JP3201687U - Laminated body - Google Patents

Abstract

Provided is a laminate having a design property on the back surface of a glass plate, which is excellent in adhesion between the glass plate and the design layer, and excellent in lightness, aesthetics, and the like. A laminated body is a laminated body in which a base layer 2 and a design layer 3 are sequentially laminated on the back surface of a transparent glass plate 1, and the base layer 2 includes at least a thermosetting resin as a binder. Features. [Selection] Figure 1

Description

  The present invention relates to a novel laminate. The present invention can be applied mainly to buildings and civil engineering structures.

  Conventionally, natural stone is often used as a surface decorative material in the wall surfaces of buildings and civil engineering structures. With such a material, it is possible to express the deep aesthetics unique to natural stone. However, natural stones have disadvantages such as high cost, difficulty in processing, and high weight. In particular, the point that it is difficult to process and is heavy may adversely affect workability and safety when applied to a wall surface or the like.

  Under such a background, various natural stone-like panels have been proposed. For example, Japanese Patent Application Laid-Open No. 7-76915 (Patent Document 1) describes a stone-like panel in which a stone-like pattern layer is formed on the back surface of a transparent acrylic plate, and a light shielding layer and a resin plate are combined together. Yes. Japanese Unexamined Patent Application Publication No. 2007-77759 (Patent Document 2) describes a stone-like panel provided with a coating layer containing an aggregate such as artificial stone on a transparent acrylic plate. Since such a stone-like panel has a transparent resin plate as a surface layer, it is difficult to obtain the deep aesthetics and high-class feeling peculiar to natural stones, and there is a risk of burning in the event of a fire, etc. It becomes a problem.

  On the other hand, Japanese Patent Application Laid-Open No. 9-76254 (Patent Document 3) describes an artificial stone plate in which the back surface of a glass plate is covered with granular materials and resin to form a stone-like pattern layer. Such a method can provide a deep aesthetics and high-class feeling unique to natural stones as compared to Patent Documents 1 and 2 above. However, in the method of Patent Document 3, the adhesion between the glass plate and the resin may be insufficient. In addition, the stone-like pattern tends to give an artificial impression, and there is room for improvement in aesthetics.

JP-A-7-76915 JP 2007-77759 A JP-A-9-76254

  The present invention has been made in view of the above-described problems. In a laminate having a design layer on the back surface of a glass plate, the glass plate and the design layer are excellent in adhesion, and lightweight, aesthetics, etc. The object is to provide an excellent laminate.

  In order to solve the above-mentioned problems, the present inventors have intensively studied and have come up with a laminate in which a specific base layer and a design layer are sequentially laminated on the back surface of the transparent glass plate, and have completed the present invention. .

  That is, the present invention has the following features.

1. A laminated body in which a base layer and a design layer are sequentially laminated on the back surface of the transparent glass plate,
The base layer includes a thermosetting resin having at least an alkoxysilyl group as a binder.

2. The base layer includes a thermosetting resin having at least an alkoxysilyl group as a binder. The laminated body as described in.

3. The design layer includes a coloring material. Or 2. The laminated body in any one of.

4). The colorant is a colored aggregate and / or colored resin particles. ~ 3. The laminated body in any one of.

Above 1. ~ 4. In this laminate, the design layer is laminated on the back surface of the transparent glass plate via a specific base layer. By interposing such a specific base layer, it is possible to obtain a laminate having excellent adhesion between the transparent glass plate and the design layer, and excellent in lightness, aesthetics and the like.
2. According to the laminate, a more excellent effect can be obtained with respect to adhesion and the like.
3. above. According to the laminate, a more excellent effect with respect to aesthetics and the like can be obtained.
4. above. According to the laminate, a design layer having various patterns can be formed, and a more excellent effect can be obtained with respect to aesthetics and the like.

It is sectional drawing which shows an example of this invention.

(1) Transparent glass plate (2) Base layer (3) Design layer

Hereinafter, the form for implementing this invention is demonstrated.
In the laminate of the present invention, a base layer and a design layer are sequentially laminated on the back surface of a transparent glass plate.

The transparent glass plate is not particularly limited as long as it has a transparency that does not impair the design of the design layer. Usually, a highly transparent glass plate may be used, but depending on the application, a translucent glass plate or a patterned glass plate, a glass plate obtained by bonding two or more different glass plates, or Alternatively, a glass plate with a coated surface may be used.
For example, ordinary glass, float glass, frosted glass, frosted glass, highly transmissive glass, template glass, heat resistant glass, colored transparent glass, tempered glass, heat reflecting glass, and the like can be used.

The thickness of the transparent glass plate may be about 1 mm to 30 mm (preferably about 2 mm to 10 mm, more preferably about 3 mm to 8 mm).
The light transmittance of the transparent glass layer is preferably about 40% or more (more preferably 60% to 99%). When the light transmittance is in such a range, an excellent design can be obtained without losing the brightness and color. In addition, it is possible to obtain a design panel (A) having a sense of depth and a sense of depth and full of luxury.
The light transmittance is all measured using an integrating sphere light transmittance measuring device in accordance with measurement method A defined in JIS K 7105-1981 5.5 “Light transmittance and total light reflectance”. It is a value of light transmittance. The light transmittance is a value measured at a wavelength of 550 nm.

  The base layer of the present invention contains at least a thermosetting resin as a binder. The thermosetting resin is a resin that forms a three-dimensional crosslinked structure by curing. Examples of the thermosetting resin include those that form a three-dimensional crosslinked structure by reaction of a reactive functional group or the like.

Examples of the reactive functional group include a carboxyl group, a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, a hydroxyl group, an isocyanate group, a carbonyl group, a hydrazide group, an epoxy group, an amino group, and an alkoxysilyl group.
Examples of such combinations of reactive functional groups include carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, carbonyl group and hydrazide group, epoxy Combinations of groups, amino groups, alkoxysilyl groups, and the like can be given.

  The thermosetting resin in the present invention has one or more kinds of combinations of such reactive functional groups. In particular, a preferable combination of reactive functional groups includes at least one selected from a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, an epoxy group and an amino group, and an alkoxysilyl group.

  In particular, in the present invention, the thermosetting resin preferably has at least an alkoxysilyl group. In a preferred embodiment, it has an alkoxysilyl group and further has one or more (preferably two or more) combinations of the above reactive functional groups (excluding alkoxysilyl groups). By using such a thermosetting resin, since it is excellent in adhesiveness with a transparent glass plate and a design layer can be firmly fixed, it is easy to form an excellent design.

As the thermosetting resin in the present invention, one having one reactive component or two or more components can be used as long as it has the reactive functional group. Specifically, those composed of one or more resins, those composed of one or more resins and one or more curing agents can be used.
For example, such resins include epoxy resins, urethane resins, silicone resins, acrylic silicone resins, alkyd resins, melamine resins, polycarbonate resins, phenol resins, acrylic resins, polyester resins, polyether resins, vinyl resins, polyamide resins, A fluororesin, an amino resin, etc. are mentioned, It does not specifically limit, such as a water dispersion type, a water soluble type, a weak solvent type, a strong solvent type, a NAD type, a powder type.
In the present invention, at least one selected from an epoxy resin, a urethane resin, a silicon resin, and an acrylic silicon resin is particularly preferably used.

  In this invention, it is preferable that an acrylic silicon resin is included. In addition, it is also preferable to use a silicon compound having a functional group capable of reacting with the resin as a curing agent in terms of excellent adhesion to a transparent glass plate. In particular, it is preferable to contain 0.4 to 40% by weight (preferably 1 to 20% by weight) of SiO2 in terms of solid content in the thermosetting resin. In such a range, the adhesion to the glass plate is more favorable. Further improvement. Moreover, when the amount of SiO2 is less than 0.4% by weight, the adhesion to the glass plate may be insufficient, and when it exceeds 40% by weight, the film forming property and transparency may be insufficient. is there.

  The base layer of the present invention has transparency to the extent that the design properties of the design layer are utilized. In addition to the binder, the base layer can contain other components as necessary as long as the design properties of the design layer are not impaired. Examples of such components include plasticizers, algaeproofing agents, antibacterial agents, deodorants, adsorbents, flame retardants, ultraviolet absorbers, light stabilizers, antioxidants, catalysts and other various additives, color pigments, and the like. And decorative materials such as extender pigments, glitter pigments, phosphorescent pigments, fluorescent pigments, aggregates and fibers. In the present invention, in particular, when a decorative material is included, it is possible to impart excellent design properties, to further enhance the depth of the design layer, and to obtain a laminate having further excellent aesthetics. This is preferable because it is possible.

The design layer of the present invention can be used without any particular limitation as long as it can give an arbitrary design. For example, a resin sheet, a resin plate, an artificial stone plate, a natural stone plate, a wood plate, a design building material such as a wallpaper, or a layer formed by a design layer forming material, to which a desired design is given in advance.
As the design layer of the present invention, a layer formed of a design layer forming material including a binder and a colorant is particularly preferable. The colorant is not particularly limited as long as it can impart design properties, and examples thereof include color pigments, colored aggregates, and colored resin particles.
Examples of such a design layer include the following aspects.
(B) A layer formed from a design layer forming material containing a color pigment as a colorant (b) A layer formed from a design layer forming material containing a colored aggregate as a colorant (c) A colored resin as a colorant Layer formed by design layer forming material containing particles

  As the binder in the design layer forming material of the present invention, various resin components can be used. For example, solvent-soluble resins, non-water-dispersed resins, solvent-free resins, water-dispersed resins, water-soluble resins Examples thereof include resins. Examples of the resin include acrylic resins, urethane resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, acrylic silicon resins, fluororesins, polyvinyl alcohol, cellulose derivatives, and composites thereof. Such a resin component preferably has a property of causing a crosslinking reaction. In the present invention, it is particularly preferable to include an acrylic silicon resin. In this case, the adhesion with the base layer can be further enhanced.

  Examples of the coloring pigment (b) include, for example, inorganic coloring pigments such as titanium oxide, zinc oxide, alumina, carbon black, ferric oxide (valve), yellow iron oxide, iron oxide, ultramarine, and cobalt green, azo , Naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, quinophthalone, and other organic color pigments, glitter pigments, interference pigments, fluorescent pigments And phosphorescent pigments. By combining one or more of these color pigments, the colored resin particles can be adjusted to a desired color tone. In addition to colored pigments, extender pigments such as calcium carbonate, barium sulfate, clay, kaolin, porcelain clay, talc, quartzite powder, and diatomaceous earth can also be used.

  In the present invention, it is particularly preferable to include a luster pigment as the color pigment. Examples of glitter pigments include aluminum flake pigments, vapor-deposited aluminum flake pigments, metal oxide-coated aluminum flake pigments, colored aluminum flake pigments, metal oxide-coated mica pigments, metal oxide-coated synthetic mica pigments, and metal oxide-coated alumina. Flake pigment, metal oxide coated silica flake pigment, metal coated glass flake pigment, metal oxide coated glass flake pigment, metal oxide coated plate iron oxide, graphite, stainless steel flake, metal titanium flake pigment, plate molybdenum sulfide, plate Bismuth chloride, holographic pigment, cholesteric liquid crystal polymer, crushed product of metal-deposited polymer film, and the like. By including such a luster pigment, it is possible to have a higher quality and enhance aesthetics due to the refraction of the transparent glass plate and the reflection action of the luster pigment.

  The content of the color pigment may be appropriately set depending on the desired design, but is preferably 0.1 to 200 parts by weight (preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the solid content of the binder. ) Is preferable.

  In the above (b), the colored aggregate is visually recognized as a pattern and has excellent design properties. Such a colored aggregate is not particularly limited as long as it is a solid particle having a certain color, and the material can be either inorganic or organic, and either natural or artificial can be used. Specifically, for example, heavy calcium carbonate, cold water stone, mica, kaolin, clay, china clay, china clay, talc, aluminum hydroxide, magnesium hydroxide, shell, barite powder, marble, granite, serpentine, granite, Minerals such as fluorite, feldspar, quartz stone, quartz sand, ceramics, ceramics, glass beads, glass, metal particles, metal particles, resin beads, resin, rubbers, plastics Organic particles such as plant fibers and plant fragments. Moreover, what gave these coloring can also be used.

  Further, as the colored aggregate, it is preferable to use an opaque colored aggregate and a transparent and / or translucent colored aggregate in combination. In such a case, the sense of depth of the design layer can be further enhanced. In the present invention, the term “opaque” means that the light transmittance is less than 3%, and the term “transparent or translucent” means that the light transmittance is 3% or more. It is a value of total light transmittance. In this measurement, a sample of a colored aggregate is filled into a transparent glass cell having an inner thickness of 5 mm and then gradually filled with water, and then the bubbles in the cell are removed by vibration. However, a sample having a particle diameter of 0.5 to 1.0 mm is selected and used.

  The average particle diameter of the colored aggregate is preferably 0.01 mm to 5 mm, more preferably 0.02 mm to 2 mm. By combining various colored aggregates having different average particle sizes, the range of design properties can be expanded. The average particle diameter of the colored aggregate is a value obtained by sieving using a metal net sieve specified in JIS Z8801-1: 2000 and calculating the average value of the weight distribution.

  The ratio of the resin component is preferably 3 parts by weight or more and 50 parts by weight or less, more preferably 4 parts by weight or more and 30 parts by weight or less, and still more preferably, in terms of solid content, with respect to 100 parts by weight of the total amount of the colored aggregate. 6 parts by weight or more and 20 parts by weight or less). If it is such a ratio, the outstanding designability derived from a colored aggregate will be provided.

  The colored resin particles (c) are formed so that colored resin materials including a binder and a colored pigment are scattered in the form of particles. The size of the colored resin particles is preferably about 0.1 to 20 mm (more preferably 0.5 to 10 mm). In the present invention, the range of designability can be expanded by combining various colored resin particles having different sizes.

  As the binder in the colored resin material, the same resin component as in (a) above can be used. Further, as the colored pigment in the colored resin material, the same colored pigment as in the above (a) can be used. By combining one or more of these colored pigments, the colored resin particles have a desired color tone. Can be adjusted. The concentration of the color pigment in the colored resin material may be set as appropriate, but preferably set to 40% by weight or less. Further, in the colored resin material, an extender pigment can be used in addition to the colored pigment.

  In particular, the colored resin particles preferably include those having translucency. The colored resin particles having translucency are formed of a transparent colored resin material. If such colored resin particles having translucency are used, the sense of depth can be further enhanced.

  The transparency of the transparent colored resin material can be imparted by setting the concentration of the color pigment low. The concentration of the color pigment in the transparent colored resin material is preferably set to 5% by weight or less (more preferably 0.001% to 3% by weight, and still more preferably 0.01% to 2% by weight). Good.

The design layer (c) of the present invention can be formed by the following method (a) or (b).
(A) A design layer forming material in which at least two or more liquid or gel colored resin particles obtained by encapsulating or gelling a colored resin material are dispersed in a dispersion medium is applied.
(B) At least two or more kinds of colored resin materials are used as they are as a design layer forming material, and this design layer forming material is applied in the form of particles.

The dispersion medium for the design layer forming material (a) is not particularly limited, but a dispersion resin of the resin component (a) or a water-soluble resin and water-based ones are preferred, and if necessary a gel Agents, other additives, etc. can also be included. Moreover, a coloring material can also be included to such an extent that the design property of a colored resin particle is not inhibited.
In said (a), a pattern surface can be formed efficiently by one coating. In the coating of the design layer forming material, various coating methods can be employed, and spray coating is particularly preferable. The coating amount of the design layer forming material is preferably about 0.1 to 1 kg / m ² .

In the above (b), a coating method capable of forming colored resin particles can be employed, and spray coating is particularly suitable. When two or more kinds of design layer forming materials are used, these design layer forming materials may be applied simultaneously or sequentially. When coating a plurality of types of design layer forming materials at the same time, a multi-head spray coating machine or the like can be used as a coating tool. The application amount of the colored resin composition is preferably about 0.01 to 3 kg / m ² (more preferably 0.05 to ² kg / m ² ).

  In addition to the above components, the design layer forming material of the above (A), (B), and (C) can contain other components as required unless the effects of the present invention are significantly impaired. Such components include, for example, plasticizers, algae inhibitors, antibacterial agents, deodorants, adsorbents, flame retardants, ultraviolet absorbers, light stabilizers, antioxidants, catalysts, colored pigments, extender pigments, glitter Pigments, phosphorescent pigments, fluorescent pigments, aggregates, fibers and the like.

In the present invention, it is preferable to have at least two different design layers. By stacking different design layers, it is possible to further enhance the sense of depth and give a sense of quality. As such a design layer, the thing of the following aspects is mentioned, for example.
(D) A layer in which the above (a) and (b) are laminated (e) A layer in which the above (a) and (c) are laminated (f) The above (b) and (c) are laminated. Layer (e) A layer in which (a), (b), and (c) above are laminated. In addition, in the above (d) to (e), each layer ((b), (b), (c)) What is necessary is just to set the order which laminates | stacks suitably by desired design property.

The manufacturing method of the laminated body of this invention is not specifically limited, A well-known method is employable. For example,
(First step) A material for forming a base layer (hereinafter also referred to as “base layer forming material”) is applied and laminated on the back surface of the transparent glass plate.
(2nd process) Laminate a designable building material on a base layer, or apply and laminate a design layer forming material,
And the like.

  In the first step, the base layer forming material can be applied uniformly over the entire back surface of the transparent glass plate or can be applied so as to form an arbitrary pattern. In particular, when the base layer forming material includes a colorant, the aesthetics can be further improved by applying the base layer forming material so as to form an arbitrary pattern.

  In the second step, when the architectural building material is laminated, it may be laminated before or after the base layer forming material is dry-cured, but in the present invention, it is preferably performed before the base layer-forming material is dry-cured. . In this case, since the base layer forming material also acts as an adhesive with the design layer, the manufacturing can be simplified.

In the second step, when the design layer forming material is applied and laminated, the design layer forming material may be applied before or after the base layer forming material is dried and cured.
Furthermore, when two or more design layers are laminated, after the second step, the second design layer forming material may be applied and laminated, and the same applies when three or more design layers are laminated. What is necessary is just to laminate. In addition, when laminating the design layer forming material, it may be before the drying and curing of the design layer forming material of the previous layer or after the drying and curing.

  In the first step and the second step, as a method of applying and laminating the base layer forming material and the design layer forming material, for example, application devices such as rollers, brushes, trowels, spatulas, guns, extrusion molding, flow coaters And a method using an apparatus such as a roll coater.

  The laminated body of this invention can also laminate | stack a base layer, a design layer, and also a fibrous layer on the back surface of a transparent glass plate. The fibrous layer of the present invention is made of woven fabric, non-woven fabric, mesh or the like. The fiber material of such a fibrous layer includes pulp fiber, polyester fiber, polypropylene fiber, aramid fiber, vinylon fiber, polyethylene fiber, polyarylate fiber, PBO fiber (polyparaphenylene benzobisoxazole fiber), nylon fiber, acrylic fiber Examples thereof include organic fibers such as fibers, vinyl chloride fibers and cellulose fibers, inorganic fibers such as glass fibers, silica fibers, silica-alumina fibers, carbon fibers and silicon carbide fibers. In the present invention, those containing inorganic fibers are preferred, and among the inorganic fibers, those containing glass fibers are preferred.

The fibrous layer is more flexible than the transparent glass plate and has air permeability. Therefore, the fibrous layer can alleviate the influence of stress due to the cohesive force of the thermosetting resin when the design layer is formed, and can prevent the transparent glass plate from being distorted.
Furthermore, the fibrous layer can suppress the breakage of the glass due to an impact or a fire, and can prevent the glass fragments from being scattered. In particular, a fibrous layer containing glass fibers is preferable because it has heat resistance and is lightweight. Further, the fibrous layer is advantageous in that the back surface can be flattened, the thickness of the laminate can be easily managed, and the construction is easy. The thickness of the fibrous layer may be about 0.1 mm to 1 mm.

  The fibrous layer may be laminated before or after the design layer forming material is dried and cured, but in the present invention, it is preferably performed before the design layer forming material is dried and cured. In this case, since the design layer forming material also acts as an adhesive for the fibrous layer, the production can be simplified. Moreover, when laminating | stacking a fibrous layer after the drying hardening of the design layer forming material, a well-known adhesive material can be used.

  The thickness of the laminate of the present invention is not particularly limited, but is preferably about 1 mm to 50 mm (preferably about 1.5 mm to 30 mm, more preferably about 2 mm to 20 mm).

The laminate of the present invention can also be applied to various uses such as building materials such as walls, floors, and ceilings.
By sticking such a laminate so that the transparent glass plate is on the front surface side and the fiber layer side is on the back surface side, a high-quality design can be expressed.

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

<Base layer>
・ Base layer forming material 1
The thermosetting resin A [aqueous acrylic silicone resin (solid content: 50%, alkoxysilyl group, carboxyl group-containing), SiO ₂ content: 0.2%] was used as the base layer forming material 1.

・ Base layer forming material 2
The thermosetting resin B [aqueous acrylic-silicon resin (solid content 50%, alkoxysilyl group, carboxyl group-containing) SiO ₂ content 10%] was used as the base layer forming material 2.

Base layer forming material 3
The thermosetting resin C [aqueous acrylic silicon resin (solid content: 50%, alkoxysilyl group, carboxyl group-containing) SiO ₂ content: 50%] was used as the base layer forming material 3.

Base layer forming material 4
The thermosetting resin D [aqueous epoxy resin (solid content: 50%, epoxy group-containing): amine compound (amino group-containing) = 70: 30 (weight ratio)] was used as the base layer forming material 4.

Base layer forming material 5
The thermoplastic resin A [aqueous acrylic resin (solid content: 50%, carboxyl group-containing)] was used as the base layer forming material 5.

・ Base layer forming material 6
Thermosetting resin B [aqueous acrylic silicon resin (solid content 50%, alkoxysilyl group, carboxyl group-containing) SiO ₂ content 10%] 100 parts by weight and coloring material A (shining scaly pigment [deposited aluminum flake pigment , Scaly, size 150 μm, thickness 10 μm] was mixed and stirred by a conventional method to obtain base layer forming material 6.

Base layer forming material 7
Thermosetting resin B [aqueous acrylic silicone resin (solid content 50%, alkoxysilyl group, carboxyl group-containing) SiO ₂ content 10%] 100 parts by weight and coloring material B (carbon black pigment) 1.5 weight, The base layer forming material 7 was obtained by mixing and stirring by a conventional method.

<Design layer>
・ Design layer forming material 1
Design layer by mixing and stirring 100 parts by weight of colored aggregate A (black colored silica sand, average particle diameter of 160 μm, light transmittance of less than 1%) and 16 parts by weight (solid content) of acrylic resin emulsion. A forming material 1 was obtained.

・ Design layer forming material 2
Design layer by mixing and stirring 100 parts by weight of colored aggregate A (black silica sand, average particle diameter of 160 μm, light transmittance of less than 1%) and 16 parts by weight (solid content) of acrylic silicon resin emulsion A forming material 2 was obtained.

・ Design layer forming material 3
Design layer by mixing and stirring 100 parts by weight of colored aggregate B (gray silica sand, average particle diameter 160 μm, light transmittance of less than 1%) and 16 parts by weight (solid content) of acrylic silicone resin emulsion A forming material 3 was obtained.

・ Design layer forming material 4
Design layer by mixing and stirring 100 parts by weight of colored aggregate C (white silica sand, average particle diameter 140 μm, light transmittance of less than 1%) and 16 parts by weight (solid content) of acrylic silicone resin emulsion by a conventional method. A forming material 4 was obtained.

・ Design layer forming material 5
80 parts by weight of colored aggregate C (white quartz sand, average particle diameter of 140 μm, light transmittance of less than 1%), 20 parts of transparent colored aggregate A (cold stone, average particle diameter of 0.8 mm, light transmittance of 16%) The design layer forming material 5 was obtained by mixing and stirring 16 parts by weight (solid content) of the acrylic silicone resin emulsion by a conventional method.

・ Design layer forming material 6
28 parts by weight of colored aggregate A (black silica sand, average particle diameter of 160 μm, light transmittance of less than 1%) and 20 parts of colored aggregate D (light yellow silica sand, average particle diameter of 100 μm, light transmittance of less than 1%) A colored aggregate E (brown silica sand, average particle size 170 μm, light transmittance of less than 1%) and 16 parts by weight (solid content) of an acrylic silicone resin emulsion were mixed and stirred by a conventional method 6 Got.

・ Design layer forming material 7
Black resin particles (acrylic resin emulsion, black iron oxide, yellow iron oxide, dial, titanium oxide, granulated resin material containing water as the main component, color pigment concentration of 3% by weight, particle diameter of about 2 mm) and dark Gray resin particles (acrylic resin emulsion, black iron oxide, titanium oxide, granulated colored resin material mainly composed of water, coloring pigment concentration 2% by weight, particle diameter about 1 mm) and light gray particles (acrylic resin emulsion, Granulated product of colored resin material containing black iron oxide, titanium oxide and water as the main component, coloring pigment concentration of 2% by weight, particle diameter of about 1 mm) in aqueous medium (acrylic resin emulsion, aqueous medium containing water as main component) A water-in-water type colored resin particle dispersion dispersed in the product was obtained as a design layer forming material 7.

・ Design layer forming material 8
Black resin particles (acrylic silicon resin emulsion, black iron oxide, yellow iron oxide, petal, titanium oxide, granulated product of colored resin material mainly composed of water, color pigment concentration of 3% by weight, particle diameter of about 2 mm), Dark gray resin particles (acrylic silicon resin emulsion, black iron oxide, titanium oxide, granulated colored resin material mainly composed of water, coloring pigment concentration 2% by weight, particle diameter about 1 mm) and light gray particles (acrylic silicon) Resin emulsion, black iron oxide, titanium oxide, granulated product of colored resin material mainly composed of water, color pigment concentration 2% by weight, particle diameter about 1 mm) in aqueous medium (acrylic silicone resin emulsion, water as the main component) A water-in-water colored resin particle dispersion dispersed in an aqueous medium) was obtained and used as a design layer forming material 8.

(Examples 1 to 16 and Comparative Examples 1 to 4)
Using the base layer forming material and the design layer forming material shown in Table 1, a laminate was produced by the following manufacturing method, and the following evaluation was performed on the obtained laminate. The results are shown in Table 1.
<Manufacture of laminates>
(First step)
A base layer forming material is applied to a transparent glass plate (400 mm × 600 mm, thickness 3 mm) with a roller at a required amount of 0.3 kg / m ² and then dried at a temperature of 70 ° C. and a relative humidity of 60% for 1 hour. A base layer was formed. The base layer had a thickness of 0.15 mm.
(Second step)
A design layer forming material was applied on the base layer, and then dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate. In addition, the coating method of the design layer forming material is shown below.
Design layer forming materials 1 and 2: Coating was applied by spray at a required amount of 5.0 kg / m ² . The thickness of the design layer was 4.2 mm.
Design layer forming materials 7 and 8: Applied by spray at a required amount of 0.6 kg / m ² . The thickness of the design layer was 0.3 mm.

<Adhesion evaluation 1>
The adhesion of the produced laminate was evaluated.
A: Good adhesion.
○: Slight lifting is recognized in the design layer.
Δ: Peeling is observed in the base layer and the design layer.

<Adhesion evaluation 2>
The prepared laminate was immersed in warm water at 50 ° C. for 48 hours, and then the adhesiveness and design change of the laminate were observed and evaluated.
A: No abnormality was observed in adhesion and design.
○: Slight lifting or the like was observed in the design layer, but an excellent design was maintained.
(Triangle | delta): The float was recognized by the base layer and the design layer, and the design was not able to be maintained.
X: The design by which peeling was recognized by the base layer and the design layer was not able to be maintained.

<Design evaluation>
The obtained laminated body was evaluated from the glass plate side and the design property was evaluated.
A: The design layer pattern was clearly visible, and there was a sense of depth and depth, and an even more luxurious design was revealed.
B: The design layer pattern was clearly visible, and a high-class design with a sense of depth and depth was revealed.
C: The design layer design is slightly unclear, but a design with a sense of depth and depth was revealed.
D: The design layer was peeled off and the design properties were insufficient.

(Example 17)
After applying the base layer forming material 2 to a transparent glass plate (400 mm × 600 mm, thickness 3 mm) with a roller at a required amount of 0.3 kg / m ² , drying is performed for 1 hour at a temperature of 70 ° C. and a relative humidity of 60%. A base layer (thickness: 0.15 mm) was formed. Next, the design layer forming material 6 was applied on the base layer by spraying at a required amount of 5.0 kg / m ² and then dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate. . The design layer had a thickness of 4.2 mm. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 18)
After applying the base layer forming material 2 to a transparent glass plate (400 mm × 600 mm, thickness 3 mm) with a roller at a required amount of 0.3 kg / m ² , drying is performed for 1 hour at a temperature of 70 ° C. and a relative humidity of 60%. A base layer (thickness: 0.15 mm) was formed. Next, the design layer forming materials 2, 3, and 4 are applied in a ball shape using a wind pressure at a weight ratio of 1: 1: 1 (the total required amount of the design layer forming materials 2, 3, and 4 is 5.0 kg). / M ² ) and then dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate. The design layer had a thickness of 4.2 mm. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 19)
A laminated body was obtained in the same manner as in Example 18 except that the design layer forming material 5 was used in place of the design layer forming material 4 in Example 18. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 20)
A laminated body was obtained in the same manner as in Example 19 except that the base layer forming material 6 was used instead of the base layer forming material 2 of Example 19. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 21)
After applying the base layer forming material 6 to a transparent glass plate (400 mm × 600 mm, thickness 3 mm) with a roller at a required amount of 0.3 kg / m ² , drying is performed for 1 hour at a temperature of 70 ° C. and a relative humidity of 60%. A base layer (thickness: 0.15 mm) was formed. Next, the design layer forming material 8 was applied at a required amount of 0.6 kg / m 2 by spraying and then dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate. The thickness of the design layer was 0.3 mm. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 22)
On the design layer of the laminate obtained in Example 21, the design layer forming materials 2, 3, 4 were further applied in a ball shape using wind pressure at a weight ratio of 1: 1: 1 (design) The total required amount of the layer forming materials 2, 3 and 4 was 5.0 kg / m ² ) and then dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate. The total thickness of the design layer was 4.5 mm. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 23)
After applying the base layer forming material 7 to a transparent glass plate (400 mm × 600 mm, thickness 3 mm) with a streaked pattern roller at a required amount of 0.3 kg / m ² , at a temperature of 70 ° C. and a relative humidity of 60%, The base layer (thickness: 0.15 mm) having a streak pattern was formed by drying for 1 hour. Next, the design layer forming material 5 was applied by spray at a required amount of 5.0 kg / m 2 and then dried at a temperature of 50 ° C. and a relative humidity of 60% for 5 hours to obtain a laminate. The design layer had a thickness of 4.2 mm. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Claims (4)

A laminated body in which a base layer and a design layer are sequentially laminated on the back surface of the transparent glass plate,
The laminated body, wherein the base layer contains at least a thermosetting resin as a binder.   The laminate according to claim 1, wherein the base layer includes a thermosetting resin having at least an alkoxysilyl group as a binder. The laminate according to claim 1, wherein the design layer includes a coloring material. The laminate according to any one of claims 1 to 3, wherein the colorant is a colored aggregate and / or colored resin particles.

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