JP2010195618A - Decorated laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide decorated laminated glass excellent in basic performances such as light resistance, heat resistance, moisture resistance and shock resistance, as well as excellent in designing property while having excellent adhesiveness between an interlayer and the glass. <P>SOLUTION: The decorated laminated glass includes a decorative sheet 11 interposed with adhesive layers 3A, 3B between two glass sheets 2A, 2B, wherein the decorative sheet includes at least a pattern layer and a protective layer successively layered on a substrate, and the protective layer is formed by crosslinking and curing an ionization radiation-curable resin composition. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a decorative laminated glass.

  Laminated glass is widely used in windows and doors for general buildings, houses, furniture, etc., and for large and small buildings, such as large stores and buildings. It sticks through the applied intermediate film. And as an intermediate film, it is common to use the resin film formed by polyvinyl butyral resin and ethylene-vinyl acetate copolymer resin (for example, patent documents 1 and 2).

  By the way, with the recent increase in awareness of the environment such as the living environment or public facilities, laminated glass with excellent design as well as mechanical performance such as adhesion between the interlayer film and glass, which has been conventionally required. Is desired. Several laminated glasses that have focused on designability have been developed so far (see, for example, Patent Document 3), but have excellent adhesion between an interlayer film and glass, and also have excellent design properties. However, the development of laminated glass satisfying these requirements at a high level is desired.

JP-A-10-194797 JP 2004-59395 A Japanese Utility Model Publication No. 6-33936

  The object of the present invention is to provide a laminated glass that has excellent basic performance such as light resistance, heat resistance, moisture resistance, impact resistance, etc., has excellent adhesion between an interlayer film and glass, and has excellent design. It is to be.

As a result of intensive studies to achieve the above object, the present inventor has found that the object can be achieved by making the decorative sheet used for the laminated glass a specific configuration. The present invention has been completed based on such findings.
That is, the present invention
(1) A decorative laminated glass in which a decorative sheet is sandwiched between two glass plates with an adhesive layer interposed between the two glass plates, the decorative sheet having a protective layer on a substrate, and the protective layer is ionizing radiation cured Decorative laminated glass formed by crosslinking and curing a functional resin composition,
(2) The decorative laminated glass according to (1), wherein the decorative sheet has a pattern layer between the base material and the protective layer,
(3) The decorative laminated glass according to (2), which has a transparent resin layer between the pattern layer and the protective layer,
(4) The decorative laminated glass according to any one of the above (1) to (3), wherein the decorative sheet is embossed from the protective layer side,
(5) The decorative laminated glass according to any one of (1) to (4), in which two decorative sheets are sandwiched, and (6) the adhesive layer is an ethylene-vinyl acetate copolymer resin adhesive The decorative laminated glass according to any one of the above (1) to (5), which is formed by
Is to provide.

  According to the present invention, a laminated glass having excellent basic properties such as light resistance, heat resistance, moisture resistance, impact resistance and the like, having excellent adhesion between the interlayer film and the glass, and having excellent design properties is obtained. be able to.

It is a schematic diagram which shows the preferable one aspect | mode of the cross section of the decorative laminated glass of this invention. It is a schematic diagram which shows the preferable one aspect | mode of the cross section of the decorative laminated glass of this invention. It is a schematic diagram which shows the preferable one aspect | mode of the cross section of the decorative sheet used for the decorative laminated glass of this invention. It is a schematic diagram which shows the test piece used by the heat-resistant creep test in an Example.

An example of the preferable aspect of the decorative laminated glass of this invention is demonstrated using FIGS. 1 and 2 are schematic views showing a cross section of an example of a laminated laminated glass having a preferred layer structure of the present invention. The decorative laminated glass 1 shown in FIG. 1 is obtained by sequentially laminating an adhesive layer 3A, a decorative sheet 11, an adhesive layer 3B, and a glass plate 2B on a glass plate 2A. Moreover, in the example shown in FIG. 2, it has the structure which has two decorative sheets, and it is the structure attached between an adhesive layer between a glass plate and a decorative sheet and between two decorative sheets. Have.
FIG. 3 is a schematic view showing an example of an embodiment having a preferred layer structure of a decorative sheet used in the laminated laminated glass of the present invention. The decorative sheet shown in FIG. 3 is obtained by sequentially laminating a pattern layer 13, an adhesive layer 15, a transparent resin layer 16, a primer layer 17, and a protective layer 14 on a base material 12, from the protective layer side. An embossed concavo-convex pattern 18 is provided.

[Glass plate 2]
The glass plate 2 used in the present invention is a colorless or colored transparent plate glass or a translucent plate glass as long as it does not lose the design of the decorative sheet. The type of glass plate may be appropriately selected depending on the application, and examples thereof include ordinary glass, float glass, frosted glass, frosted glass, highly transmissive glass, template glass, heat resistant glass, and wire mesh glass. The types of the two glass plates used may be the same or different. What is necessary is just to select the thickness of a glass plate suitably according to a use, Usually, about 1-15 mm, Preferably it is 2-12 mm, More preferably, it is 2-10 mm, The thickness of two glass plates is the same, but is different. Also good.

[Adhesive layer 3]
The adhesive layer 3 is a layer provided for bonding the glass plate and the decorative sheet, or the decorative sheets. Adhesives used for the adhesive layer 3 include acrylic resin-based, urethane resin-based, vinyl acetate resin-based, polyvinyl alcohol-based adhesives, and elastomer-based adhesives such as styrene-butadiene rubber and styrene-isoprene. In addition, a mixed adhesive that is used alone or arbitrarily mixed may be mentioned. Among these, particularly from the viewpoint of adhesion and transparency in the adhesion between the glass plate and the decorative sheet, a vinyl acetate resin adhesive is preferable, and an ethylene-vinyl acetate copolymer adhesive is particularly preferable. By using an ethylene-vinyl acetate copolymer adhesive, excellent adhesion to the protective layer 14 obtained by crosslinking and curing an ionizing radiation curable resin composition described later can be obtained.
When an ethylene-vinyl acetate copolymer adhesive is used, the vinyl acetate content in the copolymer is 5 to 50% by mass, preferably 10 to 40% by mass. In the present invention, a sheet-like adhesive made of the resin as described above can also be used.
From the viewpoint of obtaining sufficient adhesiveness while suppressing the thickness of the laminated glass, the thickness of the adhesive layer 3 is usually about 0.1 to 3 mm, preferably 0.1 to 1 mm, and preferably 0.1 to 0.5 mm. Is more preferable.

[Decorative sheet 11]
The decorative sheet 11 used in the present invention is provided for imparting a design to the decorative laminated glass of the present invention. The decorative sheet 11 has a protective layer 14 on a substrate 12, and the protective layer is an ionizing radiation curable resin. The composition is formed by crosslinking and curing.

<< Substrate 12 >>
For the base material 12, for example, paper, non-woven fabric, thermoplastic resin sheet, or a composite material thereof is used.

Examples of paper include thin paper, kraft paper, fine paper, linter paper, baryta paper, sulfate paper, and Japanese paper. Nonwoven fabrics are made of fibers such as polyester resin, acrylic resin, nylon, vinylon, and glass. Nonwoven fabric may be mentioned. The basis weight of paper or non-woven fabric is usually about ²⁰ to 100 g / m ² . Further, the paper or the nonwoven fabric may be impregnated with a resin, or may be colored for the purpose of improving design properties.

Examples of the thermoplastic resin sheet include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins, polyolefin resins, polyvinyl chloride resins, polystyrene, ABS resins, polycarbonate resins, and polyamide resins. Resins are preferred.
Polyolefin resins include polyethylene (high density, medium density, or low density), polypropylene (isotactic or syndiotactic), polybutene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer. And polyolefin resins such as olefinic thermoplastic elastomers. Examples of olefinic thermoplastic elastomers include hard segments composed of crystalline polyolefin resins as described above and elastomers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, atactic polypropylene, styrene-butadiene rubber, and hydrogenated styrene-butadiene rubber. What is obtained by mixing soft segments consisting of The mixing ratio of the hard segment and the soft segment is about [soft segment / hard segment] = 5/95 to 40/60 (mass ratio). If necessary, the elastomer component is crosslinked by a known crosslinking agent such as sulfur or hydrogen peroxide. The thermoplastic resin sheet may be colored for the purpose of improving design properties.

Examples of the layer structure of the substrate include those obtained by laminating the above-mentioned paper, nonwoven fabric, thermoplastic resin sheet, etc., in a single layer or two or more layers. Among these, a thermoplastic resin sheet is preferable, a polyolefin resin sheet is more preferable, and a sheet made of polyethylene or polypropylene is particularly preferable.
The thickness of the base sheet (total thickness in the case of a laminate) is not limited, but is generally about 25 to 500 μm. When the uneven pattern 18 is applied by embossing, the thickness is 80 to 500 μm. Preferably, 80 to 300 μm is more preferable, and 80 to 200 μm is more preferable.

<< Picture layer 13 >>
The pattern layer 13 is preferably provided in order to impart decorativeness to the decorative sheet used in the present invention, and is formed by printing various patterns using ink and a printing machine.
Patterns include stone patterns that simulate the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns that imitate fabrics and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. In addition, letters, symbols, geometric patterns, colored solids printed on the entire surface, and patterns obtained by combining these are also included.
These patterns can be formed by multicolor printing with normal yellow, red, blue, and black process colors, as well as by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. It is formed.

  As the ink used for forming the pattern layer 13, an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. The binder is not particularly limited. For example, polyurethane resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, vinyl chloride / vinyl acetate. Any one selected from a copolymer resin, a vinyl chloride / vinyl acetate / acrylic copolymer resin, a chlorinated polypropylene resin and the like may be used alone or in admixture of two or more.

Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
The thickness of the pattern layer 13 is usually about 1 to 20 μm.

<< Protective layer 14 >>
The protective layer 14 is a layer provided to protect a layer provided between the base material 12 such as the pattern layer 13 and the protective layer 14, and is a layer obtained by crosslinking and curing an ionizing radiation curable resin composition. It is. The ionizing radiation curable resin composition is a composition comprising an ionizing radiation curable resin that is cured by ionizing radiation such as ultraviolet rays and electron beams, and other components that are added as necessary.

(Ionizing radiation curable resin)
As the ionizing radiation curable resin used for the protective layer 14, a conventionally known compound may be appropriately used. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions.

  As the polymerizable monomer, typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable, and among them, a polyfunctional (meth) acrylate is preferred. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) Acrylate, dicyclopentanyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, bisphenol A diacrylate, ethylene oxide modified, propylene oxide Examples thereof include modified polyfunctional (meth) acrylates such as modified, propionic acid modified, caprolactone modified and the like. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, together with the polyfunctional (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate for the purpose of lowering the viscosity. Monofunctional (meth) acrylates such as isobornyl (meth) acrylate can be appropriately used in combination as long as the object of the present invention is not impaired. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of the polymerizable oligomer include oligomers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Can be mentioned.
Among these, urethane (meth) acrylate oligomers are preferable from the viewpoint of adhesiveness with a glass plate. More specifically, the urethane (meth) acrylate oligomer (A) having a weight average molecular weight of 1000 to 4000 having two radically polymerizable unsaturated groups in one molecule is 30 to 80% by mass, and three in one molecule. It is preferable to use a mixture comprising 20 to 70% by mass of an aliphatic urethane (meth) acrylate oligomer (B) having -15 radical polymerizable unsaturated groups as an ionizing radiation curable resin.

The urethane (meth) acrylate oligomer (A) having a weight average molecular weight of 1000 to 4000 has a diisocyanate, a polyhydric alcohol having a weight average molecular weight of 500 to 2000 having two or more hydroxyl groups in one molecule, and a hydroxyl group at the terminal. In addition, an oligomer having a weight average molecular weight of 1000 to 4000, preferably 1000 to 3000, formed by bonding with a (meth) acrylate compound having a radically polymerizable unsaturated group.
The diisocyanate is an aliphatic, alicyclic or aromatic isocyanate having two or more isocyanate groups in one molecule. For example, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6 -Hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like.

  Examples of the polyhydric alcohol having a weight average molecular weight of 500 to 2000 include polyester polyol, polyether polyol, polycarbonate polyol, and acrylic polyol having hydroxyl groups at both ends. Examples of the polyester polyol include (a) an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof or an epoxy compound, and (b) a condensation product of a polybasic acid and an alkylene glycol. And (c) a ring-opening polyester compound derived from a cyclic ester compound, and these can be used alone or in admixture of two or more. Examples of the polyether polyol include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol. Polyester diol having a weight average molecular weight of 500 to 2,000 obtained as a condensation product with alkylene glycol using adipic acid as the polybasic acid of (b) above is preferred because various physical properties are good. Used.

  The (meth) acrylate having a hydroxyl group at the terminal and a radically polymerizable unsaturated group is an ester compound of acrylic acid, methacrylic acid or a derivative thereof, and has a hydroxyl group at the terminal. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate , (Meth) acrylic acid ester compounds having one polymerizable unsaturated group such as 2-hydroxy-3-phenyloxypropyl acrylate, or other (meth) having two or more polymerizable unsaturated groups in one molecule Examples include acrylic ester compounds.

  The aliphatic urethane (meth) acrylate oligomer (B) used together with the urethane (meth) acrylate oligomer (A) described above is a radically polymerizable unsaturated group such as 3 to 15 (meth) acryloyl groups in one molecule. Polyfunctional (3-15 functional) urethane acrylate obtained by reacting with aliphatic diisocyanate, polyfunctional polyol, (meth) acrylate having a hydroxyl group at the terminal and a radical polymerizable unsaturated group It is.

Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
The (meth) acrylate having a hydroxyl group and a radically polymerizable unsaturated group is 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy. Examples thereof include (meth) acrylic acid ester compounds having one polymerizable unsaturated group such as cyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl acrylate and the like.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  When an ultraviolet curable resin composition is used as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin composition. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. In addition, for example, a photosensitizer such as p-dimethylbenzoate, tertiary amines, and a thiol sensitizer can be used.

(Various additives)
Various additives can be blended in the ionizing radiation curable resin composition depending on the desired physical properties of the protective layer to be obtained. This additive is obtained by, for example, dissolving or dispersing an abrasion resistance improver such as inorganic particles such as alumina and silica or resin particles such as acrylic, such as resins such as polypropylene and polyethylene, in an organic solvent such as an ester. In addition to waxes, weather resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, filling Agents, solvents, colorants and the like. The content of these various additives in the ionizing radiation curable resin composition is within a range that does not impair the effects of the present invention while sufficiently obtaining the additive effect of various additives, and is appropriately set. .

(Method for forming protective layer 14)
The method for forming the protective layer 14 is preferably performed as follows. A polymerizable monomer, a polymerizable oligomer, and various additives, which are ionizing radiation curable components, are homogeneously mixed at predetermined ratios to prepare a coating liquid composed of an ionizing radiation curable resin composition. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
Gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., so that the coating liquid prepared in this manner is on the surface of the substrate 12 so that the thickness after curing is within a predetermined range. The known method, preferably gravure coating, is applied to form an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the surface protective layer after curing is usually 1 to 20 μm, preferably 2 to 20 μm, more preferably 3 to 10 μm.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  The cured resin layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted.

<< Adhesive layer 15 >>
The adhesive layer 15 is a layer provided as desired when the decorative sheet 11 has a transparent resin layer 16.
The adhesive used in the adhesive layer can be appropriately selected from known or commercially available adhesives according to the components constituting the picture layer 13 or the transparent resin layer 16. For example, in addition to polyolefin resins such as polyethylene and polypropylene, thermosetting resins such as polyester resins, polyurethane resins, and epoxy resins can be used. These resins may be used in the state of an emulsion. Of these, urethane resin adhesives are preferred from the viewpoint of heat resistance. As the urethane resin adhesive, a two-component curable urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent) is preferably exemplified.

What is necessary is just to implement according to a well-known method as an adhesion | attachment method according to the kind etc. of adhesive to be used. For example, using a polyolefin-based resin such as polyethylene or polypropylene, a method of coating on the pattern layer by melt extrusion (extrusion coating method), a thermosetting resin such as a polyester-based resin, a polyurethane-based resin, or an epoxy-based resin, isocyanate, Apply an adhesive that contains a crosslinking agent such as amine, a polymerization initiator such as methyl ethyl ketone peroxide, hydroperoxide, azabisisobutyronitrile, a polymerization accelerator such as cobalt naphthenate or dimethylaniline, A dry laminating method can be employed. In the present invention, an adhesive capable of thermocompression bonding is used, and the pattern layer 15 and the transparent resin layer 16 can be laminated by thermocompression bonding.
The thickness of the adhesive layer 15 varies depending on the protective layer 14 and the type of adhesive to be used, but is usually about 0.1 to 30 μm.

<< Transparent resin layer 16 >>
The transparent resin layer 16 is not limited as long as it is transparent, and is a layer made of a resin having transparency such as colorless and transparent, colored and transparent.
As the transparent resin layer 16, for example, a layer formed of a thermoplastic resin can be suitably used. Specifically, soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Polymers, ionomers, acrylic esters, methacrylic esters and the like can be mentioned. Among these, polyolefin resins such as polypropylene are preferable.

  The transparent resin layer 16 may be colored as long as it is transparent as described above. In this case, a coloring material (pigment or dye) can be added to the thermoplastic resin as described above for coloring. As the colorant, a known or commercially available pigment or dye can be appropriately used. These can select 1 type, or 2 or more types. Further, the addition amount of the colorant may be appropriately set according to a desired color tone.

  In addition, the transparent resin layer 16 may include a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft as necessary. Various additives such as components (for example, rubber) may be included.

  As a method for forming the transparent resin layer 16, for example, a method of laminating a preformed sheet or film on an adjacent layer, a resin composition capable of forming the transparent resin layer 16 is melt-extruded, and applied onto the adjacent layer. Any of the method of laminating and the method of laminating together with adjacent layers can be employed. In the present invention, it is particularly preferable to form the transparent resin layer 16 by melt extrusion, and it is particularly desirable to form the polyolefin resin by melt extrusion. Specifically, the transparent resin layer 16 can be suitably formed by forming the adhesive layer 15 on the pattern layer 13 in advance, and melt-extruding and applying a polypropylene-based thermoplastic elastomer on the adhesive layer 15. . What is necessary is just to implement the method of melt extrusion according to the well-known method using a T die etc., for example.

  The thickness of the transparent resin layer 16 can be appropriately set depending on the use of the final product, the method of use, etc., but it is generally preferably about 50 to 250 μm, particularly about 20 to 200 μm.

Further, the surface and / or the back surface of the transparent resin layer 16 may be subjected to a physical or chemical surface treatment such as an oxidation method or a concavo-convex method as necessary in order to improve the adhesion with an adjacent layer. it can.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

<< Primer layer 17 >>
A primer layer 17 can also be formed on the front surface and / or the back surface of the transparent resin layer 16. Examples of materials for forming the primer layer 17 include polyester resins, polyurethane resins, acrylic resins, polycarbonate resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins (nitrified cotton), and others. Further, compounds such as alkyl titanate and ethyleneimine can also be used. Among these, it is preferable to use an acrylic urethane resin, urethane nitrified cotton, a two-component curable urethane resin, or the like as a binder resin. The use of fatty acid isocyanate (aliphatic isocyanate) such as hexamethylene diisocyanate (HMDI) as the isocyanate and acrylic polyol as the polyol is preferable because more excellent weather resistance and adhesion can be obtained.

The primer layer 17 can be formed as it is or in a state dissolved or dispersed in a solvent, and the primer layer can be formed according to a known printing method such as gravure printing or a coating method.
In addition, in the decorative sheet 11 used in the present invention for the purpose of enhancing the adhesiveness with the glass plate, a primer layer similar to the above is provided on the back surface of the base material 2 (the surface opposite to that provided with a pattern layer or the like). Can be provided.

<< Uneven pattern 18 >>
The decorative sheet 11 used in the present invention is preferably provided with an uneven pattern 18 by embossing for the purpose of enhancing the design.
The concavo-convex pattern 18 is formed by applying heat and pressure with an embossing plate from the upper surface of the substrate 12 on the side where the pattern layer 13 is provided when the decorative sheet 11 is at a temperature at which embossing can be performed by any means in the manufacturing process. be able to. Here, embossing may be performed before or after the protective layer 14 is provided. A well-known sheet or rotary embossing machine is used to form the concavo-convex pattern 18. The shape of the concavo-convex pattern 18 includes a wood grain pipe groove, stone plate surface unevenness, cloth surface texture, satin texture, sand texture, hairline. , There are many line grooves.

The depth of the concavo-convex pattern 18 by embossing may reach the primer layer 17 or the transparent resin layer 16 as shown in FIG. 3, for example, or may reach the substrate 12, and the depth of the concavo-convex pattern 18. May be appropriately selected based on a desired design. Although the depth of the uneven | corrugated pattern 18 is based also on the thickness of a decorative sheet, 5-160 micrometers is preferable normally and 10-140 micrometers is more preferable. If the depth of the concavo-convex pattern 18 is within the above range, it is preferable because excellent design properties can be obtained.
Further, the surface roughness Rz of the surface of the decorative sheet 11 on which the concavo-convex pattern 18 has been applied is about 1 to 300 μm, preferably 10 to 120 μm, and more preferably 30 to 90 μm. Here, Rz is a ten-point average roughness, which is a value measured with a measurement length of 4 mm and a cutoff value of 0.8 mm in accordance with JIS B 0601.

<Method for manufacturing decorative sheet>
Although the configuration of the decorative sheet 11 has been described above, the decorative sheet 11 may be prepared as described above, or a commercially available product may be used.
The decorative sheet 11 may be manufactured according to a known method, and an example of the manufacturing method will be described below.
A polypropylene resin film that has been subjected to easy adhesion treatment by corona discharge treatment on its surface is used as a base material 12, and a pattern such as a wood grain pattern is gravure printed on the base material to form a picture layer 13, and acrylic urethane is formed on the back surface thereof. A primer layer using a base resin or the like as a binder is formed by gravure printing. Next, an adhesive such as a two-component curable urethane resin is applied on the pattern layer 13 to form an adhesive layer 15, and further, a polypropylene resin is melt-extruded and applied with a T-die to form a transparent resin layer 16. Form. A primer layer 17 is formed on the transparent resin layer 16 by coating a resin such as a two-component curable urethane resin. Next, an ionizing radiation curable resin composition containing an ionizing radiation curable resin such as a polyfunctional urethane oligomer and various additives is applied on the primer layer 17 by gravure coating to form a coating film. The decorative sheet 11 can be obtained by irradiating an electron beam under the above conditions to crosslink and cure the coating film to form the protective layer 14.

  The decorative laminated glass of the present invention may have a configuration using two decorative sheets 11 as shown in FIG. When two decorative sheets are used, the two decorative sheets may have the same pattern or different patterns. By setting it as such a structure, the decorative laminated glass of this invention can be made into a thing with high designability from any direction of front and back. In addition, when using decorative sheets with different patterns, the front and back sides can have different patterns, and it is possible to meet diversifying consumer needs.

[Method for producing decorative laminated glass]
The decorative laminated glass of the present invention may be produced by a known method, and can be produced, for example, as follows. Two glass plates, a prepared decorative sheet or a commercial decorative sheet are prepared, adhesive is applied to one surface of the two glass plates, and the decorative sheet is sandwiched between the surfaces coated with the adhesive, After preheating to about 100 ° C., thermocompression bonding is performed using an autoclave or the like at a temperature of 100 to 150 ° C., a pressure of 0.1 to 1 MPa, preferably about 0.2 to 0.8 MPa. Moreover, when using a sheet-like adhesive for the adhesive, a sheet-like adhesive, a decorative sheet, and a sheet-like adhesive are sequentially laminated on one glass plate, and the glass plate is placed thereon, and the above In this way, heat pressing may be performed.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Evaluation methods)
The decorative laminated glass obtained in each example was evaluated by the following methods.
(1) Light resistance-1
A test piece (40 × 25 mm square) of a decorative laminated glass is prepared, and the irradiation condition (illuminance: 25.5 mw / cm ² , wavelength: 300 to 300 mm) is used on the front and back surfaces of the test piece using a sunshine weather tester. (700 nm) for 1 hour and 42 minutes, and rain conditions (RH 90%) for 18 minutes. This is regarded as 1 cycle (1 cycle for 2 hours), and the state after repeating until 1000 hours or 2000 hours is observed visually. The evaluation was based on the following criteria.
◯: There was no discoloration, bubbles, peeling and turbidity.
Δ: Some discoloration, foam, peeling and turbidity occurred, but no problem in practical use.
X: Significant discoloration, foam, peeling and turbidity occurred.
(2) Light resistance-2
A test piece (40 × 25 mm square) of a decorative laminated glass is prepared, and the irradiation condition (illuminance: 25.5 mw / cm ² , wavelength: 300 to 300 mm) is used on the front and back surfaces of the test piece using a sunshine weather tester. (700 nm) for 1 hour and 42 minutes, and in rain conditions (RH 90%) for 18 minutes. This was repeated as 1 cycle (1 cycle for 2 hours) until 2000 hours passed, and this test piece was subjected to JIS K6854. -2: According to 1999, the peeling force (N) was measured three times under the condition of a crosshead speed of 200 mm / min by the 180 degree peeling test method using an autograph, and the average value was taken as the peeling force (N). . The state of the test piece at this time was visually observed, and the value was evaluated as the peel strength (N / 25 mm) according to the following criteria.
○: 2N / 25 mm or more, and peeled off at the adhesive layer.
X: It is less than 2N / 25mm, or it did not peel in the adhesive layer.
(3) Evaluation of heat resistance A test piece (50 × 50 mm square) of a decorative laminated glass was prepared. After immersing this test piece in hot water kept at 65 ° C. for 3 minutes and then immersing it in boiling water for 2 hours, making this one cycle for a total of 3 cycles, the state of the test piece was visually observed, and the following criteria were used. evaluated.
◯: There was no discoloration, bubbles, peeling and turbidity.
Δ: Some discoloration, foam, peeling and turbidity occurred, but no problem in practical use.
X: Significant discoloration, foam, peeling and turbidity occurred.
(4) Evaluation of moisture resistance A test piece (100 × 100 mm square) of a decorative laminated glass was prepared. This test piece is left for 14 days under the condition of 50 ° C. and RH 95%, and then left for 14 days under the condition of 50 ° C. and RH 30%. This is regarded as one cycle, and the state of the test piece after 1-3 cycles is visually observed. And evaluated according to the following criteria.
◯: There was no discoloration, bubbles, peeling and turbidity.
Δ: Some discoloration, foam, peeling and turbidity occurred, but no problem in practical use.
X: Significant discoloration, foam, peeling and turbidity occurred.
(5) Falling ball impact test Six test pieces (610 × 610 mm square) of decorative laminated glass were prepared. According to the falling ball impact test specified in JIS R3205, the state of the test piece when a 2260 g steel ball was dropped freely from a height of 3 m onto the test piece was evaluated according to the following criteria.
○: 5 or more test pieces out of 6 sheets, the decorative sheet was not cut, and there was no exposed portion of the decorative sheet due to the missing glass plate.
X: Two or more test pieces out of six pieces were cut by the decorative sheet, or an exposed portion of the decorative sheet was generated due to a missing glass plate.
(6) Shot bag test A test piece (1930 × 864 mm square) of a decorative laminated glass was prepared. The test piece was subjected to a shot bag test in which the shot bag was dropped from a height of 120 cm in accordance with JIS R3205. The state of the glass test piece at this time was visually observed and evaluated according to the following criteria.
○: No cracks occurred in 5 or more test pieces out of 6 pieces.
X: Two or more test pieces out of six pieces were cracked, or glass pieces were scattered.
(7) Cold Heat Repeat Test A decorative laminated glass test piece (150 × 150 mm square) was prepared. This test piece was left at 80 ° C. for 2 hours, then left at −20 ° C. for 2 hours. This was regarded as one cycle, and the state of the test piece after 5 and 10 cycles was visually observed. Evaluation based on the criteria.
◯: There was no discoloration, bubbles, peeling and turbidity.
Δ: Some discoloration, foam, peeling and turbidity occurred, but no problem in practical use.
X: Significant discoloration, foam, peeling and turbidity occurred.
(8) Heat-resistant creep test In the method for producing a decorative laminated glass described in the examples, a glass plate (width: 25 mm, length: 90 mm, thickness: 3 mm) and a decorative sheet (width: 25 mm, length: 50 mm) A test piece was prepared by sticking as shown in FIG. The glass plate had a through hole (φ10 mm), the test piece was fixed to the wall using one through hole 19a, and a 500 g weight was suspended using a wire in the other through hole 19b. This was placed at 80 ° C., and a static load of 500 g / 25 mm width was applied in the vertical direction for 24 hours. The deviation due to the load at this time was measured and evaluated according to the following criteria.
○: Deviation was within 1 mm / hour.
X: The deviation was longer than 1 mm / hour.
(9) Adhesiveness-1
An example in which one glass plate and the protective layer side of the decorative sheet are bonded with the adhesive used in the example (test piece-1), and one glass plate and the base side of the decorative sheet in the example. A test piece (40 mm × 150 mm square) was prepared by bonding with the adhesive used (Test piece-2). About these test pieces, according to JISK6854-2: 1999, the average peeling force (N) was measured on condition of the crosshead speed of 200 mm / min by the 180 degree peeling test method using the autograph. The state of the sample at this time was visually observed, and the value was evaluated as the peel strength (N / 25 mm) according to the following criteria.
Separate test pieces were prepared, heat-treated (the test piece was immersed in hot water kept at 65 ° C. for 3 minutes and then immersed in boiling water for 2 hours), and wet treatment (the test piece was subjected to conditions of 50 ° C. and RH 95%). Left for 14 days, then left for 14 days under conditions of 50% RH 30%), or cold heat treatment (for 2 hours under conditions of 80 ° C., then for 2 hours under conditions of −20 ° C., This was defined as 1 cycle and 10 cycles were performed on separate test pieces, and then a cross-cut tape peeling test was performed in the same manner as described above, and evaluation was performed according to the following criteria.
○: 2N / 25 mm or more, and peeled off at the adhesive layer.
X: It is less than 2N / 25mm, or it did not peel in the adhesive layer.
(10) Adhesion-2
Test pieces similar to the test pieces 1 and 2 used in Adhesion-1 were prepared. The decorative sheet surfaces of test pieces 1 and 2 were subjected to a cross-cut tape peeling test at room temperature in accordance with JIS D0202-1988. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), the film was adhered to the film with the belly of the finger and then peeled off. Judgment is represented by the number of squares that do not peel out of 100 squares, and was evaluated according to the following criteria.
Separate test pieces were prepared, heat-treated (the test piece was immersed in hot water kept at 65 ° C. for 3 minutes and then immersed in boiling water for 2 hours), and wet treatment (the test piece was subjected to conditions of 50 ° C. and RH 95%). Left for 14 days, then left for 14 days under conditions of 50% RH 30%), or cold heat treatment (for 2 hours under conditions of 80 ° C., then for 2 hours under conditions of −20 ° C., This was defined as 1 cycle and 10 cycles were performed on separate test pieces, and then a cross-cut tape peeling test was performed in the same manner as described above, and evaluation was performed according to the following criteria.
○: 100/100 (no peeling at all).
(Triangle | delta): It was 90-99 / 100.
X: It was less than 90/100.

Production Example 1 (Production of decorative sheet A)
A polyethylene resin film (thickness 80 μm) was prepared as a substrate. After the front and back surfaces were subjected to corona discharge treatment, a woodgrain pattern layer was formed on the front surface by gravure printing. On the other hand, a primer layer using an acrylic urethane resin as a binder was formed on the back surface by gravure printing. Next, a coating solution made of a two-component curable urethane resin was applied on the pattern layer to form an adhesive layer (thickness 3 μm). Furthermore, a transparent thermoplastic resin layer (thickness: 60 μm) was formed by melt extrusion coating a polypropylene thermoplastic elastomer made of an ethylene-propylene-butene copolymer with a T-die. On the transparent resin layer, a two-component curable urethane resin composed of an acrylic-urethane block polymer (main agent) and hexamethylene diisocyanate (curing agent) was applied to form a primer layer (thickness 2 μm). .

Next, 5 parts by mass of silica particles (average particle diameter: 4 to 5 μm, spherical) and 5 parts by mass of polyethylene wax (35 parts by mass of ionizing radiation curable polyfunctional urethane oligomer / 65 parts by mass of bifunctional urethane oligomer) After forming a coating film by gravure coating with an ionizing radiation curable resin composition containing a melting point of 110 to 200 ° C., the coating film is crosslinked and cured by irradiation with an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy). Thus, a protective layer (thickness 5 μm) was formed. Finally, after heating the protective layer side with an infrared non-contact type heater, embossing is performed from the surface of the protective layer using an embossed plate by hot pressure, and by shaping the uneven pattern of the wood grain conduit groove pattern, A predetermined decorative sheet A was obtained.
The obtained decorative sheet A had a surface roughness Rz of 90 μm. Here, Rz is a ten-point average roughness, which is a value measured with a measurement length of 4 mm and a cutoff value of 0.8 mm in accordance with JIS B 0601.

Production Example 2: Cosmetic sheet B
In Production Example 1, a decorative sheet B was obtained in the same manner as in Production Example 1 except that the embossed plate was changed. The obtained decorative sheet B had a surface roughness Rz of 30 μm.

Production Example 3: Cosmetic sheet C
A polypropylene resin film (thickness 60 μm) was prepared as a base material. After the front and back surfaces were subjected to corona discharge treatment, a woodgrain pattern layer was formed on the front surface by gravure printing. On the other hand, a primer layer using an acrylic urethane resin as a binder was formed on the back surface by gravure printing. Next, a coating solution made of a two-component curable urethane resin was applied on the pattern layer to form an adhesive layer (thickness 3 μm). Furthermore, a transparent thermoplastic resin layer (thickness: 80 μm) was formed by melt extrusion coating a polypropylene thermoplastic elastomer made of an ethylene-propylene-butene copolymer with a T-die.

  Next, after the transparent resin layer side was heated with an infrared non-contact heater, embossing was performed from the surface of the transparent resin layer using an embossed plate by hot pressure, thereby forming an uneven pattern of a wood grain conduit groove pattern. Finally, after a corona discharge treatment is applied to the surface, a resin composition composed of a two-component curable urethane resin is formed on the transparent resin layer by gravure coating, and then cured to form a protective layer ( A predetermined decorative sheet C was obtained. The obtained decorative sheet C had a surface roughness Rz of 30 μm.

Example 1
Two float glass plates having a thickness of 3 mm (sizes are shown in the above evaluations), one decorative sheet A obtained in Production Example 1 as a decorative sheet, and an EVA resin sheet (“ Two sheets of “Mersen G7053 (trade name)” manufactured by Tosoh Nickemi Co., Ltd., thickness: 0.40 mm) were prepared. Of the two glass plates, an EVA resin sheet, a decorative sheet, and an EVA resin sheet were placed on the surface of one glass plate in this order, then the glass plate was placed, and the decorative sheet was sandwiched between the glass plates. This was thermocompression bonded with an autoclave at 105 ° C. and 0.7 MPa for 10 minutes to produce a decorative laminated glass. About the obtained laminated laminated glass, the result of having performed said evaluation is shown to Table 1-1 and Table 1-2.

Example 2 and Comparative Example 1
In Example 1, the decorative sheet was changed to the decorative sheet B and decorative sheet C, and the EVA resin sheet used as the adhesive was changed to 0.25 mm in thickness, and the same as in Example 1. The decorative laminated glass of Example 2 and Comparative Example 1 was prepared. About the obtained laminated laminated glass, the result of having performed said evaluation is shown to Table 1-1 and Table 1-2.

＊１，１０００時間後／２０００時間後
＊２，カッコ内の数値は、測定したはく離力（Ｎ）の平均値である。

* After 1,1000 hours / after 2000 hours * 2, the values in parentheses are average values of the measured peeling force (N).

＊１，カッコ内の数値は、測定したはく離力（Ｎ）の平均値である。
＊２，カッコ内の数値は、１００マスの内、剥離しないマス目の数を示す。
＊３，一部に浮きがみられたが、剥離はなかった。

* 1, The value in parentheses is the average value of the measured peeling force (N).
* 2. The numbers in parentheses indicate the number of squares that do not peel out of 100 squares.
* 3 Although some floats were seen, there was no peeling.

  The decorative laminated glass of the present invention is excellent in basic performance such as light resistance, heat resistance, moisture resistance, impact resistance, etc., has excellent adhesion between the interlayer film and the glass, and is excellent in design. is there. The decorative laminated glass of the present invention can be suitably used for the interior and exterior of large buildings such as windows and doors of general buildings, houses, furniture, large stores, buildings, etc. by utilizing the characteristics.

1. 1. Laminated laminated glass 2. Glass plate Adhesive layer 11. Cosmetic sheet 12. Base material 13. Pattern layer 14. Protective layer 15. Adhesive layer 16. Transparent resin layer 17. Primer layer 18. Uneven pattern 19. Through hole

Claims (6)

  A decorative laminated glass comprising a decorative sheet sandwiched between two glass plates with an adhesive layer interposed between the glass sheet, the decorative sheet having a protective layer on a substrate, and the protective layer comprising an ionizing radiation curable resin composition A decorative laminated glass made by crosslinking and curing a product.   The decorative laminated glass according to claim 1, wherein the decorative sheet has a pattern layer between the substrate and the protective layer.   The decorative laminated glass according to claim 2, wherein a transparent resin layer is provided between the pattern layer and the protective layer.   The decorative laminated glass according to any one of claims 1 to 3, wherein the decorative sheet is embossed from the protective layer side.   The decorative laminated glass according to any one of claims 1 to 4, wherein two decorative sheets are sandwiched.   The decorative laminated glass according to any one of claims 1 to 5, wherein the adhesive layer is formed of an ethylene-vinyl acetate copolymer resin adhesive.

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