JP5522778B2 - Laminated body - Google Patents

Description

  The present invention relates to a novel laminate.

  In recent years, as materials used for the wall surfaces of buildings, etc., natural stones, and design materials that image natural stones are becoming increasingly popular. As such a material, a material obtained by molding a composition containing a binder such as an acrylic resin emulsion and a natural aggregate or an artificial aggregate into a plate shape is known. For example, in JP-A-4-347251 (Patent Document 1) and JP-A-4-76151 (Patent Document 2), one surface of a plate-like object made of a spray material in which an aggregate is mixed with an acrylic resin, Or the sheet | seat material for building surface finishing which laminated | stacked the reinforcement layer which consists of a synthetic resin fabric in the middle of a plate-shaped object is described.

  In the materials described in the above-mentioned patent documents, a certain effect can be obtained in terms of improving flexibility by the action of the synthetic resin fabric. However, there is a limit to the effect of flexibility only by depending on the synthetic resin fabric.

JP-A-4-347251 JP-A-4-76151

In the material of the above-mentioned patent document, in order to obtain sufficient flexibility, a device for the spray material is required.
The first means is to set a high ratio of acrylic resin to aggregate. However, when the resin ratio is set to be high in the spray material, the natural stone-like texture expressed by the aggregate may be reduced.
A second means is to use a highly flexible synthetic resin. However, in this case, dirt easily adheres to the sheet surface, which causes a problem that aesthetics are impaired.

  The present invention has been made in view of the above-described problems, and can provide a material that can express aesthetics utilizing the texture of the aggregate and has excellent performance in terms of flexibility, contamination resistance, and the like. It is intended to do.

  In order to solve such a problem, the present inventors have intensively studied and arrived at a laminate in which a base layer and a pattern layer each made of a specific resin and an inorganic aggregate are laminated, and a network is interposed therein. The present invention has been completed.

That is, the present invention has the following characteristics.
1. A laminate in which a base layer and a pattern layer are laminated,
The base layer is 100 parts by weight of an inorganic aggregate having an average particle size of 0.01 to 3 mm.
Synthetic resin having 40 to 100% by weight of (meth) acrylic acid alkyl ester and 0 to 60% by weight of monomer copolymerizable with the (meth) acrylic acid alkyl ester as a resin component and having a glass transition temperature of 5 ° C. or lower. Is a cured product of a composition containing 1 to 30 parts by weight in terms of solid content,
The pattern layer is 100 parts by weight of an inorganic aggregate having an average particle diameter of 0.01 to 3 mm.
(Meth) acrylic acid alkyl ester 50 to 95% by weight, and a cured product of a composition containing 1 to 10 parts by weight in terms of solid content of a synthetic resin containing 5 to 50% by weight of a siloxane compound as a resin component,
A laminate used for finishing a building , characterized in that a net is present inside the laminate.
2. A laminate in which a base layer, a pattern layer, and a protective layer are laminated,
The base layer is 100 parts by weight of an inorganic aggregate having an average particle size of 0.01 to 3 mm.
Synthetic resin having 40 to 100% by weight of (meth) acrylic acid alkyl ester and 0 to 60% by weight of monomer copolymerizable with the (meth) acrylic acid alkyl ester as a resin component and having a glass transition temperature of 5 ° C. or lower. Is a cured product of a composition containing 1 to 30 parts by weight in terms of solid content,
The pattern layer is 100 parts by weight of an inorganic aggregate having an average particle diameter of 0.01 to 3 mm.
(Meth) acrylic acid alkyl ester 50 to 95% by weight, and a cured product of a composition containing 1 to 10 parts by weight in terms of solid content of a synthetic resin containing 5 to 50% by weight of a siloxane compound as a resin component,
The protective layer has transparency,
A laminate used for finishing a building , characterized in that a net is present inside the laminate.

  The laminate of the present invention can exhibit aesthetics that make use of the texture of the aggregate, and can also exhibit excellent performance in terms of flexibility, stain resistance, and the like.

  Hereinafter, modes for carrying out the present invention will be described.

  The laminate of the present invention is a laminate in which a specific base layer and a pattern layer are laminated and a network is interposed therein. In the present invention, a specific synthetic resin is used as a binder in each of the base layer and the pattern layer, and each layer is formed by combining these binders and inorganic aggregates, and further by interposing a network, the texture and flexibility It is possible to exhibit excellent performance in terms of contamination resistance and the like.

  Among these, the base layer is an inorganic aggregate (hereinafter also referred to as “component (A)”) having an average particle size of 0.01 to 3 mm, (meth) acrylic acid alkyl ester 40 to 100% by weight, and the (meth) acrylic acid. It is a cured product of a composition containing a synthetic resin (hereinafter also referred to as “component (B)”) having 0 to 60% by weight of a monomer copolymerizable with an alkyl ester as a resin component and a glass transition temperature of 5 ° C. or less. .

  As the component (A), at least one selected from natural aggregates such as natural stone and natural stone pulverized products, and artificial aggregates such as colored aggregates can be used. Specifically, for example, marble, granite, serpentine, granite, fluorite, cryolite, feldspar, quartzite, quartz sand, mica and pulverized products thereof, ceramic pulverized product, ceramic pulverized product, glass pulverized product, glass beads, Examples include shell pulverized products, metal grains, metal pieces, and the like, and those having a surface coated with a colored coating.

  (A) The average particle diameter of a component is 0.01 mm-3 mm normally, Preferably it is 0.02-1 mm. When the average particle diameter of the component (A) is out of the above range, it is disadvantageous in terms of flexibility and strength. In addition, an average particle diameter is a value obtained by sieving using the metal net sieve prescribed | regulated to JISZ8801-1: 2000, and calculating the average value of the weight distribution.

The component (B) in the base layer is composed of 40 to 100% by weight of a (meth) acrylic acid alkyl ester and 0 to 60% by weight of a monomer copolymerizable with the (meth) acrylic acid alkyl ester as a resin component, and has a glass transition temperature. Is a synthetic resin of 5 ° C. or lower. This component (B) is an essential component for imparting flexibility to the laminate of the present invention. Furthermore, (B) component is excellent also in adhesiveness with the below-mentioned (D) component.
As the component (B), a water-soluble resin and / or a water-dispersible resin is preferably used.

  Examples of the (meth) acrylic acid alkyl ester constituting the component (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, and n-to. Examples include xyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

As the monomer copolymerizable with the (meth) acrylic acid alkyl ester, a compound having a polymerizable unsaturated double bond can be used. Examples of such compounds include aromatic monomers, carboxyl group-containing monomers, amino group-containing monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, alkoxysilyl group-containing monomers. , Vinylidene halide monomers, ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, chloroprene and the like.
Among these, the aromatic monomer is a compound having an aromatic ring and a polymerizable unsaturated double bond, and specific examples thereof include, for example, styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinyl. Anisole, vinyl naphthalene, divinylbenzene, phenyl (meth) acrylate, benzyl (meth) acrylate and the like can be mentioned.

  The proportion of each component in the component (B) is (meth) acrylic acid alkyl ester 40 to 100% by weight (preferably 45 to 95% by weight), monomer 0 to copolymerize with the (meth) acrylic acid alkyl ester 0 60% by weight (preferably 5 to 55% by weight). When the ratio of the (meth) acrylic acid alkyl ester is too small, the adhesion with the pattern layer may be insufficient.

  Component (B) can be obtained by polymerizing a mixture of the above compounds. Under the present circumstances, it sets so that a glass transition temperature may be 5 degrees C or less (preferably -50--5 degreeC) combining each said compound suitably. When the glass transition temperature of the component (B) is too high, it becomes difficult to obtain sufficient flexibility. In addition, the glass transition temperature in this invention is a value calculated | required by the formula of Fox.

The base layer cures a composition containing 1 to 30 parts by weight (preferably 2 to 10 parts by weight, more preferably 2 to 5 parts by weight) of component (B) with respect to 100 parts by weight of component (A). Can be obtained. Here, when the mixing amount of the component (B) is too small, it becomes difficult to obtain sufficient flexibility, and the adhesion with the pattern layer becomes insufficient. In some cases, the effect of the net-like body is hardly exhibited. (B) When there are too many components, there exists a possibility that a crack etc. may arise in a pattern layer.
The thickness of the base layer is usually about 0.5 to 5 mm.

  The patterned layer in the laminate of the present invention comprises an inorganic aggregate having an average particle diameter of 0.01 to 3 mm (hereinafter also referred to as “component (C)”), an alkyl (meth) acrylate of 50 to 95% by weight, and a siloxane compound 5 It is a cured product of a composition containing a synthetic resin (hereinafter also referred to as “component (D)”) containing ˜50% by weight of a resin component.

  (C) As a component, the thing similar to what was illustrated by the above-mentioned (A) component can be used, and that whose average particle diameter is 0.01 mm-3 mm (preferably 0.02-2 mm) can be used. When the average particle diameter of (C) component is too small, it will become difficult to express the texture by an aggregate and it will become disadvantageous also about a flexibility. When the average particle size of the component (C) is too large, irregularities on the surface of the pattern layer become remarkable, which is disadvantageous in terms of texture, stain resistance and the like.

(D) component in a pattern layer is a synthetic resin which uses 50-95 weight% of (meth) acrylic-acid alkylesters and 5-50 weight% of siloxane compounds as a resin structural component. In the present invention, in addition to the above-described components, by adopting such a component (D) as a binder in the pattern layer, it is possible to obtain excellent performance in texture, flexibility, stain resistance, etc. Become. Furthermore, the adhesiveness between the base layer and the pattern layer can be ensured.
As the component (D), a water-soluble resin and / or a water-dispersible resin is preferably used. Moreover, as (meth) acrylic-acid alkylester in (D) component, the thing similar to what was illustrated by (B) component can be used.

The siloxane compound in the component (D) generates a silicone resin by polymerization. Examples of the siloxane compound include those having a structural unit represented by a general formula R _n SiO _{(4-n) / 2} (wherein R is a hydrocarbon group, n = 0 to 3). Examples of such a compound include a linear siloxane compound, a branched siloxane compound, a cyclic siloxane compound, and the like, among which a cyclic siloxane compound is preferable. Examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. When such a cyclic siloxane compound is polymerized, a linear siloxane compound, a branched siloxane compound, an alkoxysilane compound, or the like can be used, and a polymerization catalyst can be appropriately used. Of these, as the alkoxysilane compound, a silane compound having one or more alkoxyl groups in the molecule can be used. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ- Silane coupling agents such as (meth) acryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be used. When the cyclic siloxane compound is polymerized, by using such an alkoxysilane compound in combination, the bond of the siloxane compound in the component (D) is strengthened, which is advantageous in terms of improving the film properties such as water resistance.

  The proportion of the siloxane compound in the resin component (D) is usually 5 to 50% by weight, preferably 15 to 40% by weight. When the siloxane compound has such a ratio, excellent physical properties in terms of flexibility and stain resistance can be obtained, and the texture can be further improved. When the ratio of the siloxane compound deviates from the above ratio, it is difficult to obtain such an effect. When the ratio of the siloxane compound is too high, the adhesion between the base layer and the pattern layer may be hindered.

  Component (D) can be obtained by polymerizing a mixture of the above components. In the component (D), a monomer copolymerizable with the component (D) may be included in the constituent components. Under the present circumstances, the glass transition temperature of the acrylic resin part comprised by the monomer copolymerizable with (D) component and (D) component will be normally -20-20 degreeC (preferably -15-15 degreeC). It is desirable to set to.

A pattern layer can be obtained by hardening the composition which contains 1-10 weight part (preferably 2-5 weight part) of (D) component in conversion of solid content with respect to 100 weight part of (C) component. Here, when the mixing amount of the component (D) is too small, it becomes difficult to obtain sufficient flexibility, stain resistance, and the like, and the adhesion to the base layer may be lowered. Moreover, the effect by a mesh body may become difficult to be exhibited. (D) When there are too many components, the texture by an aggregate becomes easy to be killed.
The thickness of the pattern layer is usually about 0.5 to 5 mm.

  A net-like body is interposed in the laminate of the present invention. Such a net-like body imparts flexibility, strength and the like to the laminate of the present invention. In the present invention, the network body may be interposed in the laminated body, but is desirably interposed in the vicinity of the interface between the base layer and the pattern layer.

  As the network, a fibrous network made of various natural fibers and synthetic fibers is suitable. Examples of fibers constituting such a fibrous network include pulp fibers, polyester fibers, polypropylene fibers, aramid fibers, vinylon fibers, polyethylene fibers, polyarylate fibers, PBO fibers, nylon fibers, acrylic fibers, and vinyl chloride fibers. Organic fibers such as cellulose fibers; rock wool, glass fibers, silica fibers, silica-alumina fibers, carbon fibers, silicon carbide fibers, and the like, and inorganic fibers such as fine metal wires such as iron and copper. Among these, in the present invention, inorganic fibers are preferable, and glass fibers are particularly preferable.

  As the fiber network, fiber bundles having a diameter of about 0.05 mm to 2 mm (preferably 0.1 to 1.5 mm) are arranged in a network at intervals of 1 to 5 mm (preferably 1.5 to 3 mm). Those having the structure described above are preferred. In particular, those having a network structure with regularity such as a lattice shape are preferable. If it is such a form, a base layer and / or a pattern layer will easily bite into a mesh, and flexibility, intensity, etc. can be raised. In addition, the space | interval of a fiber bundle said here is the width | variety of the space | gap part between fiber bundles.

As long as a pattern layer is laminated | stacked on a base layer, this invention laminated body will not be specifically limited about the manufacturing method, For example, it can manufacture with the following method.
(1) A method in which a pattern layer composition is applied to the inner surface of a mold, a net is placed or embedded, a base layer composition is further laminated, and demolded after curing.
(2) A method in which the base layer composition is applied to the inner surface of the mold, and then the network is placed or embedded, the pattern layer composition is further laminated, and demolded after curing.

  In addition, as a composition for base layers, the paste-form mixture containing (A) component and (B) component can be used, and as a composition for pattern layers, the paste-form mixture containing (C) component and (D) component is used. Can be used. These compositions can be used as necessary, for example, pigments, fibers, plasticizers, antibacterial agents, catalysts, adsorbents, fungicides, insecticides, flame retardants, crosslinking agents, lubricants, film-forming aids, water repellents, hydrophilic agents. An agent, antioxidant, light stabilizer, ultraviolet absorber, anti-blocking agent, and the like may be included.

As the mold used in the above (1) and (2), for example, a mold made of silicon resin, urethane resin, metal or the like, or a mold provided with release paper can be used.
In (1), since the mold frame side is the surface of the laminate, a desired uneven pattern can be imparted to the laminate surface by adjusting the shape inside the mold. On the other hand, in (2), the mold side is the back surface of the laminate. If unevenness is formed on the back surface, the adhesiveness of the laminate can be improved. In (2), various uneven | corrugated patterns etc. can also be formed before drying of a pattern layer.
When applying each material in the above (1) and (2), for example, a method using means such as a spray, a roller, a trowel, a reciprocator, a coater, or a pouring can be employed. When embedding the net-like body, a roller, a trowel or the like can be used. Moreover, when hardening the composition for base layers and the composition for pattern layers, it can also heat.
The thickness of a laminated body should just be about 1-10 mm normally.

Moreover, if it is in the range which does not inhibit the effect of this invention, in order to improve the decorating property etc. of a pattern layer, an inorganic aggregate with an average particle diameter exceeding 3 mm can be mixed with a pattern layer, or can be spread | dispersed. . As such an aggregate, for example, the same material as the above-mentioned aggregate can be used.
In the above (1) and (2), it is also possible to apply a transparent top coat or the like to the surface of the pattern layer after demolding. With such a transparent top coating material, a protective layer can be formed on the surface of the pattern layer, and the water resistance and durability of the laminate of the present invention can be improved. The transparency of the protective layer may be as long as the pattern layer is visible. The thickness of the protective layer is usually about 0.1 to 200 μm.

  The protective layer can be formed of a transparent overcoat material containing various synthetic resins as essential components. Examples of the synthetic resin include vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic silicon resin, fluorine resin, or a composite system thereof. it can. These may have crosslinking reactivity. Moreover, the form of the synthetic resin is not particularly limited, and may be either one-component type or two-component type.

  As a synthetic resin in a protective layer, what contains 40 weight% or more of (meth) acrylic-acid alkylester as a resin structural component is desirable. Such a synthetic resin is suitable in terms of adhesion to the protective layer. As a particularly preferred synthetic resin, for example, the aforementioned component (D) and the like can be mentioned. When the component (D) is used as the synthetic resin in the protective layer, it is preferable in terms of flexibility, stain resistance, texture, and the like.

  As the transparent top coating material for forming the protective layer, a material containing a silicate compound and / or silica in addition to the above synthetic resin can be preferably used. By using such a transparent top coating material, it is possible to enhance the stain resistance of the protective layer while maintaining the texture of the pattern layer.

Examples of the silicate compound include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, tetra t-butoxysilane, tetra Examples thereof include tetraalkoxysilane compounds such as phenoxysilane, and condensates thereof. A compound obtained by modifying such a compound with an alkoxysilane compound other than the silicate compound, an alcohol, a glycol, a glycol ether, a polyoxyalkylene group-containing compound, or the like can also be used.
The mixing amount of the silicate compound may be appropriately set in consideration of the performance of the protective layer, but is usually 0.1 to 50 parts by weight (preferably 0.5 to 30 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin. Part) grade.

As silica, a granular material having a particle diameter of about 1 to 200 nm (preferably 5 to 100 nm) can be used. Such silica can be produced using, for example, a silicate such as sodium silicate, lithium silicate, or potassium silicate, or the above-described silicate compound as a raw material. When silica is used as a component in the protective layer, the surface hardness can be increased, which is also preferable in terms of scratch resistance and the like.
The mixing amount of silica may be appropriately set in consideration of the various performances of the protective layer as described above, but is usually 5 to 500 parts by weight (preferably 10 to 300 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin. Part) grade.

  In addition to the above-mentioned components, the transparent top coating material that forms the protective layer is, for example, a color pigment, an extender pigment, a matting agent, a plasticizer, an antibacterial agent, a catalyst, an adsorbent, an antifungal agent, an insecticide, a flame retardant, a crosslink Agents, lubricants, film-forming aids, water repellents, hydrophilic agents, antioxidants, light stabilizers, ultraviolet absorbers, anti-blocking agents and the like may be included.

  The laminate of the present invention can be applied mainly to building finishing. That is, at the time of distribution, finishing can be performed by handling it as a sheet-like molded body and applying it to each part of the building. Specifically, it can be applied to walls, partitions, doors, ceilings, etc. in houses, condominiums, schools, hospitals, stores, offices, factories, warehouses, restaurants, etc. Examples of the base material constituting such a part include gypsum board, plywood, concrete, mortar, tile, fiber-mixed cement board, cement calcium silicate board, and slag cement pearlite board. These base materials may be those having an existing coating film on the surface thereof, or those having already been pasted with wallpaper. The laminate of the present invention is constructed so that the base layer side is in contact with such a base material.

  What is necessary is just to stick to a base material using an adhesive agent, an adhesive, an adhesive tape, a nail, a wrinkle, etc. when constructing this invention laminated body. In addition, it can also be fixed using pins, fasteners, rails or the like. Moreover, this invention laminated body can also cut | disconnect a laminated body in arbitrary shapes at the time of construction, and can also perform the edge processing etc. of a cut surface suitably.

  Examples are given below to clarify the features of the present invention.

  The following raw materials were used to produce the base layer composition and the pattern layer composition.

-Aggregate 1: Cold water stone (average particle size: 0.3mm)
-Aggregate 2: Heavy calcium carbonate (average particle size: 0.03 mm)
Aggregate 3: colored quartz sand (a mixture of white quartz sand, brown quartz sand and black quartz sand, average particle size: 0.3 mm)
Resin 1 (water-dispersible resin, solid content: 50% by weight, resin component: 2-ethylhexyl acrylate, emulsion polymer of styrene and methacrylic acid (weight ratio 56: 42: 2), glass transition temperature: −19 ° C. )
Resin 2 (water-dispersible resin, solid content: 50% by weight, resin component: 2-ethylhexyl acrylate, emulsion polymer of styrene and methacrylic acid (weight ratio 43: 55: 2), glass transition temperature: 2 ° C.)
Resin 3 (water-dispersible resin, solid content: 50% by weight, resin component: emulsion emulsion of 2-ethylhexyl acrylate, styrene and methacrylic acid (weight ratio 35: 63: 2), glass transition temperature: 16 ° C.)

Resin 4 (water-dispersible resin, solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclo Tetrasiloxane, decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 23: 15: 20: 18: 21: 3), glass transition temperature of acrylic resin part: 2 ° C.)
Resin 5 (water dispersible resin, solid content: 50% by weight, resin constituents: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclo Tetrasiloxane, decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 25: 18: 24: 20: 10: 3), glass transition temperature of acrylic resin part: 1 ° C.)
Resin 6 (water-dispersible resin, solid content: 50% by weight, resin component: methyl methacrylate, t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, siloxane compound (hexamethylcyclotrisiloxane, octamethylcyclo Tetrasiloxane, decamethylcyclopentasiloxane) and methacrylic acid emulsion polymer (weight ratio 28: 20: 25: 22: 2: 3), glass transition temperature of acrylic resin part: 2 ° C.)

(Base layer composition 1)
The above-described aggregate 1, aggregate 2, and resin 1 were uniformly mixed so that the solid content ratio was 92: 8: 3 to obtain a composition 1 for a base layer.
(Base layer composition 2)
The above-described aggregate 1, aggregate 2, and resin 2 were uniformly mixed so that the solid content ratio was 92: 8: 3 to obtain a base layer composition 2.
(Base layer composition 3)
The above-described aggregate 1, aggregate 2, and resin 3 were uniformly mixed so that the solid content ratio was 92: 8: 3, whereby a base layer composition 3 was obtained.

(Composition 1 for pattern layer)
The above-described aggregate 3 and resin 4 were uniformly mixed so that the solid content ratio was 100: 3 to obtain a pattern layer composition 1.
(Composition 2 for pattern layer)
The above-described aggregate 3 and resin 5 were uniformly mixed so that the solid content ratio was 100: 3 to obtain a pattern layer composition 2.
(Composition 3 for pattern layer)
The above-described aggregate 3 and resin 6 were uniformly mixed so that the solid content ratio was 100: 3 to obtain a pattern layer composition 3.

(Composition 4 for pattern layer)
The above-described aggregate 3 and resin 1 were uniformly mixed so that the solid content ratio was 100: 3 to obtain a pattern layer composition 4.
(Composition 5 for pattern layer)
The above-described aggregate 3 and resin 1 were uniformly mixed so that the solid content ratio was 100: 14 to obtain a pattern layer composition 5.
(Composition 6 for pattern layer)
The above-described aggregate 3 and resin 2 were uniformly mixed so that the solid content ratio was 100: 3 to obtain a pattern layer composition 6.

Example 1
The pattern layer composition 1 is poured into the inner surface of a mold (450 mm long × 450 mm wide × 3-5 mm deep) coated with a release agent. Immediately after that, a net (lattice glass fiber network, fiber bundle) (Diameter: 0.4 mm, spacing between fiber bundles 2.5 mm, mesh shape: square) was placed and pressed with a roller. Next, after 24 hours, the composition 1 for the base layer was poured and smoothed using a trowel. After drying at 23 ° C. for 24 hours, the laminate was removed by demolding. The thickness of the base layer of this laminate was about 2 mm, and the thickness of the pattern layer was about 1 to 3 mm. The obtained laminate was confirmed for texture, flexibility and stain resistance.

Regarding the texture, the appearance of the pattern layer in the laminate is observed, and “A” indicates that the aggregate texture is sufficiently expressed, and “D” indicates that the aggregate texture is reduced 4 Evaluation was performed at the stage (excellent A>B>C> D inferior).
Regarding flexibility, the laminate is repeatedly bent with both ends, and “A” indicates that the flexible body is sufficiently flexible, and “D” indicates that it is inferior in flexibility (excellent A>B>).C> D inferior).
Concerning stain resistance, the laminate was exposed outdoors in Ibaraki City, Osaka for 3 months, and then its surface condition was observed. “A” indicates that the degree of contamination was slight, and the level of contamination was significant. Was evaluated in four stages (excellent A>B>C> D inferior), with “D” being “D”.
The results are shown in Table 1.

(Examples 2-3, Comparative Examples 1-5)
A laminate was produced in the same manner as in Example 1 except that the compositions shown in Table 1 were used as the base layer composition and the pattern layer composition, and the texture, flexibility and stain resistance were evaluated. . The results are shown in Table 1.

(Transparent top coat 1)
Water was mixed into the resin 4 to adjust the solid content to 20% by weight, whereby a transparent top coating material 1 was obtained.

(Transparent coating material 2)
Resin 7 (water-dispersible resin, solid content: 50% by weight, resin component: emulsion polymer of 2-ethylhexyl acrylate, methyl methacrylate and methacrylic acid (weight ratio 25: 74: 1), glass transition temperature: 32 ° C.) Water-dispersible silica (particle size 10-20 μm, solid content 30% by weight) is mixed so that the solid content ratio is 100: 50, and water and a film-forming aid are added to obtain a solid content concentration of 20% by weight. To obtain a transparent top coating material 2.

(Transparent top coat 3)
A solvent was added to resin 8 (solvent soluble resin, solid content: 50% by weight, resin component: polymer of n-butyl acrylate and methyl methacrylate (weight ratio 30:70), glass transition temperature: 31 ° C.). After the solid content concentration was adjusted to 18% by weight, a silicate compound (tetramethoxysilane condensate) was mixed to obtain a transparent top coating material 3. At this time, the silicate compound was mixed so that the solid content ratio between the resin solid content and the silicate compound was 100: 10.

Example 4
The pattern layer composition 1 is poured into the inner surface of a mold (450 mm long × 450 mm wide × 3-5 mm deep) coated with a release agent. Immediately after that, a net (lattice glass fiber network, fiber bundle) (Diameter: 0.4 mm, spacing between fiber bundles 2.5 mm, mesh shape: square) was placed and pressed with a roller. Then, after 24 hours, the composition for base layer 1 was poured, smoothed with a trowel, and dried at 23 ° C. for 24 hours. After demolding, the transparent overcoating material 1 was spray-coated on the surface of the resulting pattern layer and dried at 23 ° C. for 24 hours to produce a laminate. The thickness of the base layer of this laminate was about 2 mm, the thickness of the pattern layer was about 1 to 3 mm, and the thickness of the protective layer made of the transparent top coating material was 10 μm.
With respect to the obtained laminate, the texture, flexibility, and contamination resistance were evaluated in the same manner as in Example 1. The evaluation of Example 4 was “A” in all cases, but the contamination resistance and flexibility were in a better state than Example 1.

(Example 5)
A laminate was produced in the same manner as in Example 4 except that the transparent top coating material 2 was used instead of the transparent top coating material 1.
With respect to the obtained laminate, the texture, flexibility, and contamination resistance were evaluated in the same manner as in Example 1. The evaluation of Example 5 was “A” in all cases, but the contamination resistance was better than that of Examples 1 and 4.

(Example 6)
A laminate was produced in the same manner as in Example 4 except that the transparent top coating material 3 was used instead of the transparent top coating material 1.
With respect to the obtained laminate, the texture, flexibility, and contamination resistance were evaluated in the same manner as in Example 1. The evaluation of Example 6 was “A” in all cases, but the contamination resistance was in a better state than Examples 1 and 4.

Claims (1)

A laminate in which a base layer and a pattern layer are laminated,
The base layer is 100 parts by weight of an inorganic aggregate having an average particle size of 0.01 to 3 mm.
Synthetic resin having 40 to 100% by weight of (meth) acrylic acid alkyl ester and 0 to 60% by weight of monomer copolymerizable with the (meth) acrylic acid alkyl ester as a resin component and having a glass transition temperature of 5 ° C. or lower. Is a cured product of a composition containing 1 to 30 parts by weight in terms of solid content,
The pattern layer is 100 parts by weight of an inorganic aggregate having an average particle diameter of 0.01 to 3 mm.
(Meth) acrylic acid alkyl ester 50 to 95% by weight, and a cured product of a composition containing 1 to 10 parts by weight in terms of solid content of a synthetic resin containing 5 to 50% by weight of a siloxane compound as a resin component,
A laminate used for finishing a building , characterized in that a net is present inside the laminate.