JP2014061640A - Laminate having glass, curable resin layers, and transparent resin layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is lightweight, does not cause warpage, peeling, and cracking even under high and low temperatures, and is excellent in impact resistance.SOLUTION: The laminate has a configuration of glass/a curable resin layer/a transparent resin layer/a curable resin layer/glass. The curable resin layers contain a phenolic hydroxyl group-containing polyamide resin (A) and an epoxy resin (B). The phenolic hydroxyl group-containing polyamide resin (A) in the present invention is preferably a resin represented by formula (1). (In the formula (1), Ar represents a divalent aromatic group.)

Description

The present invention relates to a laminate having glass, a curable resin, and a transparent resin, and relates to a laminate excellent in lightness, environmental resistance, and impact resistance.

Glass plate is excellent in weather resistance, chemical resistance, scratch resistance, gas barrier property, and is transparent and excellent in daylighting, so it can be used for light from windows and roofs of general buildings and high-rise buildings, and covers for agricultural greenhouses. Widely used in window materials for automobiles, trains, aircrafts, etc., flat panel displays such as liquid crystal displays and organic EL displays, solar cells, lithium ion batteries, digital signage, touch panels, electronic paper, etc. It is widely used for glass substrates of these devices, substrate glasses of devices such as organic EL lighting, cover glasses (front plates), and the like. However, glass is a brittle material and has a problem of being easily damaged by being weak against physical impact. It is known that when a flying object or a high-speed object hits a glass plate, it is easily damaged, and it is also easily damaged by thermal shock.

Further, glass has a specific gravity of 2.2 to 2.6 g / cm ³ and is a substance that tends to be very heavy. In particular, there is a strong demand for weight reduction for display applications of mobile devices, but glass is still the mainstream. In order to solve this problem, many laminates in which a transparent resin layer is laminated on a thin glass plate have been proposed as an alternative to a glass plate. For example, in the following Patent Document 1, a laminated glass composed of a synthetic resin plate such as a polycarbonate plate and a glass plate is used as the laminated glass of different materials. In this case, butyral resin is used for the adhesive layer, and the laminated glass is manufactured by thermocompression bonding of both plates via the butyral resin.

However, the butyral resin is different from the difference in linear expansion coefficient between a glass plate and a polycarbonate plate (for example, 8.5 × 10 −6 / ° C. for a glass plate and 6.8 × 10 −5 / ° C. for a polycarbonate). In the autoclave method using a thermoplastic resin or the method using an ultraviolet ray or a thermosetting adhesive, there is a problem that warping, peeling, cracking, or the like occurs due to a rapid temperature change.

Furthermore, many substrates using glass as a substrate have been used. For example, a glass substrate having a thickness of about 0.2 to 1.1 mm is widely used in a liquid crystal display, an organic electroluminescence (EL) display, a touch panel, and the like. In order to solve this problem, an adhesive sheet such as the following Patent Document 2 and an ultraviolet curable resin such as the following Patent Document 3 have been proposed, but the adhesive sheet is used at a high temperature or a low temperature assuming a cold region. There is a problem that the adhesive strength is lowered, and in the case of an ultraviolet curable resin, there is a problem that a decomposition product of a photopolymerization initiator volatilizes under a high temperature condition or a vacuum deposition process.

JP-A-6-915 JP 2012-25152 A JP 2008-37094 A JP 2003-336020 A

Therefore, the present invention has an object of providing a laminate having excellent impact resistance without being warped, peeled off or cracked even at high temperatures and low temperatures under such a background. It is.

The inventors of the present invention have a cured product of a curable resin composition containing a phenolic hydroxyl group-containing polyamide resin (A) and an epoxy resin (B). By exhibiting strong adhesiveness with the resin, it was found that the glass laminate had excellent heat cycle resistance even in different types of joints having different impact resistance and different linear expansion coefficients, and the present invention was completed. .

（式（１）中ｍおよびｎは平均値で、０．００５≦ｎ／（ｍ＋ｎ）≦１．００を示し、また、ｍ＋ｎは５〜２００の正数を、ｘは平均置換基数で１〜４の正数をそれぞれ表す。Ａｒは２価の芳香族基を示す。）で表される構造を有することを特徴とする上記（１）に記載の積層体
（３）ガラスの厚みが３００μｍ以下であることを特徴とする上記（１）乃至（２）に記載の積層体
（４）熱プレスにより硬化、接着させて得られる上記（１）乃至（３）のいずれか１項に記載の積層体
（５）上記（１）乃至（４）のいずれか１項に記載の積層体を具備する窓材
（６）上記（１）乃至（４）のいずれか１項に記載の積層体を具備するディスプレイ用カバーガラス That is, the present invention provides (1) a laminate having the structure of glass / curable resin layer / transparent resin layer / curable resin layer / glass, wherein the curable resin layer is a phenolic hydroxyl group-containing polyamide resin (A), epoxy resin ( B) -containing laminate (2) The phenolic hydroxyl group-containing polyamide resin (A) described in (1) above is represented by the following formula (1):

(In the formula (1), m and n are average values, 0.005 ≦ n / (m + n) ≦ 1.00, m + n is a positive number of 5 to 200, and x is an average number of substituents of 1 to 1. 4 represents a positive number, and Ar represents a divalent aromatic group.) The laminate (3) according to (1) above has a thickness of 300 μm or less. (4) The laminate according to any one of (1) to (3), which is obtained by curing and bonding by hot pressing. Body (5) Window material comprising the laminate according to any one of (1) to (4) above (6) The laminate according to any one of (1) to (4) above Cover glass for display

The laminate of the present invention is a laminate that is lightweight and has excellent impact resistance without warping, peeling or cracking even at high and low temperatures.
The laminate of the present invention includes window materials for general buildings and high-rise buildings, window materials for vehicles such as automobiles and trains, flat panel displays such as liquid crystal displays and organic EL displays, solar cells, lithium ion batteries, and digital signage. It is extremely useful in applications such as glass substrates for devices such as touch panels and electronic paper, and substrate glasses and cover glasses for devices such as organic EL lighting.

It is sectional drawing of the laminated body which concerns on this invention, Comprising: It is a figure of the laminated body which consists of 5 layer structure of glass / curable adhesive resin / polycarbonate / curable adhesive resin / glass. It is sectional drawing of the laminated body used for the comparative example 1 of this invention, Comprising: It is a figure of the laminated body which consists of a 5 layer structure of glass / UV curing adhesive / polycarbonate / UV curing adhesive / glass. It is sectional drawing of the laminated body used for the comparative example 2 of this invention, Comprising: It is a figure of the laminated body which consists of 5 layer structure of glass / adhesive / polycarbonate / adhesive / glass. It is a figure of the receiving jig used in the iron ball drop test. It is a frame type 10 cm long x 10 cm wide x 5 mm high with a 1 cm edge width. Place the laminate here and drop an iron ball in the center of the laminate.

DESCRIPTION OF SYMBOLS 1 Glass 2 Sheet-like curable resin composition 3 Polycarbonate 4 Ultraviolet curable resin 5 Adhesive 6 Receiving jig

Hereinafter, embodiments of the present invention will be described.
In the present invention, the phenolic hydroxyl group-containing polyamide resin as component (A) is used as a curing agent for the epoxy resin as component (B). This phenolic hydroxyl group-containing polyamide resin can be synthesized according to JP-A No. 2006-124545.
In the present invention, the phenolic hydroxyl group-containing polyamide resin as the component (A) is not particularly limited as long as it has a polyamide structure and a phenolic hydroxyl group, but the structure represented by the above formula (1) Is preferred.

  In the formula (1), Ar represents a divalent aromatic group, that is, an organic group having at least one aromatic ring. Examples of the divalent aromatic group include phenylenediamine derivatives such as m-phenylenediamine, p-phenylenediamine, and m-tolylenediamine; and 4,4′-diamino. Diamino diphenyl ether derivatives such as diphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether; 4,4′-diaminodiphenyl thioether, 3,3′-dimethyl-4,4 ′ -Diaminodiphenyl thioether, such as 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether, 3,3'-dimethoxy-4,4'-diaminodiphenyl thioether Derivatives; 4,4 Diaminobenzophenone derivatives such as diaminobenzophenone and 3,3′-dimethyl-4,4′-diaminobenzophenone; diaminodiphenylsulfone derivatives such as 4,4′-diaminodiphenyl sulfoxide and 4,4′-diaminodiphenylsulfone Benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, benzidine derivatives such as 3,3′-diaminobiphenyl; p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, etc. Examples include xylylenediamine derivatives, and two or more of these may be used in combination. Among them, phenylenediamine derivatives or diaminodiphenyl ether derivatives are preferable, and 3,4'-diaminodiphenyl ether or 4,4'-diaminodiphenyl ether is particularly preferable from the viewpoint of solvent solubility and flame retardancy of the polymer obtained.

The epoxy resin as the component (B) is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolak type epoxy resin, dicyclopentadiene phenol condensation type epoxy resin, xylylene skeleton-containing phenol novolak type epoxy resin, biphenyl skeleton containing novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbiphenol Examples thereof include, but are not limited to, type epoxy resins.
Two or more of these epoxy resins can be used in combination.

In the curable resin composition for forming the curable resin layer in the laminate of the present invention, as the curing agent component, other curing agents may be used in addition to the phenolic hydroxyl group-containing polyamide resin. Curing agents that can be used in combination include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, anhydrous Pyromellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, triphenylmethane and their modified products, imidazo -Le, BF ₃
-Examples include, but are not limited to, amine complexes and guanidine derivatives. When these are used in combination, the proportion of the phenolic hydroxyl group-containing polyamide resin in the total curing agent is usually 20% by weight or more, preferably 30% by weight or more.

The curable resin composition may contain a curing accelerator. Specific examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo. And tertiary amines such as (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

The curable resin composition may contain an organic solvent. Examples of the organic solvent include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, Sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, Examples thereof include ketone solvents such as cyclohexanone and aromatic solvents such as toluene and xylene. The resin concentration in the curable resin composition is usually 10 to 80% by weight, preferably 15 to 70% by weight.

Further, various compounding agents such as a UV absorber, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and a pigment can be added to the curable resin composition.

Further, for the purpose of preventing coloring, the curable resin composition can contain an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant.

As an example of the amine compound that is the light stabilizer, the following commercially available products can be used. The commercially available amine compound is not particularly limited. LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.

As an example of the phosphorus compound, the following commercially available products can be used. It does not specifically limit as a phosphorus compound marketed, For example, as an ADEKA product, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, Adekas tab TPP and the like.

As an example of the phenol compound, the following commercially available products can be used. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, AGANOX 1520L, Adeka 1520L, and AGANOX 1520L manufactured by Ciba Specialty Chemicals , ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, Sumitizer GA-80 , Sumilizer MDP-S, Sumili zer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer
GP etc. are mentioned.

In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as those manufactured by Ciba Specialty Chemicals.

It is preferable to contain at least one or more of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but with respect to the total weight of the curable resin composition of the present invention, It is in the range of 0.005 to 5.0% by weight.

Furthermore, an organic filler and an inorganic filler can be added to the curable resin composition according to the transparency required for the glass laminate. Specific examples of the organic filler include epoxy resin, melamine resin, urea resin, acrylic resin, phenol resin, fluororesin, saturated or unsaturated polyester resin, aliphatic or aromatic polyamide resin, cellulose short fiber, polyphenylene ether resin, etc. Examples thereof include fine powder, fine particles, and fine powder and fine particles of a super engineering plastic resin such as a liquid crystal polymer resin, a polyether ketone resin, a polyimide resin, and a polysulfone resin. These organic fillers may be low molecular weight resin powders and fine particles, or may be high molecular weight or crosslinked resin powders and fine particles. Specific examples of the inorganic filler include silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, alumina, talc, and short glass fiber, but the average particle in terms of the elastic modulus and mechanical strength of the resulting resin. Small particle sizes of the system 0.5-5 μm are preferred. These may be used alone or in a mixture of two or more. The blending amount is preferably an amount occupying 1 to 30% by weight in the curable resin composition.

The curable resin composition can be obtained by uniformly mixing the components (A) and (B) and, if necessary, other curing agents, curing accelerators, organic solvents and other components. As a mixing method, a planetary mixer, a roll mill, a dissolver, or the like can be used.

In the present invention, as an embodiment for forming a curable resin layer, when using a curable resin composition formed into a sheet shape, or when applying a curable resin composition containing an organic solvent to a glass surface Etc. can be exemplified.
Sheets using a curable resin composition support a curable resin composition containing an organic solvent in a planar manner by various coating methods such as gravure coating methods, screen printing, metal mask methods, and spin coating methods. It is obtained by drying after coating so that the thickness after drying on the body becomes a predetermined thickness, for example, 3 to 60 μm. As drying temperature, it is 80-200 degreeC normally, Preferably it is 100-180 degreeC.

Examples of the planar support include various polymers such as polyamide, polyamideimide, polyarylate, polyethylene terephthalate (PET), polybutylene terephthalate, polyetheretherketone, polyetherimide, polyetherketone, polyketone, polyethylene, and polypropylene, and / or Or the film and aluminum foil which are made from the copolymer can be used. A release agent such as silicon may be treated on the surface of these base materials.

A curable resin composition layer can be formed on glass by peeling the base material and laminating the sheet formed on the base material with glass by a laminating process. The temperature of the laminating process is usually 100 to 180 ° C.
It is also possible to select glass as the planar support and apply it directly by the above method.

In the present invention, the glass is preferably a thin glass having a thickness of 500 μm or less called a glass film, particularly preferably 50 μm to 300 μm. Glass films are manufactured by AF45 (Matsunami Glass Industrial Co., Ltd.), Asahi Glass Co., Nippon Electric Glass Co., Nippon Sheet Glass Co., Shot Co., Corning Co., etc. It is not something.

In the present invention, the transparent resin layer is preferably polycarbonate (PC), a polymer alloy of PC and polyethylene, stretched polyethylene terephthalate, or polymethyl methacrylate, and particularly preferably polycarbonate because of its strength and transparency. Polycarbonate is sold under the trade name of Panlite (manufactured by Teijin), Iupilon (manufactured by Mitsubishi Gas Chemical Co., Ltd.), Diamond Light (manufactured by Mitsubishi Rayon Co., Ltd.), etc. It is not a thing.

The curable resin composition used in the present invention is such that the cured product exhibits flexibility and high elastic modulus, and strong adhesiveness with glass and transparent resin. Even in different types of joints, they have excellent heat cycle resistance. Particularly suitable applications of the laminate of the present invention using this are those that require weather resistance, chemical resistance, scratch resistance, gas barrier properties, transparency, and daylighting, for example, as a glass substitute material, lightweight. Window materials for general buildings and high-rise buildings, etc. that are required to be converted to light, light from the roof, covering materials for greenhouses for agriculture, vehicles for vehicles such as automobiles, trains, and aircraft.
Moreover, since the laminate of the present invention is resistant to physical shock and thermal shock, devices such as flat panel displays such as liquid crystal displays and organic EL displays, solar cells, lithium ion batteries, digital signage, touch panels, electronic paper, etc. It is suitable for a glass substrate, a substrate glass of a device such as organic EL lighting, a cover glass (front plate), and the like.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the following description, “parts” means “parts by weight” unless otherwise specified.
Example 1
While subjecting a flask equipped with a thermometer, condenser, fractionator, and stirrer to nitrogen purge, 18.2 parts of 5-hydroxyisophthalic acid, 149 parts of isophthalic acid, 200 parts of 3,4'-diaminodiphenyl ether, lithium chloride 10.9 parts, 1156 parts of N-methylpyrrolidone and 231 parts of pyridine were added and dissolved by stirring, and then 501 parts of triphenyl phosphite was added and subjected to a condensation reaction at 95 ° C. for 4 hours to obtain a polyamide resin reaction solution. It was. While stirring this reaction solution, 1100 parts of water was added dropwise at 90 ° C. over 3 hours, further stirred at 90 ° C. for 1 hour, cooled to 60 ° C. and allowed to stand for 30 minutes. Since the upper layer was separated into an aqueous layer and the lower layer was separated into an oil layer (resin layer), the upper layer was removed by decantation. The oil layer (resin layer) was diluted by adding 1000 parts of N, N-dimethylformamide. The polyamide resin was washed by repeating this water washing step by addition of water, layer separation, decantation, and solvent addition four more times. The washed polyamide solution was sprayed into 5000 parts of stirred water using a two-fluid nozzle to precipitate it as a fine powder having a particle size of 5 to 50 μm, and the precipitate was separated by filtration. The obtained wet cake was dispersed in 2700 parts of methanol and refluxed for 2 hours with stirring. Next, methanol was filtered off, washed with 2700 parts of water, and dried to obtain the following formula (3).

The aromatic polyamide resin part represented by these was obtained. When the amount of elements contained in the aromatic polyamide resin was quantified with a fluorescent X-ray measuring apparatus, the total phosphorus amount was 150 ppm and the total chlorine amount was 20 ppm. The intrinsic viscosity of the obtained aromatic polyamide resin was 0.53 dl / g (dimethylacetamide solution, 30 ° C.). In the formula, the value of m was about 36, and the value of n was about 4.

10 parts of NC-3000 as an epoxy resin with respect to 100 parts of the obtained aromatic polyamide resin (A) (Nippon Kayaku Co., Ltd., epoxy equivalent 275 g / eq), 2-phenyl-4,5-as a curing accelerator A curable resin composition was obtained by adding 2 parts of dihydroxymethylimidazole (2PHZ), LA-81 (manufactured by ADEKA) as a light stabilizer, and 260 parts of dimethylformamide as a solvent.

The above curable resin composition is applied on a PET film with a die coater so that the thickness after drying is 10 μm, dried at 130 ° C. for 1 minute to remove the solvent, and a sheet-like curable resin composition is obtained. Obtained.

The sheet-like curable resin composition obtained above is made of glass (AF45, Matsunami Glass Industrial Co., Ltd., thickness 100 μm, length 10 cm × width 10 cm) / sheet-like curable resin composition (thickness 10 μm, length 10 cm × width 10 cm) / PC (Nippon Test Panel Kogyo Co., Ltd., thickness 2 mm, length 10 cm × width 10 cm) / sheet-like curable resin composition (thickness 10 μm, length 10 cm × width 10 cm) / glass (Matsunami Glass Industry AF45, thickness 100 μm, length 10 cm × 10 cm in width (FIG. 1), and a hot press machine at 150 ° C. and 1 MPa for 20 minutes to obtain a laminate.

(Comparative Example 1)
An ultraviolet curable adhesive was obtained by the method described in Example 1 of Patent Document 3. That is, 97 parts of hexafunctional urethane acrylate having an isophorone structure (“UV7600B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2 parts of 3-acryloxypropyltrimethoxysilane (“KBM5103” manufactured by Shin-Etsu Chemical Co., Ltd.), 1-hydroxycyclohexyl One part of phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy Co., Ltd.) was stirred at 60 ° C. until uniform, and an ultraviolet curable adhesive was obtained.

The obtained ultraviolet curable adhesive is dropped on glass (AF45 manufactured by Matsunami Glass Industrial Co., Ltd., thickness 100 μm, length 10 cm × width 10 cm), and then coated by spin coating so that the UV curable adhesive layer becomes 10 μm. did.

Prepare two glass and polycarbonate (Nippon Test Panel Kogyo Co., Ltd., thickness 2 mm, length 10 cm × width 10 cm) having the above UV curable adhesive layer, and glass / UV curable adhesive layer / polycarbonate / UV curable adhesive layer. / Laminated so as to have a glass structure, and after depressing with a hand roller, an autoclave (manufactured by Hirayama Seisakusho) was introduced at 50 ° C. and 0.5 MPa for 30 minutes for defoaming treatment.

The laminate obtained above is irradiated with ultraviolet rays from both sides with an illuminance of 200 mW / cm 2 and a light amount of 5 J / cm 2 using a metal halide lamp, and is composed of glass / ultraviolet curable adhesive / polycarbonate / ultraviolet curable adhesive / glass. A laminate of 2 was obtained.

(Comparative Example 2)
A pressure-sensitive adhesive molded into a 10 μm sheet was obtained between the release polyethylene terephthalate (PET) films by the method described in Example 1 of Patent Document 4. That is, a sheet of 10 μm is placed between 100 μm of smooth release PET film by heating and stirring 0.1 part by weight of glycidyl methacrylate and 1.0 part by weight of benzophenone with respect to 100 parts by weight of the uncrosslinked acrylate copolymer. Then, a cross-linked sheet-like pressure-sensitive adhesive was obtained by irradiating with ultraviolet light at an integrated light quantity of 4000 mJ / cm 2 using a high-pressure mercury lamp through a release PET film. In addition, the composition of the acrylic ester copolymer is a copolymer of 78.4% by weight of n-butyl acrylate, 19.6% by weight of 2-ethylhexyl acrylate, and 2.0% by weight of acrylic acid. is there.

Using the pressure-sensitive adhesive obtained above, Glass (AF45, Matsunami Glass Industry Co., Ltd., thickness 100 μm, length 10 cm × width 10 cm) / pressure-sensitive adhesive (thickness 10 μm, length 10 cm × width 10 cm) / PC (Nippon Test Panel Industry Co., Ltd.) Made of 2 mm thick, 10 cm long × 10 cm wide) / adhesive (10 μm thick, 10 cm long × 10 cm wide) / glass (Matsunami Glass Industrial AF45, 100 μm thick, 10 cm long × 10 cm wide) After pressing with a roll, an autoclave (manufactured by Hirayama Seisakusho) was subjected to defoaming treatment at 50 ° C. and 0.5 MPa for 30 minutes to obtain the laminate of FIG.

The laminated body obtained above was evaluated by the following method. The results are shown in Table 1.
Appearance The appearance of the obtained laminate was visually confirmed. When the light of the fluorescent lamp was projected on the glass laminate, and there was no undulation in the reflection of the fluorescent lamp, it was determined to be acceptable (indicated by ○ in Table 1).
The total light transmittance of the laminate was measured with a transparency spectrophotometer (manufactured by Hitachi, Ltd.), and when the transmittance was 80% or more, it was determined to be acceptable (indicated by ○ in Table 1).
Constant temperature and humidity test The laminate was set in a constant temperature and humidity machine (manufactured by ESPEC Co., Ltd.) and allowed to stand at 80 ° C. and 85% relative humidity for 100 hours. Then, after naturally drying in a room for 24 hours, visual observation was performed, and when there was no discoloration, peeling, cracking, or distortion, it was determined to be acceptable (indicated by ○ in Table 1).
Heat cycle test When the laminate is set in a heat cycle tester (manufactured by Espec Corp.) and subjected to visual observation after repeating a heat cycle of -50 ° C to 85 ° C for 100 cycles, there is no discoloration, peeling, cracking or distortion Was a pass (indicated by a circle in Table 1).
Iron ball drop test 130 g, an iron ball having a diameter of 3.5 cm was dropped from a height of 25 cm to the center of the laminate.
The laminated body is not fixed in a state where it is placed on the receiving jig shown in FIG.
Visual observation of the laminated body after dropping was carried out, and when there was no peeling and a crack, it was set as the pass (it shows with (circle) in Table 1).

As described above, the laminate of the present invention is lightweight, is not destroyed in the iron ball drop test, and does not cause peeling or cracking even in a heat cycle test at -50 ° C to 85 ° C. showed that. From these results, the laminate of the present invention can be used for window materials for general buildings and high-rise buildings, window materials for vehicles such as automobiles and trains, flat panel displays such as liquid crystal displays and organic EL displays, solar cells, and lithium ions. It is extremely useful for applications such as glass substrates for devices such as batteries, digital signage, touch panels, and electronic paper, and substrate glasses and cover glasses for devices such as organic EL lighting.

Claims (6)

In a laminate having the structure of glass / curable resin layer / transparent resin layer / curable resin layer / glass, the curable resin layer contains a phenolic hydroxyl group-containing polyamide resin (A) and an epoxy resin (B). A laminate characterized by the above. The phenolic hydroxyl group-containing polyamide resin (A) according to claim 1 is represented by the following formula (1):

(In the formula (1), m and n are average values, 0.005 ≦ n / (m + n) ≦ 1.00, m + n is a positive number of 5 to 200, and x is an average number of substituents of 1 to 1. The laminate according to claim 1, wherein each of the laminates represents a positive number of 4. Ar represents a divalent aromatic group. The laminated body according to claim 1, wherein the glass has a thickness of 300 μm or less. The laminate according to any one of claims 1 to 3, which is obtained by curing and bonding by hot pressing. The window material which comprises the laminated body of any one of Claims 1 thru | or 4. The display cover glass which comprises the laminated body of any one of Claims 1 thru | or 4.

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