; a halogen such as a chloro group). A silane compound having at least two different reactive groups such as an organic functional group (for example, amino group, vinyl group, epoxy group, methacryloxy group, acryloxy group, isocyanate group). As Component B of the present invention, a silane coupling agent having an epoxy group as an organic functional group is used. Component B can have a chemical bond or strong interaction with Component A or Component C by having an epoxy group. Thereby, moderate hardness is given to an adhesive and the problem of a dent can be solved. In addition, although component B has a hydrolyzable group, it has a hardness that can increase the adhesive strength with glass and solve the problem of dents, but it does not peel in the foam insulation filling process. The problem can be solved. Furthermore, since the organic functional group is an epoxy group, the miscibility with Component C or Component D is excellent.

Examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. can be mentioned. As said component B, these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component B is 0.01 parts by mass or more, preferably 0.03, from the viewpoint of solving the problem of peeling in the foam heat insulating material filling step and the problem of dents with respect to 100 parts by mass of the component A. More than part by mass. On the other hand, from the viewpoint of improving heat cycle resistance and alkali resistance, it is 3 parts by mass or less, preferably 1.5 parts by mass or less.

(C) Compound having two or more epoxy groups in one molecule The component C has two or more epoxy groups in one molecule, and is chemically bonded to or strongly interacts with the components A and B. be able to. Thereby, moderate hardness is provided to an adhesive and the problem of a dent can be solved. Further, it exhibits a specific high compatibility with the above component D, and can maintain adhesive strength and transparency even in a high temperature and high humidity environment.

The component C is clearly distinguished from the component B in that it does not have a hydrolyzable group. In the present invention, the compound having two or more epoxy groups in one molecule and having a hydrolyzable group is Component B.

Examples of the component C include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, and diglycidylamine. Bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. Can give. As said component C, these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component C is 0.01 parts by mass or more, preferably 0.03 parts by mass with respect to 100 parts by mass of the component A, from the viewpoint of solving the problem of dents and the problem in a high temperature and high humidity environment That's it. On the other hand, from the viewpoint of improving the heat-resistant adhesion, it is 0.5 parts by mass or less, preferably 0.3 parts by mass or less.

(D) Organic polyvalent metal compound The component D functions to assist the chemical reaction and interaction between the component C and the component A or component B. As a result, an appropriate hardness is imparted to the pressure-sensitive adhesive, and the problem of dents can be solved. In addition, it exhibits specific high compatibility with Component C, and can maintain adhesive strength and transparency even in a high temperature and high humidity environment.

As the component D, for example, a polyvalent metal such as aluminum, zirconium, and titanium is covalently or coordinately bonded to an organic compound such as an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. Can give you what

Examples of the organoaluminum compound include aluminum trisacetylacetonate, aluminum ethylacetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate, aluminum trisethylacetoacetate, aluminum ethylate, aluminum isopropylate, aluminum diacetate. Examples thereof include isopropylate monosecondary butyrate and aluminum secondary butyrate.

Examples of the organic zirconium compound include n-propyl zirconate, n-butyl zirconate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, and zirconium ethylacetoacetate.

Examples of the organic titanium compound include tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, and di-i-propoxy bis (acetyl). Acetonato) titanium, propanedioxytitanium bis, tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n- Butoxycarbonylbenzoyloxy) tributoxytitanium and di-n-butoxy-bis (triethanolaminato) titanium.

As said component D, these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component D is 0.01 parts by mass or more, preferably 0.03 parts by mass or more from the viewpoint of obtaining the effect of the component D with respect to 100 parts by mass of the component A. On the other hand, from the viewpoint of improving the heat-resistant adhesion, it is 0.5 parts by mass or less, preferably 0.3 parts by mass or less.

In the pressure-sensitive adhesive of the present invention, an optional component other than the components A to D can be further included as desired, as long as the object of the present invention is not adversely affected. Examples of the optional component include a photopolymerization initiator, a compound having two or more isocyanate groups in a molecule, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, and a printability improving agent. And additives such as antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, pigments, and fillers. The compounding quantity of the said arbitrary component is about 0.01-10 mass parts by making component A into 100 mass parts.

2. Decorative sheet The decorative sheet of the present invention is characterized by having a layer comprising the pressure-sensitive adhesive of the present invention. The decorative sheet of the present invention is not limited except that the layer composed of the pressure-sensitive adhesive of the present invention is usually provided on the side of the bonding surface with glass, and can be of any configuration. Hereinafter, a preferable embodiment will be described with reference to an example in which it is used by being attached to a glass front panel.

The thickness of the layer made of the pressure-sensitive adhesive of the present invention is not particularly limited, but may be usually 15 μm or more, preferably 20 μm or more from the viewpoint of adhesive strength. Moreover, from a viewpoint of thickness reduction, it may be 100 micrometers or less normally, Preferably it may be 60 micrometers or less.

A 1st aspect is a decorative sheet used by affixing on the back side of a glass front panel, and directly or on the surface of the transparent resin sheet on the front side (bonding surface side with glass). And a layer made of the pressure-sensitive adhesive of the present invention.

The transparent resin sheet is not limited and any transparent resin sheet can be used. For example, polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene and polymethylpentene; cellophane, triacetylcellulose, diacetylcellulose, acetylcellulose butyrate, etc. Cellulose resin: polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene resin such as styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / butadiene / styrene copolymer; polyvinyl chloride -Based resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; others, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone It may be mentioned a transparent resin sheet such as; nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. These sheets include an unstretched sheet, a uniaxially stretched sheet, and a biaxially stretched sheet. Moreover, the laminated sheet which laminated | stacked 1 or more types of these 2 or more layers is included. One or more of these can be used as the transparent resin sheet.

When the said transparent resin sheet is a lamination sheet, a lamination method is not restrict | limited, It can laminate | stack by arbitrary methods. For example, after each resin sheet is obtained by an arbitrary method, dry lamination or heat lamination is performed; each constituent material is melted by an extruder, and T-die co-processing by a feed block method, a multi-manifold method or a stack plate method is used. A method obtained by extrusion; an extrusion laminating method in which at least one resin sheet is obtained by an arbitrary method, and then another resin sheet is melt-extruded on the resin sheet; A method of applying and drying a paint containing a solvent, separating the formed resin sheet from the film substrate and transferring it onto another resin sheet, and a method of combining two or more of these; it can.

When the said transparent resin sheet is a lamination sheet, in order to improve a design feeling, you may emboss between arbitrary layers if desired.

When the said transparent resin sheet is a lamination sheet, in order to improve a design feeling, you may provide a printing layer between arbitrary layers if desired. The printing layer can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine. At this time, from the viewpoint of further enhancing the sense of depth, printing may be provided partially or using a transparent ink. Further, the print layer is not limited to 1, and may be 2 or more.

The method of forming the layer made of the pressure-sensitive adhesive of the present invention on the surface of the transparent resin sheet on the front side (bonding surface side with glass) directly or via an anchor coat is not limited and is publicly known. Web coating methods can be used. For example, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used. In forming the pressure-sensitive adhesive layer, the pressure-sensitive adhesive is diluted to a concentration at which it can be easily applied. If desired, known dilution solvents such as 1-methoxy-2-propanol, isopropanol, ethyl acetate, nbutyl acetate, toluene , Methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone can be used.

A colored resin sheet may be further laminated on the back surface of the transparent resin sheet.

The colored resin sheet is not limited, and any colored resin sheet can be used. For example, polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins; polycarbonate resins; poly (meth) acrylimide resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellophane, triacetyl Cellulosic resins such as cellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, and styrene / ethylene / butadiene / styrene Styrene resins such as copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; other, polyvinyl alcohol, ethyl It can be mentioned colored resin sheet such as; vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. These sheets include an unstretched sheet, a uniaxially stretched sheet, and a biaxially stretched sheet. Moreover, the laminated sheet which laminated | stacked 1 or more types of these 2 or more layers is included. One or more of these can be used as the colored resin sheet.

A printing layer may be provided between the transparent resin sheet and the colored resin sheet to enhance the design feeling, if desired. The said printing layer is provided in order to provide high designability to the decorative sheet of this invention, and it can form it by printing arbitrary patterns using arbitrary ink and arbitrary printing machines. Moreover, you may form the said printing layer as a concealing layer instead of a colored resin sheet.

Printing can be carried out directly or via an anchor coat on the back surface of the transparent resin sheet or on the front surface of the colored resin sheet, in whole or in part. The patterns include metal-like patterns such as hairlines, wood grain patterns, stone patterns imitating the surface of rocks such as marble, fabric patterns imitating cloth and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, And patchwork. As printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used. In addition, in order to give a metallic design, aluminum, tin, titanium, indium and oxides thereof are directly or via an anchor coat on the back surface of the transparent resin sheet or the front side of the colored resin sheet. The entire surface or a part of the surface may be deposited by a known method.

The lamination of the transparent resin sheet and the colored resin sheet is not particularly limited, and can be performed by any method. For example, methods such as thermal lamination and dry lamination can be used.

For the purpose of imparting a design with high brightness to the decorative sheet of the present invention, as an adhesive when dry-laminating the transparent resin sheet and the colored resin sheet directly or via an anchor coat or a printing layer (P1) 100 parts by mass of a transparent adhesive; and (p2) a surface having an average particle size of 10 to 250 μm, and the surface is coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. An adhesive containing 0.01 to 9 parts by mass of glass particles may be used.

The component p1 includes the component p2 and serves to bond the transparent resin sheet and the colored resin sheet. The component p1 is transparent in order to effectively exhibit the design effect due to the color of the component p2 and the colored resin sheet.

The component p1 is preferably not transparent when the decorative sheet is produced but also when an article including the decorative sheet is manufactured or used, and is preferably transparent.

As said component p1, it is not restrict | limited except having sufficient adhesive force and being transparent, Arbitrary adhesives can be used. For example, polyester, polyurethane, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, epoxy, polychloroprene, polyacryl, polymethacryl, polystyrene, polyamide, cellulose, And an adhesive comprising one or a mixture of two or more adhesives such as styrene-butadiene copolymer.

Among these, from the viewpoint of adhesive strength and transparency, polyester-based, polyurethane-based, polyvinyl chloride-based, polyacryl-based, polymethacryl-based, and polyvinyl acetate-based adhesives are preferable.

In the present specification, the “transparent adhesive” means an adhesive having a visible light transmittance of 30% or more, preferably 50% or more, more preferably 80% or more. Here, the visible light transmittance is a transmission spectrum at a wavelength of 380 to 780 nanometers of an adhesive using a spectrophotometer “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation and a quartz cell having an optical path length of 10 mm. This is a value calculated as a ratio of the integral area of the transmission spectrum of the adhesive to the integral area of the transmission spectrum when it is assumed that the transmittance in the entire range of wavelengths from 380 to 780 nanometers is 100%.

In this specification, the term “transparent adhesive” is used as a term including a transparent adhesive.

The component p2 serves to impart a high-luminance design to the decorative sheet as a high-luminance pigment and to effectively exert the design effect due to the color of the colored resin sheet.

The component p2 is a glass particle whose surface is coated with one or more metal oxides selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. The glass and the metal oxide are transparent substances, and the light reflected by the component p2, that is, the light reflected on the surface of the glass particles or the surface of the metal oxide coating layer is small, but the surface of the glass particles. Since a large path difference occurs depending on whether the light is reflected by the metal oxide coating layer or the metal oxide coating layer, even a small amount makes the human eye feel a high luminance feeling. Moreover, since much light permeate | transmits the component p2, the design effect by the color of the said colored resin sheet is not impaired.

Among the metal oxides, titanium oxide is preferable from the viewpoint of design.

The component p2 has an average particle size of 10 to 250 μm. When the average particle size is 10 μm or more, preferably 20 μm or more, more preferably 40 μm or more, both high brightness and the design effect by the color of the colored resin sheet can be achieved. Further, when the thickness is 250 μm or less, preferably 200 μm or less, more preferably 120 μm or less, the effect of making the dispersion unevenness of the component p2 inconspicuous and the design effect by the color of the colored resin sheet can be obtained.

In this specification, the average particle size is the cumulative particle size from the smaller particle in the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. The particle diameter is 50% by mass.

The compounding amount of the component p2 is 0.01 to 9 parts by mass with respect to 100 parts by mass of the component p1. When the blending amount is 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, a high luminance feeling can be obtained. Moreover, the design effect by the color of the said colored resin sheet can be acquired by being 9 mass parts or less, Preferably it is 5 mass parts or less, More preferably, it is 1 mass part or less.

Examples of the commercially available component p2 include “Metashine (trade name)” manufactured by Nippon Sheet Glass Co., Ltd.

The adhesive containing the high-intensity pigment can further contain optional components other than the component p1 and the component p2 as desired, as long as the object of the present invention is not adversely affected. Examples of the optional component include a photopolymerization initiator, a compound having two or more isocyanate groups in a molecule, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, and a printability improving agent. And additives such as antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, pigments other than component p2, and fillers. The compounding quantity of the said arbitrary component is about 0.01-10 mass parts with respect to 100 mass parts of component p1.

The method of applying the adhesive containing the high brightness pigment on the transparent resin sheet or the colored resin sheet directly or via an anchor coat is not particularly limited, and a known web coating method is used. can do. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. At this time, any dilution solvent such as 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary.

On the surface on the front side of the transparent resin sheet, a printing layer may be provided entirely or partially, directly or via an anchor coat. In order to make use of the transparency of the transparent resin sheet as a design, the printing layer may be provided partially or using a transparent ink. The method for providing the print layer has been described above.

The thickness of the decorative sheet of the present invention is not particularly limited, but may be usually 25 μm or more, preferably 35 μm or more, more preferably 45 μm or more from the viewpoint of imparting a scattering prevention function. Moreover, from a viewpoint of solving the problem of a dent more reliably, it may be usually 25 μm or more, preferably 50 μm or more, more preferably 100 μm or more. Further, from the viewpoint of meeting the demand for thinner articles, it may be usually 1500 μm or less, preferably 800 μm or less, more preferably 400 μm or less.

A 2nd aspect is a decorative sheet used by affixing on the back side of a glass front panel, and is directly or on the surface of the colored resin sheet on the front side (bonding surface side with glass). And a layer made of the pressure-sensitive adhesive of the present invention. A design can be given by the color of the colored resin sheet. Moreover, what exists in the back side (for example, foam heat insulating material etc.) can be concealed.

The colored resin sheet is not limited, and any colored resin sheet can be used. Specific examples have been described above. One or more of these can be used as the colored resin sheet.

The method of forming the layer made of the pressure-sensitive adhesive of the present invention on the surface of the colored resin sheet on the front side (bonding surface side with glass) directly or via an anchor coat is not limited and is publicly known. Web coating methods can be used. The specific method has been described above.

On the surface on the front side of the colored resin sheet, an arbitrary print layer may be provided on the entire surface or partially. The said printing layer is provided in order to provide high designability to the decorative sheet of this invention, and it can form it by printing arbitrary patterns using arbitrary ink and arbitrary printing machines. The method for providing the print layer has been described above.

The thickness of the decorative sheet of the second aspect is not particularly limited and is arbitrary. The preferred range has been described above in the description of the first aspect.

A 3rd aspect is a decorative sheet used by affixing on the front side of a glass front panel, and in order to make use of the transparency of glass as a design, preferably on the back side surface of the transparent resin sheet, directly or It has the layer which consists of an adhesive of this invention through an anchor coat. By sticking the decorative sheet to the front side of the front panel made of glass, the scattering prevention function is easily developed.

The transparent resin sheet is not limited and any transparent resin sheet can be used. Specific examples have been described above. One or more of these can be used as the transparent resin sheet.

The method of forming the layer made of the pressure-sensitive adhesive of the present invention on the surface of the transparent resin sheet on the back side (bonding surface side with glass) directly or via an anchor coat is not limited, and is publicly known. Web coating methods can be used. The specific method has been described above.

An arbitrary print layer may be provided on the front surface of the transparent resin sheet and / or on the back surface. The said printing layer is provided in order to provide high designability to the decorative sheet of this invention, and it can form it by printing arbitrary patterns using arbitrary ink and arbitrary printing machines. In order to make use of the transparency of glass as a design, the printing layer is preferably provided partially or using a transparent ink. The method for providing the print layer has been described above.

It is preferable to have a surface protective layer on the outermost surface on the front side of the decorative sheet of the third aspect. The damage resistance and solvent resistance of the decorative sheet can be improved.

An example of the surface protective layer is a hard coat. As the paint used for forming the hard coat, those having high transparency and high gloss are preferable from the viewpoint of design. Examples of such a hard coat forming coating material include an active energy ray-curable resin composition.

The active energy ray-curable resin composition can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. Examples of the composition include a compound having two or more isocyanate groups (—N═C═O) and / or a photopolymerization initiator.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Methoxy) acryloyl group-containing bifunctional reactive monomers such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and dipentaerythritol Examples of the resin include one or more selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as hexaacrylate or the like, or one or more of the above as constituent monomers. As said active energy ray curable resin, these 1 type, or 2 or more types of mixtures can be used.

In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates A crosslinking agent can be used. These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. These can be used alone or in combination of two or more.

In addition, the active energy ray-curable resin composition includes an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain prevention agent, a printability improving agent, an antioxidant, and a weather resistance stabilizer as necessary. In addition, one or more additives such as a light-resistant stabilizer, an ultraviolet absorber, a heat stabilizer, a colorant, and a filler may be included.

Among the optional components used as necessary for the active energy ray-curable resin composition, fine particles having an average particle diameter of 1 nm to 300 nm can be exemplified. The hardness of the hard coat can be increased by using the fine particles in an amount of 1 to 300 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the active energy ray-curable resin component.

As the fine particles, either inorganic fine particles or organic fine particles can be used. Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal fine particles; metal sulfide fine particles; metal nitride fine particles; Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. These can be used alone or in combination of two or more.

In addition, for the purpose of increasing the dispersibility of the fine particles in the paint or increasing the hardness of the resulting hard coat, the surface of the fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; Coupling agent; Organic compound having an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group and allyl group and reactive functional group such as epoxy group; Surface treatment agent such as fatty acid and fatty acid metal salt You may use what was processed.

Among these, in order to obtain a hard coat having higher hardness, fine particles of silica and aluminum oxide are preferable, and fine particles of silica are more preferable. Examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd., Quartron (trade name) manufactured by Fuso Chemical Industries, Ltd., and the like.

The average particle diameter of the fine particles is usually 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of maintaining the transparency of the hard coat and ensuring the effect of improving the hardness of the hard coat. On the other hand, there is no particular lower limit on the average particle size, but normally available particles are at most about 1 nm at most.

In this specification, the average particle size of the fine particles is the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. It is the particle diameter at which the accumulation is 50% by mass.

Moreover, since the said active energy ray curable resin composition is diluted to the density | concentration which is easy to apply, it may contain the solvent as needed. The solvent is not particularly limited as long as it does not react with the components of the curable resin composition and other optional components or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components. For example, 1-methoxy-2-propanol, isopropanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone, and the like can be given.

The active energy ray-curable resin composition can be obtained by mixing and stirring these components.

The method for forming a hard coat using a paint such as an active energy ray-curable resin composition is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The thickness of the hard coat is not particularly limited, but is preferably 0.5 μm or more, more preferably 5 μm or more, from the viewpoint of trauma resistance and solvent resistance. On the other hand, from the viewpoint of web handling properties, the thickness of the hard coat is preferably 100 μm or less, and more preferably 50 μm or less.

The anchor coating agent used for forming the transparent anchor coat is not limited except that it is transparent, and for example, known ones such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane may be used. it can.

The method for forming the transparent anchor coat using the anchor coat agent is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The thickness of the transparent anchor coat is usually about 0.1 to 5 μm, preferably 0.5 to 2 μm.

As the surface protective layer, for example, a resin film having a high transparency and a high glossiness such as a vinylidene fluoride resin film and a biaxially stretched polyethylene terephthalate film and having an excellent damage resistance and solvent resistance is laminated. May be.

The vinylidene fluoride resin film can be obtained by forming a vinylidene fluoride resin film by an arbitrary method. Examples of the vinylidene fluoride resin include a vinylidene fluoride homopolymer and a copolymer containing 70 mol% or more of vinylidene fluoride as a structural unit, and one or a mixture of these. Can be used. Examples of the monomer copolymerized with vinylidene fluoride include ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride, ethylene trifluoride chloride, and vinyl fluoride. Or 2 or more types can be used. Further, within the range not contrary to the object of the present invention, the vinylidene fluoride resin includes a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent, a surfactant, a nucleating agent, Color materials, plasticizers and the like may be included.

The melting point of these vinylidene fluoride resins is usually in the range of 145 to 180 ° C., but it is preferable to use one having a melting point of 150 to 170 ° C. from the viewpoint of processability.

In this specification, a Diamond DSC differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. is used, and the sample is held at 230 ° C. for 5 minutes, then cooled to −50 ° C. at a temperature decrease rate of 10 ° C./min, The melting point was defined as the peak top on the highest temperature side in the melting curve obtained by performing DSC measurement with a temperature program of holding at 50 ° C. for 5 minutes and then heating to 230 ° C. at a rate of 10 ° C./min .

The method for laminating the transparent resin sheet and the vinylidene fluoride resin film is not limited and can be laminated by any method. For example, a method in which a transparent resin sheet and a vinylidene fluoride resin film are obtained by an arbitrary method, followed by dry lamination or heat lamination; each constituent material is melted in an extruder, and a feed block method or a multi-manifold method or A method obtained by T-die coextrusion by a stack plate method; an extrusion laminating method in which one of a transparent resin sheet or a vinylidene fluoride-based resin film is obtained by an arbitrary method, and the other is melt-extruded thereon; it can.

The biaxially stretched polyethylene terephthalate film is widely commercially available, and any film can be used.

The method for laminating the transparent resin sheet and the biaxially stretched polyethylene terephthalate film is not limited and can be laminated by any method. For example, a method in which a transparent resin sheet and a biaxially stretched polyethylene terephthalate film are obtained by an arbitrary method and then dry laminated; an extrusion laminate method in which a transparent resin sheet is melt-extruded on a biaxially stretched polyethylene terephthalate film, etc. Can do.

Further, a hard coat may be formed directly or via an anchor coat on the biaxially stretched polyethylene terephthalate film or the vinylidene fluoride resin film.

The decorative sheet of the present invention has an adhesion strength with glass of preferably 15 N / 25 mm or more, more preferably 20 N / 25 mm or more, and further preferably 25 N / 25 mm or more. In consideration of reworkability, it may be preferably 50 N / 25 mm or less, more preferably 45 N / 25 mm or less. Here, the adhesion strength with glass is a value measured according to the following test (A).

The decorative sheet of the present invention has an adhesion strength with glass of preferably 5 N / 25 mm or more, more preferably 10 N / 25 mm or more, and further preferably 15 N / 25 mm or more after heat treatment at a temperature of 60 ° C. for 10 minutes. . Here, the adhesion strength with the glass after the heat treatment at a temperature of 60 ° C. for 10 minutes is a value measured according to the following test (b).

The decorative sheet of the present invention is exposed to an environment where the adhesive strength residual ratio with glass is -30 ° C. and a relative humidity of 90% for 6 hours, and then exposed to an environment of a temperature of 60 ° C. and a relative humidity of 90% for 6 hours. It is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more after the heat cycle treatment in which the treatment is one cycle for a total of 3 cycles. There is no particular upper limit on the adhesive strength residual rate. Here, the adhesion strength residual ratio with the glass after the heat cycle treatment under the above conditions is a value measured according to the following measurement method (c).

The decorative sheet of the present invention has an adhesive strength residual ratio of 5% by mass and a sodium hydroxide aqueous solution at a temperature of 25 ° C., after immersion for 24 hours, preferably 70% or more, more preferably 80%. More preferably, it is 90% or more. There is no particular upper limit on the adhesive strength residual rate. Here, the adhesion strength residual ratio with the glass after the immersion treatment under the above conditions is a value measured according to the following test (D).

3. Article The article of the present invention is such that, for example, the decorative sheet of the present invention including a layer made of the pressure-sensitive adhesive of the present invention is bonded to the back side or the front side of a glass front panel. Features. Therefore, the glass front panel of the article and the decorative sheet are adhered with sufficient strength, and problems such as peeling, whitening, and dents in a high temperature and high humidity environment are solved.

The article of the present invention includes articles such as refrigerators, washing machines, cupboards, and clothes racks; doors and lids of these articles; and all parts to be incorporated into the doors and lids.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measuring method (b) Adhesion strength of decorative sheet:
180 degree with respect to the test plate at a temperature of 23 ° C. at a rate of 300 mm / min according to JIS A 5759: 2008, using a float plate glass (thickness 3 mm) defined in JIS R3202: 2011 of Test Piece Co., Ltd. as a test plate The peel adhesion was measured.

(B) Heat-resistant adhesion:
After the heat treatment at a temperature of 60 ° C. for 10 minutes, the adhesive strength after the heat treatment was measured in the same manner as in the above test (A) except that the adhesive strength was measured.

(C) Heat cycle resistance:
After 6 hours of exposure in an environment at a temperature of −30 ° C. and a relative humidity of 90% for 6 hours, the exposure to an environment of a temperature of 60 ° C. and a relative humidity of 90% for 6 hours was performed for a total of 3 cycles. Except having measured adhesive force, it carried out similarly to the said test (I) and measured the adhesive force after a heat cycle. Subsequently, the ratio of the adhesive strength after the heat cycle with respect to the value of the test (A) was calculated.

(D) Alkali resistance:
Adhesive strength after immersion treatment was carried out in the same manner as in the above test (A) except that the adhesive strength was measured after performing immersion treatment for 24 hours in an aqueous sodium hydroxide solution having a concentration of 5 mass% and a temperature of 25 ° C. Was measured. Subsequently, the ratio of the adhesive strength after the immersion treatment with respect to the value of the test (A) was calculated.

(E) Scratch resistance:
From the decorative sheet side of the test piece prepared in the same manner as in the above test (I), the decorative sheet was visually observed from the glass surface side while pressing a 1 mm diameter stainless steel ball with a force of 1 N, and evaluated according to the following criteria: did.
○: The pressed part of the sphere cannot be visually recognized.
X: The location where the ball is pressed is clearly visible.

(F) Moisture and heat release resistance:
The adhesive strength after wet heat treatment was measured in the same manner as in the above test (A) except that the adhesive strength was measured after exposure to an environment of 60 ° C. and 98% relative humidity for 400 hours. Subsequently, the ratio of the adhesive strength after the immersion treatment with respect to the value of the test (A) was calculated.

(G) Moisture and heat whitening resistance:
In the above test (f), before measuring the adhesive strength after wet heat treatment, the adhesive layer was visually observed and evaluated according to the following criteria.
○: No change is observed in the transparency of the adhesive layer before exposure.
(Triangle | delta): It is recognized that it whitened compared with before exposure.
X: Clearly whitened.

(H) Reworkability:
After carrying out the test (A), the remaining state of the pressure-sensitive adhesive on the glass plate was visually observed and evaluated according to the following criteria.
〇: Not left at all.
Δ: Some remain ×: Remains on the entire surface

Raw material used (A) Acrylic polymer having a glass transition temperature of −50 to −25 ° C .:
(A-1) “Acrybase LKG-1010 (trade name)” by Fujikura Kasei Co., Ltd., glass transition temperature of −34 ° C., acid value of 1.9 mgKOH / g, molecular weight of 850,000.
(A-2) “Acrybase LKG-1007 (trade name)” by Fujikura Kasei Co., Ltd., glass transition temperature of −44 ° C., acid value of 2.1 mgKOH / g, molecular weight of 1 million.
(A-3) “Acrybase LKG-1001 (trade name)” by Fujikura Kasei Co., Ltd., glass transition temperature −40 ° C., acid value 7 mgKOH / g, molecular weight 1 million.

(A ′) Comparative acrylic polymer:
(A′-1) “Acrybase LKG-1011 (trade name)” by Fujikura Kasei Co., Ltd., glass transition temperature −53 ° C., acid value 1.9 mgKOH / g, molecular weight 1 million.
(A′-2) “Acrybase LKG-1101 (trade name)” by Fujikura Kasei Co., Ltd., glass transition temperature −22 ° C., acid value 0.3 mgKOH / g, molecular weight 430,000.

(B) Silane coupling agent having an epoxy group:
(B-1) 3-Glycidoxypropyltrimethoxysilane “KBM-403 (trade name)” of Shin-Etsu Chemical Co., Ltd.
(B-2) 3-Glycidoxypropyltriethoxysilane “KBE-403 (trade name)” of Shin-Etsu Chemical Co., Ltd.

(B ′) Comparative silane coupling agent:
(B′-1) 3-methacryloxypropyltrimethoxysilane “Z-6030 (trade name)” manufactured by Toray Dow Corning Co., Ltd.
(B′-2) 3-aminopropyltrimethoxysilane “KBM-903 (trade name)” of Shin-Etsu Chemical Co., Ltd.
(B′-3) Vinyltrimethoxysilane “KBM-1003 (trade name)” from Shin-Etsu Chemical Co., Ltd.
(B′-4) 3-Mercaptopropyltrimethoxysilane “KBM-803 (trade name)” from Shin-Etsu Chemical Co., Ltd.
(B′-5) 3-isocyanatopropyltriethoxysilane “KBM-9007 (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd.

(C) Compound having two or more epoxy groups in one molecule:
(C-1) 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane.

(D) Organic polyvalent metal compound:
(D-1) Aluminum trisacetylacetonate.

(E) Resin sheet:
(E-1) A transparent biaxially stretched polyethylene terephthalate-based resin film with easy adhesion treatment on both sides. Thickness 25 μm.
(E-2) Colored polyvinyl chloride resin film of black (lightness 2.3 measured according to JISZ8721: 1993). Thickness 80 μm.

Example 1
100 parts by mass of the component (A-1), 0.057 parts by mass of the component (B-1), 0.077 parts by mass of the component (C-1), and 0 of the component (D-1) in terms of solid content. 0.023 parts by mass was mixed and stirred to obtain an adhesive. Subsequently, printing was performed on one side of the above (E-1), and the above (E-2) was dry laminated on the formed printed layer. Furthermore, on the surface opposite to the surface on which the printing layer of (E-1) is formed, the adhesive obtained above is used, and the adhesive having a film thickness of 20 μm is used using a comma coating type coating apparatus. A layer was formed to obtain a decorative sheet. The above tests (a) to (h) were conducted. The results are shown in Table 1.

Examples 2-10, Comparative Examples 1-9
Except having changed the mixing | blending of the adhesive as shown in any one of Tables 1-3, it carried out similarly to Example 1 except having changed. The results are shown in any one of Tables 1-3.

Comparative Example 10
100 parts by mass of the component (A-1), 0.057 parts by mass of the component (B′-2), 0.077 parts by mass of the component (C-1), and the component (D-1) in terms of solid content. When 0.023 parts by mass of the mixture was mixed and stirred, the obtained pressure-sensitive adhesive was strongly yellowed. Since it is not preferable for a glass-fitted decorative sheet, the evaluation test was not performed.

Comparative Example 11
100 parts by mass of the component (A-1), 0.057 parts by mass of the component (B′-3), 0.077 parts by mass of the component (C-1), and the component (D-1) in terms of solid content. When 0.023 parts by mass of the mixture was mixed and stirred, the obtained pressure-sensitive adhesive was strongly cloudy. Since it is not preferable for a glass-fitted decorative sheet, the evaluation test was not performed.

Comparative Example 12
100 mass parts of said component (A-1) in conversion of solid content, 0.057 mass part of said component (B'-4), 0.077 mass part of said component (C-1), and said component (D-1) ) When 0.023 parts by mass was mixed and stirred, the resulting pressure-sensitive adhesive was strongly cloudy. Since it is not preferable for a glass-fitted decorative sheet, the evaluation test was not performed.

Comparative Example 13
100 mass parts of said component (A-1) in conversion of solid content, 0.057 mass part of said component (B'-5), 0.077 mass part of said component (C-1), and said component (D-1) ) When 0.023 parts by mass were mixed and stirred, the resulting pressure-sensitive adhesive was gelled. Therefore, the evaluation test was not performed.

The decorative sheet of the present invention having a layer made of the pressure-sensitive adhesive of the present invention expresses physical properties suitable for glass application. On the other hand, in the comparative example, at least one of adhesion strength, heat-resistant adhesion, heat cycle resistance, alkali resistance, dent resistance, moist heat and heat peel resistance, moist and heat whitening resistance, and reworkability is insufficient.

Application of high-luminance design As an adhesive for dry-laminating a transparent resin sheet and a colored resin sheet, (p1) 100 parts by mass of a transparent adhesive; and (p2) an average particle diameter of 10 to 250 μm on the surface is oxidized. The case where an adhesive containing 0.01 to 9 parts by mass of glass particles coated with one or more selected from the group consisting of titanium, indium oxide, zinc oxide, and tin oxide is used will be described with reference to examples. .

Measuring method (li) Brightness (luminance):
In a dark place, light from a 40 W white fluorescent lamp (300 lux) is incident perpendicularly from a position 50 cm away from the front surface of the multilayer resin sheet, and 45 ° from the front surface of the multilayer resin sheet. The multilayer resin sheet was visually observed from a position at an angle and a distance of 50 cm, and evaluated according to the following criteria.
A: The glitter is very high.
○: High brightness.
Δ: Low glitter.
X: There is almost no glitter.

(Nu) Transparency (design effect by color of the colored resin sheet):
In a dark place, light from a 40 W white fluorescent lamp (300 lux) is irradiated in parallel so that the surface on the front side of the multilayer resin sheet is separated from the light from the fluorescent lamp by a distance of 50 cm, and the multilayer resin sheet on the light source side The multilayer resin sheet was visually observed from a position at an angle of 45 ° with the surface on the front side and a distance of 50 cm, and evaluated according to the following criteria.
(Double-circle): The design effect by the color of a colored resin sheet is not impaired at all.
○: The design effect by the color of the colored resin sheet is hardly impaired.
(Triangle | delta): The design effect by the color of a colored resin sheet is impaired a little.
X: The design effect by the color of a colored resin sheet is spoiled greatly.

(Le) Darkness:
In a dark place, light from a 40 W white fluorescent lamp (300 lux) is irradiated in parallel so that the surface on the front side of the multilayer resin sheet is separated from the light from the fluorescent lamp by a distance of 50 cm, and the multilayer resin sheet on the light source side The multilayer resin sheet was visually observed from a position at an angle of 45 ° with the surface on the front side and a distance of 50 cm, and evaluated according to the following criteria.
A: Darkness is very high.
○: Darkness is high.
Δ: Low darkness.
X: There is no darkness.

Raw material (p1) transparent adhesive used:
(P1-1) Vinyl chloride / vinyl acetate / acrylic copolymer adhesive “VTP-NT (trade name)” from DIC Graphics, Inc., total light transmittance 92%.

(P2) Glass particles:
(P2-1) Titanium oxide coated glass particles “Metashine 1080RS (trade name)” manufactured by Nippon Sheet Glass Co., Ltd., particle size of 80 μm.
(P2-2) Titanium oxide-coated glass particles having a particle diameter of 20 μm.
(P2-3) Titanium oxide-coated glass particles having a particle diameter of 40 μm.
(P2-4) Titanium oxide-coated glass particles having a particle diameter of 120 μm.
(P2-5) Titanium oxide-coated glass particles having a particle diameter of 200 μm.

(P′2) Comparative component:
(P′2-1) Titanium oxide-coated glass particles having a particle diameter of 5 μm.
(P′2-2) Titanium oxide-coated glass particles having a particle diameter of 300 μm.
(P′2-3) Silver-coated glass particles “Metashine 1080PS (trade name)” manufactured by Nippon Sheet Glass Co., Ltd., particle size of 80 μm.

Example P1
On one side of the resin sheet (E-1), an adhesive containing 100 parts by mass of the component (p1-1) and 0.5 parts by mass of the component (p2-1) is dried to a thickness of 15 μm. It apply | coated using the knife coater, and after drying, the said resin sheet (E-1) was laminated on the conditions with the surface temperature of a lamination roll of 150 degreeC on the application surface. Subsequently, on the surface opposite to the dry laminate surface of the resin sheet (E-1), the pressure-sensitive adhesive prepared in Example 1 was used, and the adhesive having a film thickness of 20 μm was used using a comma coating type coating apparatus. An agent layer was formed to obtain a decorative sheet. The above (i) to (le) were evaluated. The results are shown in Table 4.

Examples P2-P9, Reference Examples P1-P5
Except having changed the raw material and compounding ratio to be used as shown in Table 4 or 5, it carried out similarly to Example P1. The results are shown in Table 4 or 5.

As an adhesive for dry laminating the transparent resin sheet and the colored resin sheet, (p1) 100 parts by mass of the transparent adhesive; and (p2) titanium oxide, indium oxide, zinc oxide on the surface having an average particle diameter of 10 to 250 μm, and By using an adhesive containing 0.01 to 9 parts by mass of glass particles coated with one or more selected from the group consisting of tin oxides, a design having a high brightness feeling is imparted to the decorative sheet of the present invention. can do.

It is a conceptual diagram which shows an example of the decorative sheet of this invention.

1: Adhesive layer 2: Transparent resin sheet layer 3: Colored resin sheet layer 4: Adhesive layer 5: Print layer

Claims (8)

(A) 100 parts by mass of an acrylic polymer having a glass transition temperature of −50 to −25 ° C .;
(B) Silane coupling agent having an epoxy group 0.01 to 3 parts by mass;
(C) 0.01 to 0.5 parts by mass of a compound having two or more epoxy groups in one molecule; and (D) 0.01 to 0.5 parts by mass of an organic polyvalent metal compound;
A pressure-sensitive adhesive for glass-applied decorative sheets.
A decorative sheet comprising a layer made of the pressure-sensitive adhesive according to claim 1.
The decorative sheet according to claim 2, wherein the adhesion strength with glass is 5 N / 25 mm or more after heat treatment at a temperature of 60 ° C for 10 minutes.
Residual strength of adhesion with glass is a cycle of 6 hours exposure in an environment with a temperature of −30 ° C. and a relative humidity of 90% for 6 hours and then an environment with a temperature of 60 ° C. and a relative humidity of 90%. The decorative sheet according to claim 2 or 3, wherein the decorative sheet is 70% or more after heat cycle treatment for 3 cycles.
5. The residual strength of adhesion to glass is 70% or more after immersion treatment in a sodium hydroxide aqueous solution having a concentration of 5 mass% and a temperature of 25 [deg.] C. for 24 hours. The decorative sheet according to item 1.
It has a layer of a transparent resin sheet, an adhesive layer, and a layer of a colored resin sheet in this order,
The adhesive layer is
(P1) 100 parts by mass of a transparent adhesive; and (p2) the surface of which has an average particle diameter of 10 to 250 μm and is coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide 0.01-9 parts by mass of glass particles;
The decorative sheet according to any one of claims 2 to 5, comprising an adhesive containing
An article comprising the pressure-sensitive adhesive according to claim 1.
An article comprising the decorative sheet according to any one of claims 2 to 6.

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