JP2001179899A - Decorative material having excellent weather resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material showing good weather resistance and good adhesion between a surface layer and a base material even when the surface layer giving surface properties such as flaw resistance and the like is formed on a polyolefin-based resin layer. SOLUTION: A decorative material S comprises a base material 1 such as a resin sheet or the like, a decorative treatment layer as indicated by a decorative layer 3 and a surface layer 2 wherein the surface layer 2 is composed of a crosslinked cured acryl-urethane resin from an acrylic polyol as a major agent and an aliphatic and/or alicyclic isocyanate as a crosslinking agent, the crosslinked cured acryl-urethane resin containing iso-octyl-3-(3-(2H- benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate represented by formula as a benzotriazole-based ultraviolet absorbing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building interior material, a surface decoration of a fitting, and a cosmetic material used for various cosmetic applications. In particular, the present invention relates to a decorative material having good weather resistance and adhesion to the surface layer even when the surface layer is formed on a layer that is difficult to adhere to, such as a polyolefin resin layer.

[0002]

2. Description of the Related Art Conventionally, as a decorative material, for example, a decorative sheet in the form of a sheet, a decorative sheet having a configuration in which a vinyl chloride resin sheet is used as a base material and which is subjected to decoration processing by printing, embossing or the like is used. Have been. However, since vinyl chloride resin emits hydrochloric acid gas when burned at the time of disposal, a cosmetic material using another resin containing no chlorine has been desired from the viewpoint of global environmental problems. Accordingly, in recent years, as a non-PVC-based decorative sheet, an olefin-based decorative sheet using a polyolefin-based resin sheet such as polyethylene, polypropylene, or an olefin-based thermoplastic elastomer as a base material (JP-A-54-62255, No. 6-79830). For example, as in the decorative material Sa illustrated in the cross-sectional view of FIG. 5, in order from the back side, the base material 31 includes a colored polyolefin-based resin layer, a decorative layer 32, an adhesive layer 33, and a transparent polyolefin-based resin layer. This is a decorative sheet having a configuration in which a transparent base material 34 is laminated.

[0003]

However, cosmetic materials having a polyolefin-based resin layer on the outermost surface have poor scratch resistance because the polyolefin-based resin has poor abrasion resistance. It was easy to happen. Therefore, there has been proposed a decorative material having a structure in which a surface layer made of an acrylic resin or the like is further provided on the surface of a polyolefin resin layer, such as a decorative sheet disclosed in Japanese Patent Application Laid-Open No. 3-243342. However, the surface layer made of an acrylic resin has a problem that the weather resistance is excellent, but the adhesion to the polyolefin resin layer is poor.

On the other hand, Japanese Patent Application Laid-Open No. 6-16832 discloses a decorative sheet having a surface layer formed of a two-component curable urethane resin or the like. Indeed, even when the surface of the surface layer is made of a polyolefin resin having generally poor adhesion, after the surface is subjected to corona discharge treatment, if a surface layer made of a two-component curable urethane resin is formed by coating, The adhesion between the surface layer and the polyolefin-based resin layer is improved. For example, as a two-component curable urethane resin,
In consideration of weather resistance, a two-component curable acrylic urethane resin using methyl methacrylate-2-hydroxyethyl methacrylate copolymer-based acrylic polyol as a main agent and hexamethylene diisocyanate as an aliphatic isocyanate as a curing agent is used. This is used to form a surface layer by applying a coating liquid of this resin.

[0005] However, although the initial adhesion immediately after the formation of the surface layer is good, the adhesion to the weather is insufficient, and the adhesion of the surface layer decreases with time. In a configuration having a polyolefin-based resin layer immediately below the surface layer, an organic ultraviolet absorber is usually added to the polyolefin-based resin layer in order to obtain weather resistance. (Bleed-out), and there was also a problem that the weather resistance of the surface layer was reduced with time.

[0006] Therefore, an object of the present invention is to provide a decorative material such as a decorative sheet having good weather resistance of the surface layer even when the surface layer is formed on the polyolefin resin layer.

[0007]

In order to solve the above-mentioned problems, a cosmetic material of the present invention comprises a decorative material-treated base material and a cosmetic material having a surface layer on the outermost surface. The layer is made of a cross-linked cured product of an acrylic urethane resin comprising a main component of an acrylic polyol and a cross-linking agent of an aliphatic and / or alicyclic isocyanate, and has a chemical structural formula as a benzotriazole-based ultraviolet absorber

Embedded image Represented by the formula: isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4
-A composition containing hydroxyphenylpropionate.

As described above, the surface layer is made of a crosslinked and cured product of a specific two-component curable acrylic urethane resin and contains a specific ultraviolet absorber, whereby the weather resistance of the surface layer is good. It can be used as a decorative material such as a decorative sheet. The surface layer can impart surface properties such as scratch resistance.

It is preferred that the ultraviolet absorber is contained in an amount of 2 to 3% by mass based on the resin content. If the above-mentioned ultraviolet absorber is used in this range, good weather resistance and adhesion can be obtained. If the ratio exceeds this range, problems such as a decrease in the initial adhesion of the surface layer and blocking are likely to occur.

Further, the cosmetic material of the present invention has a constitution in which a silicone slip agent is further contained in the surface layer. By containing the silicone slip agent, the scratch resistance is further improved.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the decorative material of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view illustrating some examples of the form of the decorative material of the present invention, and FIG. 2 is a cross-sectional view illustrating some examples of the form in which two layers of the base material are laminated with the decorative material of the present invention. 3 and 4 are cross-sectional views illustrating another embodiment of the decorative material of the present invention, and FIG. 5 is a cross-sectional view illustrating an example of a conventional decorative material.

[Summary] The decorative material of the present invention is, for example, shown in FIG.
Like the decorative material S illustrated in the cross-sectional view of (A), a base material 1 decorated in a sheet shape or the like and a surface layer 2 as a layer forming at least one outermost surface are decorative materials made of a specific material. . In the decoration process of the base material 1, in the case of FIG. 1A, a decoration layer 3 for expressing a pattern is formed on the back side (the lower side in the drawing) of the base material 1 by printing or the like. In the present invention, the surface layer 2 is made of a cross-linked cured product of an acrylic urethane resin composed of a main component of an acrylic polyol and a cross-linking agent of an aliphatic and / or alicyclic isocyanate. As a benzotriazole-based UV absorber, its chemical structural formula

Embedded image Represented by the formula: isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4
A specific UV absorber, hydroxyphenylpropionate;

As described above, the decorative material of the present invention is characterized in that the above-mentioned specific material is used for the surface layer 2 in order to improve the weather resistance of the surface layer. And
Various conventionally known configurations as a decorative material in the form of a decorative sheet or the like can be employed. Therefore, there is no particular limitation on the material of the base material and the contents of the decoration process. However, preferably, in some cases, the surface layer may be in contact with the substrate, the use of a chlorine-free resin polyolefin resin,
It is desirable in terms of environmental response. Further, the weather layer has good weather resistance even when the surface layer is provided in contact with a layer made of a polyolefin resin, which usually has poor adhesion. Therefore, in the layer configuration in which the base material is in contact with the surface layer as shown in FIG. 1A, a decorative material having a configuration using a polyolefin resin for the base material 1 is a decorative material having a preferable configuration.

Here, some of the other embodiments of the cosmetic material of the present invention will be exemplified. In the decorative material S illustrated in the cross-sectional view of FIG. 1B, the base material 1 is a base material that has been subjected to a coloring process in which a coloring agent such as a coloring pigment is kneaded into a resin and colored. This decorative material S has a configuration in which only the surface layer 2 is laminated on the colored base material 1. The resin of the substrate 1 is, for example, a polyolefin resin. The colored substrate 1 itself can also be referred to as the decorative layer 3. Further, a plurality of base materials may be stacked. For example, as in the case of the decorative material S illustrated in FIG. 1 (C), the base material 1a and the base material 1b are laminated as the base material 1 with the decoration layer 3 interposed therebetween, and the surface of the base material 1b on the front side is formed. This is a configuration in which a layer 2 is formed. For example, the substrate 1a is a colored opaque resin sheet such as a polyolefin resin, and the substrate 1b is a transparent resin sheet such as a polyolefin resin.

Hereinafter, the decorative material of the present invention will be described in detail for each layer in order from the substrate.

[Substrate] The shape, material and the like of the substrate 1 are basically not particularly limited. For example, the shape is typically a sheet, but it may be a plate, a three-dimensional object, or the like, and the material is paper, resin, metal, wood, inorganic nonmetal, or the like. A typical substrate is a resin sheet.

The base material is, for example, a sheet. When the material is resin, polyolefin resin such as polyethylene, polypropylene, olefin-based thermoplastic elastomer, acrylic resin, polyester resin, vinyl chloride resin, styrene resin, acrylonitrile-butadiene- Resin sheets (films) such as styrene copolymer (ABS resin) and cellulosic resin, and the material is paper, tissue paper, kraft paper,
For paper such as titanium paper, high quality paper, coated paper, and metal,
Metal foil such as aluminum, iron, stainless steel, and copper. The substrate may be a laminate of these.

When the form is a board, the base material may be wood veneer, wood plywood, particle board, wood board such as medium density fiber board (MDF), gypsum board, gypsum slag board, calcium silicate board, Cement board such as asbestos slate board, ALC (lightweight cellular concrete) board, hollow extruded cement board, pulp cement board, asbestos cement board, wood chip cement board, G
RC (glass fiber reinforced concrete) plate or inorganic non-metal plate such as ceramic plate made of ceramic, porcelain, set, earthenware, glass, enamel, etc., iron plate, galvanized steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, Metal plates such as copper plates, polyolefin resins such as polyethylene, polypropylene, and olefin thermoplastic elastomers, acrylic resins, polyvinyl chloride, styrene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), and thermoplastic resins such as polycarbonate Thermoplastic resin plate, phenolic resin, urea resin, unsaturated polyester resin, urethane resin, epoxy resin, thermosetting resin plate made of thermosetting resin such as melamine resin, phenolic resin,
So-called FRP (resin such as urea resin, unsaturated polyester resin, urethane resin, epoxy resin, melamine resin, diallyl phthalate resin, etc.) There is a resin plate such as a fiber reinforced plastic plate.

Examples of the base material having a three-dimensional structure include columnar objects made of various materials listed in the above-mentioned plate material, and three-dimensional objects having other shapes. For example, it is a pillar-shaped wood, a three-dimensional three-dimensional resin molded product, or the like.

When the substrate is a sheet, the decorative material obtained is a decorative sheet. When the substrate is a plate, the decorative material is a decorative plate, and when the substrate is a three-dimensional object, the decorative material is a decorative member or a cosmetic product. The thickness of the substrate is not particularly limited. For example, when the substrate is a resin sheet, the thickness is usually 20 to
It is about 300 μm.

When the base material is made of a resin, a polyolefin resin is one of the preferable resins in that it does not generate hydrochloric acid gas at the time of disposal and is environmentally friendly. In addition, a substrate made of a polyolefin resin is a preferable substrate in that the surface layer of the present invention can exhibit excellent weather resistance and adhesion to the polyolefin resin layer.
Therefore, the polyolefin-based resin will be further described.

Examples of the polyolefin resin include highly crystalline non-elastomeric polyolefins such as polyethylene (low density or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer and propylene-butene copolymer. Resin or various olefinic thermoplastic elastomers are used. As the olefin-based thermoplastic elastomer, for example, the following can be used.

(1) The soft segment described in JP-B-6-23278 (A) has a number average molecular weight Mn of 25,000 or more and a ratio Mw / Mn of the mass average molecular weight Mw to the number average molecular weight Mn. 10 to 90% by mass of atactic polypropylene soluble in boiling heptane of ≦ 7,
(B) A soft polypropylene comprising, as a hard segment, a mixture of 90 to 10% by mass of a heptane-insoluble isotactic polypropylene having a melt index of 0.1 to 4 g / 10 min.

Among the olefinic thermoplastic elastomers of this type, isotactic polypropylene which is less likely to cause so-called "necking" and has good suitability for forming into various shapes by heat and pressure or embossing is exemplified by isotactic polypropylene. The mixing ratio with the atactic polypropylene is 5% by mass or more and 50% by mass or less by mass ratio of the atactic polypropylene. The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when used in a conventionally known application such as a packaging container, the weight ratio of the atactic polypropylene as a soft segment is 5 to emphasize strength. Those having less than mass% were exclusively used. However, when forming or embossing into a three-dimensional shape or a concavo-convex shape, necking occurs as described above, and good processing cannot be performed. Therefore, contrary to the conventional design of the composition, in the olefin-based thermoplastic elastomer of polypropylene, the mass ratio of the atactic polypropylene is set to 5% by mass or more, thereby embossing or three-dimensional shape or the like. It is possible to eliminate non-uniform sheet deformation due to necking in forming an uneven article surface shape, and resulting defects such as wrinkles and pattern distortion. Particularly, the case where the mass ratio of the atactic polypropylene is 20% by mass or more is preferable. On the other hand, if the mass ratio of the atactic polypropylene increases too much, the sheet itself is easily deformed, and the sheet is deformed when the sheet is passed through a printing machine, the pattern is distorted, or the register is misregistered in the case of multicolor printing. And the like easily occur. Further, it is not preferable because it is easily broken during molding. As the upper limit of the mass ratio of the atactic polypropylene, the decorative layer is printed using a normal rotary printing machine such as rotary gravure printing, and embossing of the sheet, vacuum forming, V-cut processing, simultaneous lamination of injection molding, and the like. When employed, the content is 50% by mass or less, more preferably 40% by mass or less.

(2) A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin. Here, as the butene, any of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. Preferred specific examples of the ethylene-propylene-butene copolymer, which is a random copolymer and partially includes an amorphous portion, include the following (i) to (iii). (i) Those described in JP-A-9-111055. It is a random copolymer of a terpolymer of ethylene, propylene and butene. The mass ratio of the monomer components is 90% by mass or more of propylene. The melt flow rate is preferably 1 to 50 g / 10 minutes at 230 ° C. and 2.16 kg. And, for 100 parts by mass of such a ternary random copolymer, 0.01 to 50 parts by mass of a transparent nucleating agent containing a phosphate aryl ester compound as a main component,
It is obtained by melting and kneading 0.003 to 0.3 parts by mass of a fatty acid amide having 12 to 22 carbon atoms. (ii) Those described in JP-A-5-77371. this is,
80 to 0% by mass of a crystalline polypropylene is added to 20 to 100% by mass of an amorphous polymer having a propylene content of 50% by mass or more, which is a terpolymer of ethylene, propylene and 1-butene. It is. (iii) Those described in JP-A-7-316358. This is a terpolymer of ethylene, propylene, and 1-butene, and the content of propylene and / or 1-butene is 50% by mass or more and 20 to 100% by mass of the low crystalline polymer. 0.5% by mass of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester is added to a composition in which 80 to 0% by mass of a crystalline polyolefin such as isotactic polypropylene is mixed. It becomes.

The ethylene-propylene-butene copolymer resin may be used alone, or may be used in the above (i) to (iii).
If necessary, another polyolefin-based resin may be mixed and used.

(3) As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partial cross-linking Monoolefin copolymer rubbers such as ethylene-propylene copolymer rubber and unsaturated ethylene-propylene-non-conjugated diene terpolymer rubber are used as soft segments, and these are uniformly blended and mixed. . In addition,
Monoolefin rubber / olefin polymer = 50 / 50-
Mix at a ratio of 90/10 (mass ratio).

(4) As described in JP-B-53-34210, (B) an uncrosslinked monoolefin copolymer rubber (soft segment) and (A) an olefin copolymer (crystalline, hard segment) ) And a cross-linking agent, and is heated to apply shear stress to dynamically partially cross-link an olefin-based elastomer. (B) monoolefin rubber / (A) olefin copolymer = 60/40 to 80/20
(Mass ratio).

(5) As described in JP-B-56-15741, (A) isotactic polypropylene, propylene-ethylene copolymer, propylene-butene-1
A peroxide-decomposable olefin polymer (hard segment), which decreases its molecular weight when mixed and heated with a peroxide such as a copolymer to increase fluidity, and (B) ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene Peroxide-crosslinked monoolefin copolymer rubber (soft segment), which crosslinks and reduces fluidity by mixing and heating with a peroxide such as an original copolymer rubber, (C)
Peroxide non-crosslinked hydrocarbon rubber (soft segment / fluidity-modifying component) that does not crosslink even when mixed and heated with peroxides such as polyisobutylene and butyl rubber and has constant fluidity, and (D) paraffinic and naphthene An olefin-based elastomer obtained by mixing a mineral oil-based softener such as an oil-based or aromatic oil-based softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by mass, (B) is 10 to 60 parts by mass.
In parts by mass, (A) + (B) = 100 parts by mass.
(C) and / or (D) have a compounding ratio of 5 to 100 parts by mass.

(6) An olefin-based thermoplastic elastomer comprising an ethylene-styrene-butylene copolymer as described in JP-A-2-139232.

(7) The olefin-based thermoplastic elastomer according to the above (1) to (6), having a hydroxyl group and / or a carboxyl group as a polar group. For example, an olefin-based thermoplastic elastomer having a hydroxyl group introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like and a carboxyl group introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either or both of the hydroxyl group and the carboxyl group may be used in combination, and these polar groups have an effect of improving adhesion to other layers such as a decorative layer and a surface layer.

The above polyolefin resin can be formed into a sheet (film) by a film forming method such as a calendering method, an inflation method, a T-die extrusion method and the like.

When a resin is used as the substrate,
Various additives are appropriately added to the resin as needed. Additives include, for example, fillers such as calcium carbonate, inorganic powders such as clay, flame retardants such as magnesium hydroxide, antioxidants, foaming agents, lubricants, ultraviolet absorbers, light stabilizers, and various types of colorants such as colorants. Add additives.

In particular, in applications where improvement in weather (light) resistance is required, one or preferably both of a UV stabilizer such as a benzotriazole type and a light stabilizer such as a hindered amine-type ragashil scavenger are used as a light-resistant agent. It is preferable to improve the weather (light) resistance by adding it to the inside. The amount of addition is usually in the range of 0.1 to 5% by mass.

Further, the substrate may be subjected to a known adhesion strengthening treatment, if necessary. It is particularly desirable when a polyolefin-based resin is used for the substrate. The adhesion strengthening treatment is, for example, corona discharge treatment, plasma treatment, ozone treatment, or formation of an adhesion strengthening layer (see reference numeral 7 in FIG. 4) by coating or printing. Further, an adhesive layer may be used (see reference numeral 4 in FIGS. 2 and 4). The adhesion-enhancing layer and the adhesive layer may be appropriately selected from known primers and the like according to the material of the target layer and the like, and are made of, for example, a two-component curable urethane resin such as a thermosetting type. The layer may be formed by a coating method, a printing method, or the like.

When two or more base materials are used, a decorative layer or the like may be interposed therebetween, or the base materials may be laminated so as to be in direct contact with each other. For example, when the base material is made of a resin, a decorative layer or the like is required on the laminated surface of the formed resin sheet as the base material, in addition to laminating the resin sheets as the base material with an adhesive or heat fusion. Can be formed simultaneously with the formation of a resin layer as a substrate by a melt extrusion coating method (extrusion coating). The lamination of the resin sheets may be performed by a known lamination method such as a dry lamination method using an adhesive such as a two-component curing type polyurethane resin or a polyester resin, or a fusion method by hot pressing.

[Decoration treatment] As the decoration treatment for the base material, coloring (transparent coloring or opaque coloring) by adding a coloring agent to the base material itself when the base material is transparent with resin or the like.
[Refer to FIG. 1 (B)], the application of the decorative layer 3 by printing or the like for expressing a pattern or the like [refer to FIG. 1 (A)], the shaping of the concavo-convex pattern 5 by embossing etc. FIG. 3 (C)
Reference], etc. As described above, the decoration process may be any of various conventionally known decoration processes for a general decorative material such as a decorative sheet, and is not particularly limited. Various decoration processes may be used in combination as appropriate depending on the application.

(Coloring treatment) First, when the material of the base material is a transparent material such as a resin, the coloring treatment may be performed by kneading a coloring agent such as a dye or a pigment into the base material. Examples of coloring agents include inorganic pigments such as titanium white, zinc white, red petals, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine blue. ,
Organic pigments (or dyes) such as Indaslenbury RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate; Used. These are added to the substrate as powder, or scale-like foil pieces,
It is dispersed. The coloring may be transparent coloring or concealing coloring. However, when the base material on the upper side (surface layer side) of the decoration layer is colored, the coloring is transparent.

(Decoration Layer) The decoration layer 3 may be formed by a known printing method (or coating method) such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.
Alternatively, it is formed by ink (or paint) using a hand-drawing method or the like. Examples of the pattern of the decorative layer include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid surface. The decorative layer is on the side opposite to the surface layer forming surface of the substrate, or on the same side, or both.

As the ink (or paint), chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride
One or a mixture of two or more vinyl acetate copolymers, cellulose resins, and the like are used. A material obtained by adding a known coloring agent such as a pigment to the above is used.

The decorative layer may be a metal thin film layer. The metal thin film layer is formed using a metal such as aluminum, chromium, gold, silver, and copper by a method such as vacuum evaporation and sputtering. Alternatively, a combination of these may be used. The metal thin film layer may be provided on the entire surface or partially in a pattern.

(Shaping of Uneven Pattern) As the uneven pattern 5,
Wood-grained pipe conduits, stone-plate surface irregularities (granite cleavage planes, etc.), cloth surface texture, satin finish, grain, hairlines, and linear grooves. The uneven pattern is formed by embossing, hairline processing, or the like. For example, as the embossing, a substrate made of a resin sheet is heated and softened, pressurized and shaped with an embossing plate, and formed by cooling and fixing, and a known single-wafer or rotary embossing machine is used. Can be The uneven pattern is usually on the front side, but may be on the interlayer or the back side. As illustrated in FIG. 2 (D), if necessary, a known wiping method (Japanese Patent Publication No. 58-1)
No. 4312), the colored portion 6 can also be formed by filling a colored ink. The coloring ink can be the same as the decorative layer. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

(Example of Decoration Processing in the Case of Two-Layer Substrate) Here, some examples of the form in which two layers of the substrate are laminated are illustrated in the cross-sectional view of FIG. As the substrate 1 in the decorative material S shown in FIG. 2A, there are two layers, a transparent substrate 1b on the surface layer side and a colored substrate 1a. This is a decorative material having a configuration bonded and laminated by No. 4. Then, a surface layer 2 made of a specific material is formed on the surface of the transparent substrate 1b.
Are formed. Further, in the decorative material S of FIG.
The base material 1 is a two-layer base material 1a and a base material 1b similar to FIG. 2 (A). Between these, in addition to the adhesive layer 4, a base material further colored with the adhesive layer 4 is provided. Decoration layer 3 between material 1a
It is a makeup material of the composition provided with. In addition, the decorative material of FIG. 2C has a configuration in which the concavo-convex pattern 5 (which reaches the base 1b) is formed on the surface of the surface layer 2 in the configuration of FIG. 2B. . Further, the decorative material S in FIG.
In contrast to the configuration of (C), the decorative material has a configuration in which a colored portion 6 is further formed in the concave portion of the uneven pattern 5.
This is a configuration formed after the formation of the uneven pattern 5 and the colored portion 6. In each of FIGS. 2 (A) to 2 (D), the substrate 5
a is usually concealed coloring. In addition, these FIG.
In (D) to (D), the colored substrate 1a is basically a single-layer substrate such as a resin sheet. A sheet having a three-layer structure in which a resin layer to which no agent or filler is added may be used as the base material 5a that has been colored. The resin layer is formed by melt extrusion coating, multilayer melt extrusion, or the like.

[Surface Layer and Composition for Surface Layer] The surface layer 2 using a specific material is a layer for improving the surface physical properties of the decorative material such as abrasion resistance, solvent resistance, etc. It is a layer that can appropriately provide a feeling of design such as a gloss adjustment and a painted feeling, as appropriate.

The surface layer 2 is made of a cross-linked cured product of a two-component curable acrylic urethane resin whose main component is an acrylic polyol and a cross-linking agent is an aliphatic and / or alicyclic isocyanate. As a chemical structural formula

Embedded image Represented by the formula: isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4
-Contains a benzotriazole-based ultraviolet absorber such as hydroxyphenylpropionate.

As described above, as the curable urethane resin,
Acrylic polyol with excellent weather resistance is used as the main agent,
In addition, by using an aliphatic or alicyclic isocyanate excellent in weather resistance as a cross-linking agent, and using a specific benzotriazole-based UV absorber in combination with this resin, the weather resistance of the surface layer can be improved. Can be good. Therefore,
Good surface properties such as scratch resistance due to the surface layer can be maintained.

Examples of the acrylic polyol which is a main component of the acrylic urethane resin include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth).
(Meth) acrylic acid alkyl esters such as acrylate and octyl (meth) acrylate; and 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate An acrylic polyol obtained by copolymerizing a (meth) acrylate having a hydroxyl group in the molecule can be used.

Specific examples of such an acrylic polyol include methyl (meth) acrylate-2hydroxyethyl (meth) acrylate copolymer, octyl (meth) acrylate-ethylhexyl (meth) acrylate-2
There are hydroxyethyl (meth) acrylate copolymer, methyl (meth) acrylate-butyl (meth) acrylate-2 hydroxyethyl (meth) acrylate-styrene copolymer and the like. In addition, (meth) acrylate is
It means acrylate or methacrylate. Therefore, specifically, it is a methyl methacrylate-2 hydroxyethyl methacrylate copolymer or the like. In addition, the acrylic polyol which is a methyl methacrylate-2hydroxyethyl methacrylate copolymer is one of the preferred acrylic polyols in that good surface properties and weather resistance are obtained.

The monomers to be copolymerized to synthesize the acrylic polyol are one or more alkyl (meth) acrylates and one or more (meth) acrylates having a hydroxyl group in the molecule. Two or more,
If necessary, one or more other polymerizable monomers are used. For example, butyl methacrylate, 2-
Hydroxyethyl methacrylate and acrylic acid are copolymerized, or methyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and styrene are copolymerized.

The acrylic polyol to be used is not limited to one kind, and two or more kinds may be mixed and used. For example,
An acrylic polyol consisting of methyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate;
It is a mixture with acryl polyol composed of octyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. This mixed system is also a preferred use example of an acrylic polyol in that good surface properties and weather resistance are obtained.

On the other hand, as the isocyanate to be used as a crosslinking agent, aliphatic and alicyclic isocyanates are preferred in view of weather resistance. Therefore, in the present invention, an aliphatic and / or alicyclic isocyanate is used as the isocyanate. As the aliphatic or alicyclic isocyanate, a polyisocyanate having two or more isocyanate groups in a molecule is used. For example, 1,6-hexamethylene diisocyanate or the like is used as the aliphatic isocyanate, and isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or the like is used as the alicyclic isocyanate. Further, adducts of these various isocyanates,
Alternatively, a multimer such as a trimer can be used. The isocyanate used may be one or more aliphatic isocyanates, one or more alicyclic isocyanates, or a combination of an aliphatic isocyanate and an alicyclic isocyanate. You may.

A preferred embodiment of the mixing ratio of the acrylic polyol and the isocyanate is the number (mol number) of isocyanate groups (—NCO groups) in the isocyanate.
Is reacted with the hydroxyl group of the polyol (-OH group)
(Reaction equivalent number) to ensure that unreacted isocyanate groups remain in large numbers even after the polyol and isocyanate have reacted. In this case, the ratio of -NCO group / -OH group is up to about 1.4 at the maximum. By leaving the isocyanate group in the surface layer in this way, the ultraviolet absorber in the surface layer reacts with the hydroxyl group in the molecule, and the ultraviolet absorber bleeds out to the surface of the surface layer. Can be prevented. As a result, the effect of improving the weather resistance by the ultraviolet absorber is prevented from decreasing over time, and the weather resistance adhesion of the surface layer is prevented from decreasing over time. The same applies to the case where an ultraviolet absorber having a hydroxyl group in the molecule (for example, a benzotriazole-based ultraviolet absorber) is contained in the lower layer of the surface layer.

The content of the specific benzotriazole-based ultraviolet absorber is 2 parts per 100 parts by mass of the resin.
It is preferred that the content be contained in an amount of 2 to 3 parts by mass (2 to 3% by mass).
If the ultraviolet absorber is used in this range, good weather resistance can be obtained. On the other hand, if it exceeds this range, the adhesion of the surface layer becomes insufficient due to the initial adhesion, and problems such as occurrence of blocking easily occur. On the contrary, if it is less than this range, sufficient weather resistance cannot be obtained.

The surface layer is formed by diluting the uncured acrylic urethane resin comprising the acrylic polyol and the isocyanate with the specific benzotriazole-based ultraviolet absorber, usually with a diluting solvent. Then, a coating liquid (or ink) may be applied to a surface of the substrate or the like on which it is to be formed by a known coating method (or printing method), and then crosslinked and cured to form a crosslinked cured product. In addition, the coating method is gravure coating, roll coating, spray coating, etc., the printing method is gravure printing, screen printing, etc., depending on the shape, flexibility, and formation surface of the object to be formed of the surface layer as appropriate. Just choose.

For example, the surface layer may be formed by coating the decorative layer on a substrate made of a flexible resin sheet after printing, or by forming a two-layer substrate as shown in FIG. In the configuration,
For example, a decorative material may be formed by coating a transparent resin sheet substrate 1b and coating it with a colored resin sheet substrate 1a having the decorative layer 3 formed thereon.

Although the thickness of the surface layer depends on the application, it is usually 1 to 3.
It is about 20 μm. If the thickness is too thin, the effect of improving the surface physical properties, the effect of improving the weather resistance such as the weather resistance and adhesion by the ultraviolet absorber cannot be sufficiently obtained.
When a decorative material is used as a decorative sheet, its flexibility is reduced.

The surface layer itself is excellent in scratch resistance because it is a three-dimensional network polymer, but if it is necessary to further improve the scratch resistance, a silicone-based surface layer may be used. It is preferable to include a slip agent. As the silicone-based slip agent, a silicone-based slip agent having a dimethylsiloxane skeleton, a silicone-modified slip agent, or the like is used. A silicone-based slip agent with a dimethylsiloxane skeleton deteriorates the recoating property (suitability for post-coating) and the adhesiveness of cellophane tape (an adhesive tape or the like can be applied to the surface when using a cosmetic material). It is preferable in that it can be obtained. On the other hand, the silicone-modified slip agent has a better recoating property and cellophane tape adhesiveness than the silicone-based slip agent having a dimethylsiloxane skeleton, but has a poor slipping effect. The content of the silicone-based slip agent was 0.0 to 100 parts by mass of the resin component.
It is about 1 to 1 part by mass (% by mass).

Incidentally, the surface layer may be formed in a pattern with gloss on the surface. For example, as illustrated in the decorative material S of FIG. 3, a high gloss surface layer 2a is formed on the entire surface,
The low gloss surface layer 2b is partially formed. A gloss mat pattern can be expressed by a pattern of high gloss (gloss) and low gloss (mat). A matting agent (matting agent) may be added to the low gloss surface layer 2b. On the other hand, no matting agent is added to the high gloss surface layer 2a. Matting agent,
For example, a known matting agent made of a powder such as silica, alumina, and calcium carbonate may be used. The pattern of the low-gloss surface layer expressed by a mat is, for example, a wood grain conduit groove pattern. Needless to say, even when only one surface layer is provided, the entire surface may be made high gloss or low gloss such as mat.

[Applied Body of Decorative Sheet] The use of the decorative material obtained by the present invention is not particularly limited. For example, in the case of a decorative material in the form of a decorative sheet, the decorative material is laminated on the surface of various adherends and used for decorative purposes. Further, the decorative material in the form of a three-dimensional object is used as a decorative member or the like after being laminated on an adherend as necessary.

The adherend is a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, a sheet (or film), or the like. For example, wood veneer, wood plywood, particle board, wood material such as wood fiber board such as MDF (medium density fiber board), wood board material used as three-dimensional article, plate material such as iron and aluminum, three-dimensional article or Ceramics used as metal materials used as sheets, ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates, etc. -Based materials, acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber and other plate materials, three-dimensional shape A resin material used as an article or sheet, or High-quality paper to be used as,
Examples include paper such as Japanese paper, nonwoven fabric or woven fabric made of fibers such as carbon, asbestos, glass, and synthetic resin.

[Method of Laminating a Decorative Sheet on an Adherend] In the case where the decorative material is in the form of a decorative sheet, the method of laminating a decorative sheet on various adherends as described above includes, for example, an adhesive A method of laminating a plate-shaped substrate by pressing with a pressure roller with an agent interposed therebetween, JP-B-50-19
No. 132, Japanese Patent Publication No. 43-27488, etc., after a decorative sheet is placed between both male and female molds for injection molding, a molten resin is injected and filled into the mold to form a resin molded product. At the same time, a so-called simultaneous injection molding laminating method in which a decorative sheet is adhered and laminated on the surface thereof, Japanese Patent Publication No. 56-457.
No. 68, Japanese Patent Publication No. 60-58014, etc., a decorative sheet is opposed to or placed on the surface of a three-dimensional article such as a molded article with an adhesive therebetween, and the three-dimensional article side So-called vacuum press lamination method, which laminates a decorative sheet on the surface of a three-dimensional article by a pressure difference caused by vacuum suction from
As described in JP-B-61-5895 and JP-B-3-2666, a decorative sheet is supplied in the longitudinal direction of a columnar base material such as a column or a polygonal column via an adhesive therebetween. Meanwhile, there is a so-called lapping method in which decorative sheets are sequentially pressed and laminated on a plurality of side surfaces constituting a columnar substrate by a plurality of rollers having different directions.

As a further processing method for a decorative sheet obtained by laminating decorative sheets, Japanese Utility Model 15-311
No. 22, JP-A-48-47972, a decorative sheet is first laminated on a plate-like base material with an adhesive therebetween to form a decorative sheet, and the surface opposite to the decorative sheet is used. To
Cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped substrate, and then apply an adhesive in the groove and bend the groove to form a box or column. Is a so-called V-cut or U-cut processing method.

[Use of Cosmetic Material] The cosmetic material obtained by the present invention is used for various applications by laminating on various adherends or subjecting it to a predetermined molding process as required. For example, walls, ceilings,
For interior decoration of buildings such as floors, surface decoration of fittings such as window frames, doors, handrails, surface decoration of furniture or cabinets of light electric / OA equipment, interior decoration of vehicles such as cars, trains, aircraft, ships, etc., and makeup of window glass. is there.

[0064]

The present invention will be further described below with reference to examples and comparative examples. In the description, “parts” and “%” are all based on mass.

Example 1 As a decorative material, a decorative sheet having a layer structure as shown in FIG. 4 was produced as follows. As the color concealing base material 1a, an 80 μm-thick polypropylene-based thermoplastic elastomer (a hard segment composed of a polypropylene random copolymer and a soft segment composed of a hydrogenated styrene-butadiene rubber are mixed. After a corona discharge treatment is applied to both front and back surfaces of a resin sheet comprising titanium white, carbon black and graphite), a resin film having a thickness of 2 μm comprising a polyester polyol and 1,6-hexamethylene diisocyanate is formed on one surface thereof. An adhesion-enhancing layer 7 is formed by coating, on which a binder resin is a two-part curable acrylic urethane resin comprising methyl methacrylate-2-hydroxyethyl methacrylate copolymer acrylic polyol and 1,6-hexamethylene diisocyanate. , The coloring pigment is mainly red The decorative layer 3 having a wood grain pattern was formed by a gravure printing method using a colored ink.

On this decorative layer 3, a two-part curable acrylic urethane resin-based adhesive consisting of methyl methacrylate-2-hydroxyethyl methacrylate copolymer acrylic polyol and 1,6-hexamethylene diisocyanate was further added on a solids basis. An adhesive layer 4 was provided by coating so as to have a coating amount of 15 g / m ^2, and a non-colored transparent substrate 1 b was formed through the adhesive layer 4 as ethylene-propylene-1.
-Laminate a transparent 60-μm-thick olefin-based thermoplastic elastomer sheet made of a resin composition obtained by adding 8000 ppm of a benzotriazole-based UV absorber to a butene terpolymer, and emboss the surface of the substrate 1b by hot pressing. Thus, the uneven pattern 5 of the wood grain conduit groove was formed.

Next, on the surface on which the uneven pattern 5 is formed,
The main agent is an acrylic polyol of a methyl methacrylate-2-hydroxyethyl methacrylate copolymer system, and the crosslinking agent is 1,6-hexamethylene diisocyanate.
Chemical structural formula for liquid-curable acrylic urethane resin as an ultraviolet absorber

Embedded image Represented by the formula: isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4
An organic material containing 2% of a benzotriazole-based ultraviolet absorber (ultraviolet absorber A), which is a hydroxyphenylpropionate (2 parts per 100 parts of resin, the same applies hereinafter), and 1% of a dimethylsiloxane-based silicone-based slip agent; After applying a coating solution comprising a solvent solution by a gravure coating method,
By heating and drying, the surface layer was cross-linked and cured to form a surface layer 2 having a thickness of 3 μm, and a decorative sheet as a decorative material S was obtained.

Example 2 A cosmetic material was obtained in the same manner as in Example 1, except that the content of the ultraviolet absorber used in the surface layer was changed from 2% to 3%. Was.

Example 3 A cosmetic material was obtained in the same manner as in Example 1, except that the content of the ultraviolet absorber used in the surface layer was changed from 2% to 1%. Was.

Comparative Example 1 The procedure of Example 1 was repeated, except that the content of the ultraviolet absorber used in the surface layer was changed from 2% to 0% (not contained). A cosmetic material was obtained.

Comparative Example 2 A cosmetic material was obtained in the same manner as in Example 1, except that the content of the ultraviolet absorber used in the surface layer was changed from 2% to 4%. Was.

Comparative Example 3 In Example 2, the content of the ultraviolet absorber used in the surface layer was kept at 3%, and the following chemical structural formula was used.

Embedded image 2,4-di-tert-butyl-6- (5
A cosmetic material was obtained in the same manner as in Example 1 except that a benzotriazole-based ultraviolet absorber (ultraviolet absorber B) of (-chlorobenzotriazol-2-yl) phenol was used.

Comparative Example 4 In Example 2, the content of the ultraviolet absorbent used in the surface layer was kept at 3%, and the following chemical structural formula was used.

Embedded image A benzotriazole-based ultraviolet absorber (ultraviolet absorber C) represented by 2- (2H-benzotriazol-2-yl) -1,6-di-tert-pentylphenol
Except having changed to, a cosmetic material was obtained in the same manner as in Example 1.

[Performance evaluation] For each of the obtained decorative materials,
The performance was evaluated for weather resistance and abrasion resistance by the following methods.

Weathering adhesion: First, a test piece of a decorative material was
UV weathering tester (Iwasaki Electric Co., Ltd., Super U
V tester, model SUV-W13), black panel temperature 63 ° C., humidity 70% RH, UV irradiation 60
The test time was set to 50 hours (corresponding to one year of outdoor exposure) under the condition that irradiation time of mW / cm ² was repeated for 20 hours and non-condensation was performed for 4 hours as one cycle, and the test time was 75 hours.
The accelerated weathering test was performed for four types of time, 100 hours and 120 hours. Next, the surface of the test piece (surface layer surface)
Into the base material in a grid pattern at intervals of 2 mm to reach the transparent substrate 1b whose depth is directly below,
After making a total of 100 cells of × 10, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., “Cellotape” (registered trademark) 24 mm width, industrial use) was adhered at 20 ° C.
It peeled off vigorously, and it was evaluated whether the surface layer peeled off from the substrate 1b and peeled off together with the tape. A sample with no peeling was evaluated as good (も の), and a sample with peeling was measured as poor (x). Rise

Scratch resistance: The appearance of the test piece of the decorative sheet was rubbed 10 times back and forth, and the appearance was visually observed and evaluated. Those with no remaining scratches and glossy scratches after leaving the nail were good, and those with scratches and glossy scratches remaining after the nail were poor.

[0077]

[Table 1]

In Table 1, "A" in the column of ultraviolet absorbent represents isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-.
Represents hydroxyphenylpropionate, wherein "B" is
Represents 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol;
Is 2- (2H-benzotriazol-2-yl)-
Represents 1,6-di-tert-pentylphenol.

As shown in Table 1, the weather resistance was as shown in Example 1 where the UV absorber content was 2% and Example 2 where the UV absorber content was 3%.
Means that the test time was 120 hours in the weather resistance acceleration test, respectively, and excellent weather resistance was exhibited. Further, in Example 3 in which the content was as low as 1% than in these examples, the test time was 1%.
Although the test was poor at the time of 00 hours, the test was good until the test time of 75 hours. While the content of 0% was poor at the test time of 75 hours, the film exhibited a certain degree of weather resistance. However, in Comparative Example 2 having a large content of 4%, the initial adhesion of the surface layer was poor and the blocking resistance was also poor. Therefore, it was found that excellent results were obtained when the content of weather resistance and adhesion was in the range of 2 to 3%.

On the other hand, Comparative Examples 3 and 4 using different benzotriazole-based ultraviolet absorbers B and C were:
In each case, despite the content of 3%, the test time was good for 75 hours and the test time was good for 100 hours, but the performance was almost the same as the content of 1% when the ultraviolet absorbent A was used. No weather resistance was obtained.

The scratch resistance was good in all Examples and Comparative Examples.

[0082]

According to the cosmetic material of the present invention, the weather resistance of the surface layer is excellent. The surface layer can impart surface properties such as scratch resistance. In addition, by setting the content of the specific ultraviolet absorber to be contained in the surface layer to be 2 to 3% by mass with respect to the resin component, excellent weather resistance and adhesion can be obtained. If the ratio exceeds this range, poor adhesion of the surface layer and blocking are likely to occur. Further, if the surface layer contains a silicone slip agent, the scratch resistance is further improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating some embodiments of a cosmetic material of the present invention.

FIG. 2 is a cross-sectional view illustrating some examples of embodiments when the base material has two layers in the decorative material of the present invention.

FIG. 3 is a cross-sectional view illustrating another embodiment of the cosmetic material of the present invention.

FIG. 4 is a cross-sectional view illustrating another embodiment of the cosmetic material of the present invention.

FIG. 5 is a sectional view showing an example of a conventional decorative material.

[Explanation of symbols]

 Reference Signs List 1 base material 1a (colored) base material 1b (transparent) base material 2 surface layer 2a high-gloss surface layer 2b low-gloss surface layer 3 decorative layer 4 adhesive layer 5 uneven pattern 6 colored portion 7 adhesion reinforcing layer 31 Colored base material 32 decorative layer 33 adhesive layer 34 transparent base material S, Sa cosmetic material

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 33/00 B32B 33/00 B44C 3/02 B44C 3/02 A B44D 5/00 B44D 5/00 F term (Reference) 2B002 AA03 AA08 BA01 BA17 BB06 BB12 DA02 DA06 2B200 AA01 BA01 BB07 BB20 CA11 DA04 EA06 EE13 FA24 FA50 2B250 AA06 AA11 BA03 CA11 DA04 EA02 EA13 FA18 FA21 FA28 FA31 FA33 GA03 4K100 AK52H AK64 AL01 AL06B AR00A BA02 CA07B CA19B EJ39 EJ55 GB08 GB31 GB48 GB81 HB00A JK06 JK16 JL00 JL09 YY00B YY00H

Claims (3)

[Claims] 1. A decorative material comprising a decorative-treated base material and having a surface layer on the outermost surface, wherein the surface layer comprises a main component of an acrylic polyol and a crosslinking agent of an aliphatic and / or alicyclic isocyanate. A crosslinked cured product of an acrylic urethane resin consisting of: and as a benzotriazole-based ultraviolet absorber, a chemical structural formula: Represented by the formula: isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4
-A cosmetic material containing hydroxyphenyl propionate. 2. The method according to claim 1, wherein the ultraviolet absorbent is used in an amount of 2
The cosmetic material according to claim 1, wherein the cosmetic material contains 材 3% by mass. 3. The decorative material according to claim 1, wherein the surface layer further contains a silicone slip agent.