JP6913779B2 - Laminates and laminated glass - Google Patents

Description

The present invention relates to laminates and laminated glass.

A resin obtained by neutralizing a copolymer of ethylene and an unsaturated carboxylic acid with a metal ion and cross-linking between the molecules of the copolymer via a metal ion is known as a typical ionomer. Ionomers obtained by neutralizing such ethylene / unsaturated carboxylic acid copolymers with metal ions (hereinafter referred to as "ethylene-based ionomers") are relatively easy to process into sheets and films, and are relatively It has excellent transparency and relatively large adhesiveness. For this reason, ethylene-based ionomers are widely used in products that require light transmission and in laminates with other materials such as paper, glass, and resin. Typical applications for such ethylene-based ionomers are an interlayer film of laminated glass, a solar cell encapsulant in a solar cell module, and a packaging material composed of a laminate with another resin layer.

Laminated glass is a double glazing in which two or more flat glasses are bonded via an interlayer film made of a transparent resin. Since the interlayer film has extremely high flexibility compared to glass and is firmly adhered to the glass, the laminated glass prevents the glass from cracking, and even if the glass breaks, the fragments are hard to scatter. There are advantages such as the board is hard to come off from the frame. Such laminated glass is used as an automobile windshield, an instrument monitor glass, and a building glass. Laminated glass and its processed products with particular emphasis on safety are sometimes referred to as safety glass, tempered glass, security glass, disaster prevention glass, and the like. Laminated glass is also used as soundproof glass because it has excellent sound insulation.

Laminated glass using an ethylene ionomer as an interlayer film is described in Patent Document 1 (Japanese Patent Laid-Open No. 2013-28486) and Patent Document 2 (Japanese Patent Laid-Open No. 9-30846).

Patent Document 1 describes that an ionomer, which is a binary copolymer of ethylene and (mare) acrylic acid or (mare) acrylic acid ester, is particularly suitable for an interlayer film of laminated glass. Patent Document 1 describes that such an interlayer film of laminated glass has sufficient adhesiveness to a glass plate and is also excellent in transparency.

Patent Document 2 describes that a thermosetting resin obtained by blending an ionomer resin of an ethylene-methacrylic acid copolymer with an organic peroxide and a silane coupling is used as an interlayer film of laminated glass. Patent Document 2 describes that the use of such an interlayer film of laminated glass improves the adhesiveness associated with thermosetting, and that the obtained laminated glass is excellent in impact resistance and transparency. There is.

The sealing material in the solar cell module is a material that adheres to both the front and back surfaces of a power generation element composed of a solar cell and an interconnector to seal the element in the solar cell module. Through this sealing material, the power generation element adheres to the light receiving layer of the solar cell module and the back surface layer of the solar cell module. The encapsulant in the solar cell module has high transparency for the incident light passing through the light receiving layer to reach the solar cell without loss, prevents dust and moisture from entering the solar cell module, and allows the power generation element from the outside world. The function to protect from the impact of is required. Therefore, the sealing material is required to have good adhesiveness to the light receiving layer and the back surface layer. As the light receiving layer, a glass layer called a cover glass is generally used. A weather resistant resin film is generally used as the back surface layer.

Patent Document 3 (Japanese Patent Laid-Open No. 2008-503366) also describes that a multilayer laminated film containing a different type of ethylene-based ionomer film is used as a sealing material for a solar cell module. Patent Document 3 describes that a glass plate, which is a light receiving layer, and a power generation element are adhered to each other via such a sealing material.

As described above, a laminated glass interlayer film using an ethylene ionomer or a sealing material for a solar cell module is required to have both high transparency and high adhesiveness to glass.

Japanese Unexamined Patent Publication No. 2013-28486 Japanese Unexamined Patent Publication No. 9-30846 Japanese Patent Application Laid-Open No. 2008-503366

Here, the above-mentioned laminated glass or glass used for a solar cell module will be referred to. Many of these glasses belong to a type called float glass. Float glass is flat glass produced by a method called the float method. In the float method, molten glass is poured over molten metallic tin, and the glass is cooled and solidified on the molten tin to obtain a flat glass having high smoothness. The solidified flat glass is separated from the molten tin without being turned inside out, and the cutter is applied from the side where the molten tin was not in contact (upper side) while supporting the side where the molten tin was in contact (lower side). Is cut to a predetermined size. Tin is always attached to the lower surface of the float glass manufactured by such a float method, but tin is not attached to the upper surface thereof. Thus, the float glass inevitably has a surface to which tin is attached (tin surface) and a surface to which tin is not attached (non-tin surface).

It is expected that such tin and non-tin surfaces will differ in surface properties, such as affinity for other substances. Therefore, the adhesiveness of the interlayer film of laminated glass containing ethylene ionomer or the sealing material of the solar cell module to the glass as described above is when they are in contact with the tin surface of the glass and when they are in contact with the non-tin surface of the glass. It is expected that there will be a difference between.

However, until now, when examining the adhesive strength of a laminated glass interlayer film containing an ethylene ionomer or a sealing material for a solar cell module to glass, the difference between the adhesive strength of the glass to the tin surface and the adhesive force to the non-tin surface of the glass has been examined. Or, no example can be found that considers the balance between the adhesive strengths of both. In fact, in the inventions described in Patent Documents 1 to 4 described above, when evaluating the adhesive strength between the layer containing an ethylene ionomer and the glass plate, the adhesive surface is either a tin surface of glass or a non-tin surface. It does not consider whether it is. As described above, in the conventional technique, the performance improvement of the interlayer film of the laminated glass containing the ethylene ionomer or the sealing material of the solar cell module has not been sufficiently achieved.

In the present invention, the above-mentioned interlayer film or the above-mentioned sealing is a new viewpoint that has not been considered in the approach for improving the performance of the interlayer film of laminated glass containing an ethylene ionomer or the sealing material of a solar cell medium. The adhesive force between the material and the tin surface of the glass, the adhesive force between the interlayer film or the sealing material and the non-tin surface of the glass, and the balance of these two types of adhesive forces were added. By such an approach, in the present invention, it is used as an interlayer film of laminated glass or a sealing material for a solar cell module, which has a better balance between adhesiveness to glass and transparency and has higher practicality than before. It is an object of the present invention to obtain a laminate containing a resin sheet layer mainly composed of ethylene ionomer and a glass layer.

By the approach as described above, in the present invention, the resin sheet containing a specific ethylene ionomer has an excellent balance of transparency, adhesiveness to the glass tin surface, and adhesiveness to the glass non-tin surface, and is also excellent in workability. I found.

That is, the present invention is as follows.
(Invention 1) A zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent are contained, and the unsaturated carboxylic acid content of the ethylene / unsaturated carboxylic acid copolymer is 16% by mass or more. A resin sheet layer (A) made of a resin composition, wherein the ethylene / unsaturated carboxylic acid copolymer has a degree of neutralization by zinc ions of 10 to 40%.
Including the glass layer (B)
Haze is 5.0 or less and
The difference between the adhesive strength to the glass tin surface and the adhesive strength to the non-glass tin surface of the resin sheet layer (A) measured by the following measuring method (c) is 17 N / 15 mm or less, and the resin sheet layer (A) Adhesive strength to the non-tin surface of glass is 15 to 100 N / 15 mm .
Laminated body.
Measuring method (c): A resin sheet made of the resin composition and a tin surface of a float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the glass tin surface. Further, the resin sheet made of the resin composition and the non-tin surface of the float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the non-tin surface of the glass.
(Invention 2) A zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent are contained, and the unsaturated carboxylic acid content of the ethylene / unsaturated carboxylic acid copolymer is 16% by mass or more. A resin sheet layer (A) made of a resin composition, wherein the ethylene / unsaturated carboxylic acid copolymer has a degree of neutralization by zinc ions of 10 to 40%.
Including the glass layer (B)
Haze is 5.0 or less and
The difference between the adhesive strength to the glass tin surface and the adhesive strength to the non-glass tin surface of the resin sheet layer (A) measured by the following measuring method (c) is 17 N / 15 mm or less, and the resin sheet layer (A) Adhesive strength to the non-tin surface of glass is 15 to 100 N / 15 mm .
Laminated glass.
Measuring method (c): A resin sheet made of the resin composition and a tin surface of a float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the glass tin surface. Further, the resin sheet made of the resin composition and the non-tin surface of the float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the non-tin surface of the glass.

The laminate of the present invention is characterized by containing a fat sheet (A) made of a resin composition containing a specific ethylene ionomer as a main component and a glass layer (B), and having excellent transparency. The laminate of the present invention is also characterized in that the resin composition exhibits high adhesiveness in a well-balanced manner to both the glass tin surface and the glass non-tin surface. In such a laminated body of the present invention, not only is it excellent in transparency, but also whether the surface of the glass layer (B) in contact with the resin sheet layer (A) is a tin surface or a non-tin surface. The adhesive strength between the resin sheet layer (A) and the glass surface (B) is high. Such a laminate of the present invention can be used as a laminated glass having a higher quality than the conventional product. Further, such a laminate of the present invention has high utility value as a portion of a solar cell encapsulant and a cover glass of a solar cell module.

[Zinc ionomer of ethylene / unsaturated carboxylic acid copolymer]
The resin sheet (A) constituting the laminate of the present invention contains a zinc ionomer of a specific ethylene / unsaturated carboxylic acid copolymer. The unsaturated carboxylic acid, which is a comonomer of the ethylene / unsaturated carboxylic acid copolymer which is the base polymer of the zinc ionomer, is one or more selected from acrylic acid, methacrylic acid, maleic anhydride, and maleic anhydride ester. .. Acrylic acid or methacrylic acid is preferable as such an unsaturated carboxylic acid. The proportion of unsaturated carboxylic acid units in the ethylene / unsaturated carboxylic acid copolymer (hereinafter referred to as "unsaturated carboxylic acid content") is 16% by mass or more (the total of ethylene units and unsaturated carboxylic acid units). It is 100% by mass), preferably 16 to 22% by mass, and more preferably 16 to 20% by mass.

The ethylene / unsaturated carboxylic acid copolymer may contain other comonomer units of 30% by mass or less, preferably 25% by mass or less, based on 100% by mass of the total of ethylene and unsaturated carboxylic acid. Examples of such other comonomers include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. A (meth) acrylic acid ester such as isobutyl methacrylate can be used.

The ethylene / unsaturated carboxylic acid copolymer is produced by polymerizing ethylene and an unsaturated carboxylic acid, or in some cases, these and the other comonomer by a so-called high-pressure radical method. The zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer is produced by reacting the obtained ethylene / unsaturated carboxylic acid copolymer with a zinc compound such as zinc oxide or zinc acetate.

The degree of neutralization of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer is 10 to 40%, preferably 15 to 35%, and more preferably 15 to 30%.

The melt flow rate (MFR; conforming to JIS K7210-1999) of the ethylene / unsaturated carboxylic acid copolymer zinc ionomer used in the present invention at 190 ° C. and a load of 2160 g is within a range suitable for processing into a resin sheet. Not limited. Such an MFR is generally 0.1 to 150 g / 10 minutes, preferably 0.5 to 50 g / 10 minutes, and more preferably 1.0 to 40 g / 10 minutes. The melting point of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer is not particularly limited. In order to impart the heat resistance required for the interlayer film of laminated glass and the solar cell encapsulant of the solar cell module to the laminate of the present invention, the melting point of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer is set. It preferably has a melting point of 90 ° C. or higher, and more preferably 95 ° C. or higher.

[Silane coupling agent]
As the silane coupling agent used in the present invention, any silane coupling agent that has been conventionally blended with an ethylene-based ionomer in an interlayer film of laminated glass or a solar cell encapsulant can be used. Such silane coupling agents include, for example, γ-methacryloxypropyltrimethoxycisilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxycisilane, γ-acryloxypropylmethyldimethoxysilane, γ- Glycydoxypropyltrimethoxysilane and the like can be used.

Furthermore, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldi Ethoxysilane, N- (2-aminoethyl) -3-aminopropylethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-methyldimethoxysilyl-N- (1,3-) Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropylethyldiemexisilane, N-phenyl-3-aminopropylethyldiethoxysilane and the like can also be used.

Among such silane coupling agents, a silane coupling agent having an amino group and two alkoxy groups, such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, is particularly preferable.

The blending amount of the silane coupling agent is not limited as long as it contributes to the improvement of the adhesiveness between the resin sheet layer (A) and the glass layer (B) of the present invention. Usually, the function of the silane coupling agent is exhibited by blending 0.01 parts by weight or more of the silane coupling agent with respect to 100 parts by mass of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer. From an economical point of view, the blending amount of the silane coupling agent of the present invention is preferably 0.01 to 1 part by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer. It is preferably 0.02 to 0.5 parts by mass, and most preferably 0.05 to 0.4 parts by mass.

[Resin sheet layer (A)]
The resin sheet layer (A) of the present invention comprises a resin composition containing the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent. In addition to the above-mentioned zinc ionomer of ethylene / unsaturated carboxylic acid copolymer and silane coupling agent, such a resin composition may optionally contain various kinds of ultraviolet absorbers, light stabilizers, antioxidants and the like. Conventional additives can be added.

Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2carboxybenzophenone and 2-hydroxy-4-n-oct. Benzophenone systems such as xibenzophenone; 2- (2'-hydroxy-3', 5'-dit-butylphenyl) benzotriazole, 2- (2'-hydroxy-5-methylphenyl) benzotriazo and 2- ( Benzotriazoles such as 2'-hydroxy-5-t-octylphenyl) benzotriazole; salicylate esters such as phenylsalicylate and p-octylphenylsalicylate are used.

As the light stabilizer, a hindered amine type is used. Examples of hindered amine-based light stabilizers include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, and 4-acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6,6-tetramethylpiperidine, 4-( o-Chlorobenzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7, 9,9-Tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2) , 6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tris (2,2,6,6-tetramethyl-4-piperidyl) ) Benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-acetoxypropane-1,2,3-tricarboxylate, tris (2,2) 2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) triazine-2, 4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2 , 3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) Propane-1,1,2,3-tetracarboxylate, tetrakis (2,2,6,6-tetra Methyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate and the like can be mentioned.

As the antioxidant, various hindered phenol-based and phosphite-based ones are used. Specific examples of hindered phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, and 2, , 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-Methylenebis (2,6-di-t-butylphenol), 2,2'-Methylenebis [6- (1-methylcyclohexyl) -p-cresol], Bis [3,3-bis (4-hydroxy) -3-t-Butylphenyl) Butylic Acid] Glycolester, 4,4'-Butylidenebis (6-t-Butyl-m-Cresol), 2,2'-Echilidenebis (4-sec-Butyl-6-t) -Butylphenol), 2,2'-Etilidenebis (4,6-di-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadesiloxyphenol, tetrakis [methylene-3-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-thiobis (6-t-Butyl-m-cresol), tocopherol, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] Ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzylthio) -1,3,5 -Triazine can be mentioned. Specific examples of the phosphite-based antioxidant include 3,5-di-t-butyl-4-hydroxybenzylphosphanate dimethyl ester and bis (3,5-di-t-butyl-4-hydroxy). Ethyl benzylphosphonate, tris (2,4-di-t-butylphenyl) phosphanate and the like can be mentioned.

There is no limitation on the amount of the antioxidant, the light stabilizer, and the ultraviolet absorber as long as each function is exhibited. Usually, each is added in an amount of 5 parts by mass or less, preferably 0.01 to 3 parts by mass, with respect to 100 parts by mass of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer.

If necessary, the resin composition may further contain additives such as a colorant, a light diffusing agent, and a flame retardant and a metal deactivator.

As the colorant, known pigments, inorganic compounds, dyes and the like can be used. Various known colorants can be used as these colorants. As the white colorant, titanium oxide, zinc oxide, calcium carbonate and the like can be used. Examples of the pigment include white inorganic pigments such as titanium oxide, zinc flower, lead white, lithopon, barite, precipitated barium sulfate, calcium carbonate, soap, precipitated silica, and other white inorganic pigments, carbon black, lamp black, and the like. Black inorganic pigments such as titanium black and synthetic iron black, gray inorganic pigments such as zinc powder, lead phosphite, and slate powder, red inorganic pigments such as cadmium red, cadmium mercury red, silver vermilion, bengara, molybdenum red, and lead tan, amber. , Brown inorganic pigments such as iron oxide tea, yellow inorganic pigments such as cadmium yellow, zinc yellow, oak, siena, synthetic oca, yellow lead, titanium yellow, and chromium oxide green, cobalt green, and chromium can be used. Further, as pigments, for example, organic pigments such as Permanent Red 4R, Para Red, First Yellow G, First Yellow 10G, Disazo Yellow G, Disazo Yellow GR, Disazo Orange, and Pyrazolone Orange , Brilliant Carmin 3B, Brilliant Carmin 6B, Brilliant Scarlet G, Brilliant Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmin FB, Resole Red R, Resole Red B, Lake Red C, Lake -Azo pigments such as Red D, Brilliant Fast Scarlet, Pyrazolon Red, Bon Maroon Light, Bon Maroon Medium, Fire Red, Nitroso pigments such as Naftor Green B, Nitro such as Naftor Yellow S Pigments, basic dye-based rakes such as Rhodamine B rake and Rhodamine 6G rake, medium-dye dye-based rakes such as Alizarin rake, and construction dye-based pigments such as indanslen blue, phthalocyanine blue, phthalocyanine green, fast Phthalocyanine pigments such as Sky Blue and dioxazine pigments such as dioxazine violet can be used. In addition, organic fluorescent pigments and pearl pigments can also be used.

As the light diffusing agent, for example, glass beads, silica beads, silicon alkoxide beads, hollow glass beads and the like, which are inorganic spherical substances, are used. Further, for example, plastic beads such as acrylic or vinylbenzene, which are organic spherical substances, are also used.

As the flame retardant, for example, a halogen-based flame retardant such as bromide, a phosphorus-based flame retardant, a silicone-based flame retardant, and a metal hydrate such as magnesium hydroxide and aluminum hydroxide are used.

As the metal deactivator, a well-known compound that suppresses metal damage of the thermoplastic resin can be used. Two or more kinds of metal inactivating agents may be used in combination. Preferred examples of the metal deactivator are hydrazide derivatives or triazole derivatives. Preferred examples of hydrazide derivatives are decamethylene dicarboxyl-disalicyloyl hydrazide, 2', 3-bis [3- [3,5-ditert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide, isophthalic acid. Bis (2-phenoxypropionyl-hydrazide). Preferred examples of triazole derivatives are 3- (N-salicyloyl) amino-1,2,4-triazole. In addition to hydrazide derivatives and triazole derivatives, 2,2'-dihydroxy-3,3'-di- (α-methylcyclohexyl) -5,5'-dimethyl diphenylmethane, tris- (2-methyl-4-hydroxy-) 5-Tri-butylphenyl) butane, a mixture of 2-mercaptobenzimidazole and a phenol derivative, and the like can be used.

There is no limitation on the thickness of one layer of the resin sheet layer (A) of the present invention. The thickness of the resin sheet layer (A) can be set in any way depending on the use of the laminate of the present invention. In particular, when the laminate of the present invention is used for an interlayer film of laminated glass or a solar cell module, the thickness of one layer of the resin sheet layer (A) is usually appropriately selected from the range of 1 μ to 10 mm.

[Glass layer (B)]
As the glass layer of the present invention, plate-shaped or sheet-shaped glass can be used without limitation. For example, ordinary float glass, a processed product of float glass, or glass to which a specific function is added can be used. That is, in addition to float glass, heat-resistant glass, fireproof glass, frosted glass, design glass such as polished glass and template glass, colored glass, high-performance glass such as non-reflective glass and heat-resistant glass, chemically strengthened glass, and heat-reinforced glass. A wide range of glass such as tempered glass such as glass and highly transparent glass can be used. The material of the glass layer (B) can be selected in any way depending on the use of the laminate of the present invention. In particular, when the laminate of the present invention is used for a product that requires high transparency, such as an interlayer film of laminated glass or a solar cell encapsulant, highly transparent glass with particularly high transparency is preferable.

The thickness of the glass layer (B) is not particularly limited. The thickness of the glass layer (B) can also be selected in any way depending on the use of the laminate of the present invention. In particular, when the laminate of the present invention is used for a product that requires high transparency, such as an interlayer film of laminated glass or a solar cell module, the thickness of one layer of the glass layer (B) is usually set. It is 10 mm or less, preferably 5 mm or less.

[Laminate]
The laminate of the present invention is a multilayer molded product containing at least the above-mentioned resin sheet (A) and the above-mentioned glass layer (B). The resin sheet (A) contained in the laminate of the present invention may be one layer or two or more layers. When the resin sheet layer (A) has two or more layers, each material contains a zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent, and the above ethylene / unsaturated carboxylic acid copolymer is contained. Corresponding to a resin composition in which the unsaturated carboxylic acid content of the carboxylic acid copolymer is 16% by mass or more and the degree of neutralization of the ethylene / unsaturated carboxylic acid copolymer by zinc ions is 10 to 40%. However, the composition of each may be the same or different. For example, a resin sheet (A1) and a resin sheet (A2) corresponding to the above resin composition but having different compositions are placed next to each other as in (A1)-(A2), (A1)-(A2)-(A1). ), Or (A2)-(A1)-(A2). In the case of three or more layers, the intermediate layer does not have to contain a silane coupling agent. There is no limitation on the thickness of each resin sheet layer (A) (for example, the resin sheet layer (A1) or the resin sheet layer (A2)).

Similarly, the glass layer (B) contained in the laminate of the present invention may be one layer or two or more layers. When the laminate of the present invention has two or more glass layers (B), each glass layer (B) may be the same glass or different glasses.

Further, in the laminated body of the present invention, as long as the condition that the haze is 5.0 or less is satisfied, the resin sheet layer (A) or the glass layer (B) may be placed at a position not in contact with the glass layer (B). It can have other layers that are not. Such other layers can be selected in any way depending on the use of the laminate of the present invention. For example, a printing layer, a colored layer, a reinforcing layer made of metal or resin, or the like is used as such another layer.

In the laminate of the present invention, the resin sheet layer (A) and the glass layer (B) manufactured in advance by a known film / sheet molding method such as a T-die extrusion method, a calendar molding method, or an inflation method are heated. It is manufactured by adhering it underneath and cooling it after sufficient adhesion between the two.

[Laminated glass]
The laminate of the present invention is preferably used as a laminated glass having a haze of 5.0 or less. The layered structure of the laminated glass of the present invention is preferably one in which a glass layer (B), one or more resin sheet layers (A), and a glass layer (B) are laminated in this order. Highly transparent glass is preferable as the glass layer (B). When the resin sheet layer (A) has two or more layers, each material contains a zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent, and the above ethylene / unsaturated carboxylic acid copolymer is contained. Corresponding to a resin composition in which the unsaturated carboxylic acid content of the carboxylic acid copolymer is 16% by mass or more and the degree of neutralization of the ethylene / unsaturated carboxylic acid copolymer by zinc ions is 10 to 40%. However, the composition of each may be the same or different. For example, a resin sheet (A1) and a resin sheet (A2) corresponding to the above resin composition but having different compositions are placed next to each other as in (A1)-(A2), (A1)-(A2)-(A1). ), Or (A2)-(A1)-(A2). There is no limitation on the thickness of each resin sheet layer (A) (for example, the resin sheet layer (A1) or the resin sheet layer (A2)). Further, the thickness of each resin sheet layer (A) (for example, resin sheet layer (A1) and resin sheet layer (A2)) is not limited as long as the functions of laminated glass such as building glass and disaster prevention glass are not impaired. As long as the condition that the haze is 5.0 or less is satisfied, another layer that is neither the resin sheet layer (A) nor the glass layer (B) can be provided at a position that does not contact the glass layer (B). Such other layers can be selected in any way depending on the function required for the laminated glass of the present invention. For example, a printing layer, a colored layer, a reinforcing layer made of metal or resin, or the like is used as such another layer.

The laminated glass of the present invention typically has one or more resin sheet layers (A) manufactured in advance by a known film / sheet molding method such as a T-die extrusion method, a calendar molding method, or an inflation method. ) And the glass layer (B) are adhered under heating using a vacuum laminator, a vacuum bag, a nip roll, an autoclave, etc., or by combining these methods, and after the two are sufficiently adhered to each other. Manufactured by slow cooling under appropriate conditions. A typical condition for the above cooling is natural cooling in the atmosphere.

[Solar cell module]
The laminate of the present invention can also be used as a constituent member of the solar cell module. If the resin sheet (A) of the present invention is used as a solar cell encapsulant and the cover glass is adhered to the glass layer (B) to the resin sheet (A), the transparency on the light receiving side is high, and the cover glass and the solar cell are sealed. It is possible to manufacture a high-quality solar cell module having excellent adhesion to a stop material. In such a solar cell module, the transparent cover glass, one layer or two or more layers of the resin sheet layer (A), the solar cell element, one layer or two or more layers of the resin sheet layer (in order from the light receiving side to the back surface). A), the lower protective material is laminated and bonded.

Examples of solar cell elements include group IV semiconductors such as monocrystalline silicon, polycrystalline silicon, and amorphous silicon; group III-V semiconductors such as gallium-arsenic, copper-indium-selenium, copper-indium-gallium-selenium, and cadmium-tellu. In addition, solar cell elements such as II-VI group compound semiconductors are used.

[Haze of laminated glass and laminated glass]
The laminate and laminated glass of the present invention are characterized by having a haze of 5.0 or less, preferably 3.0 or less. The haze value is measured according to JIS-K7105.

[Adhesive strength between resin layer sheet (A) and glass layer (B)]
In the laminated glass and laminated glass of the present invention, the adhesiveness between the resin layer sheet (A) and the glass layer (B) is limited to a more preferable state in consideration of the tin surface and the non-tin surface of the glass. .. That is, in the laminated glass and laminated glass of the present invention, when the resin sheet layer (A) is measured by the following measuring method (c), it is 10 N / 15 mm or more, preferably 10 to 150 N / 15 mm, more preferably 15. It is made of a resin composition exhibiting adhesive strength to a glass non-tin surface of ~ 100 N / 15 mm. When measuring the adhesive strength between the resin layer sheet (A) and the tin surface of the glass layer (B), the opposing surfaces can be changed and other conditions can be measured by the same method.

Measuring method (c): A resin sheet made of the resin composition and a non-tin surface of a float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm).

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[Example of zinc ionomer of ethylene / unsaturated carboxylic acid copolymer and its control product]
"Content (%)" indicates the ratio (mass%) of the monomer unit in which the total of the ethylene unit and the unsaturated carboxylic acid unit is 100% by mass. "MFR" indicates the melt flow rate (based on JIS K7210-1999, unit: g / 10 minutes) at 190 ° C. and a load of 2160 g.
-Ethylene ionomer 1 (IO-1):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, neutralization degree: 20%, MFR: 9)
-Ethylene ionomer 2 (IO-2):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, neutralization degree: 25%, MFR: 6)
-Ethylene ionomer 3 (IO-3):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, neutralization degree: 30%, MFR: 4)
In addition, the following was used.
-Ethylene / methacrylic acid copolymer (EMAA):
(Ethylene content: 82%, methacrylic acid content: 18%, MFR: 60)
-Control ethylene ionomer 4 (IO-4):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 85%, methacrylic acid content: 15%, neutralization degree: 23%, MFR: 5)
-Control ethylene ionomer 5 (IO-5):
Mg ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, metacrylic acid content: 15%, neutralization degree: 54%, MFR: 1)
-Control ethylene ionomer 6 (IO-6):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, neutralization degree: 45%, MFR: 1)

The following were used as the silane coupling agent and the glass.
[Silane Coupling Agent] N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane was used.
[Glass] A float plate glass manufactured by Asahi Glass Co., Ltd. having a thickness of 3.2 mm was used.

[Production example of resin sheet]
Any of the above IO-1 to IO-6 and EMAA and the above silane coupling agent were mixed, melted and kneaded in a 40 mm diameter short shaft extruder at the blending ratios shown in Table 1. The obtained resin composition was molded into a sheet at a resin temperature of 160 ° C. by a cast molding machine to obtain a resin sheet having a thickness of 0.4 mm. The obtained resin sheet was used as the resin sheet layer (A) or a control product thereof.

[Evaluation of processability of resin sheet]
The processability of the above-mentioned resin sheet was evaluated. If a resin sheet having a predetermined thickness can be produced without any problem in the above-mentioned production of the resin sheet, ◯ is displayed in Table 1. If there is a problem, x is displayed in Table 1.

[Manufacturing example of laminated body]
Using a vacuum heating laminating machine (double vacuum tank laminating machine LM-50x50S manufactured by NPC), the resin sheet and the glass were bonded under the conditions of a heating temperature of 140 ° C. and a heating time of 8 minutes. Then, the bonded material was allowed to stand in the air and slowly cooled by natural cooling. In this way, the laminate of the present invention composed of the resin sheet layer (A) of the present invention composed of the above resin sheet or the control layer thereof and the glass layer (B) or the laminate of the control product thereof was obtained.

[Measurement of haze of laminated body]
The haze (cloudiness, unit:%) of the obtained laminate was measured using a haze meter manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS-K7105. Table 1 shows the haze values of each laminate.

[Adhesive strength of laminate (non-tin surface)]
Using a vacuum heating bonding machine (NPC double vacuum tank bonding machine LM-50x50S), the resin sheet and the non-tin surface of the glass are bonded under the conditions of a heating temperature of 140 ° C. and a heating time of 8 minutes. I matched it. Then, the bonded material was allowed to stand in the air and slowly cooled by natural cooling. A slit having a width of 15 mm was inserted into the sheet portion of the completed laminate to prepare a test piece, which was installed in a tensile tester. The resin sheet and the glass were separated from each other at a tensile speed of 100 mm / min, and the maximum stress was determined as the adhesive strength (N / 15 mm). The obtained adhesive strength is shown in Table 1 as the adhesive strength of the non-tin surface of the glass in each laminate.

[Adhesive strength of laminated body (tin surface)]
Using a vacuum heating laminating machine (NPC double vacuum tank laminating machine LM-50x50S), the resin sheet and the tin surface of the glass are bonded under the conditions of a heating temperature of 140 ° C. and a heating time of 8 minutes. rice field. Then, the bonded material was allowed to stand in the air and slowly cooled by natural cooling. A slit having a width of 15 mm was inserted into the sheet portion of the completed laminate to prepare a test piece, which was installed in a tensile tester. The resin sheet and the glass were separated from each other at a tensile speed of 100 mm / min, and the maximum stress was determined as the adhesive strength (N / 15 mm). The obtained adhesive strength is shown in Table 1 as the adhesive strength of the glass tin surface in each laminate.

From the measurement results shown in Table 1, in Examples 1, 2 and 3, which are examples of the laminated body of the present invention, the resin sheet and the glass layer are firmly adhered to the glass, and the transparency is high. Can be understood. It can also be seen that in Examples 1, 2 and 3, the adhesive strength of the non-tin surface of the glass is high.

Comparative Example 1 is a rejected product of the present invention. In Comparative Example 1, a resin sheet made of a resin assembly containing no ionomer is used. In Comparative Example 1, the glass adhesive strength is excellent, but the transparency is inferior.

Comparative Example 2 is a rejected product of the present invention. Comparative Example 2 uses a resin sheet made of a resin composition containing no silane coupling agent. In Comparative Example 2, relatively good transparency is obtained, but the glass adhesive strength is inferior. In particular, the adhesive strength of the non-tin surface of glass is inferior.

Comparative Example 3 is a rejected product of the present invention, similarly to Comparative Example 2. Comparative Example 3 uses a resin sheet made of a resin composition containing no silane coupling agent. In Comparative Example 3, relatively good transparency is obtained, but the glass adhesive strength is inferior. In particular, the adhesive strength of the non-tin surface of glass is inferior.

Comparative Example 4 is a rejected product of the present invention. Comparative Example 4 uses a resin sheet made of a resin composition containing an ethylene-based ionomer having a methacrylic acid content lower than the specified range. In Comparative Example 4, good glass adhesive strength can be obtained, but the transparency is extremely inferior.

Comparative Example 5 is a rejected product of the present invention. Comparative Example 5 uses a resin sheet made of a resin composition containing an ethylene ionomer crosslinked with magnesium ions and not containing a silane coupling agent. In Comparative Example 5, the transparency was excellent, but the glass adhesive strength was extremely inferior.

Comparative Example 6 is a rejected product of the present invention. In Comparative Example 6, a resin sheet made of an ethylene-based ionomer resin composition in which the degree of neutralization by zinc ions exceeds a specified range is used. In Comparative Example 6, the MFR was too low to process with a formulation containing a silane coupling agent.

From the results of such Examples and Comparative Examples, the laminate of the present invention containing a resin sheet composed of a resin composition containing a specific ethylene ionomer as a main component and a silane coupling and a glass layer is transparent. It can be seen that it has both properties and high glass adhesive strength, particularly excellent adhesive strength on the non-tin surface of glass, and also excellent workability of the resin sheet of the laminated body.

If such a laminate of the present invention is used as an interlayer film of laminated glass, it is expected that a laminated glass having excellent transparency and having glass plates on both sides adhere to the interlayer film with equal high adhesive strength can be obtained. Will be done. Such laminated glass can be expected as a safer and more beautiful glass. Such laminated glass has high utility value as automobile glass and architectural glass.

Claims (2)

It contains a zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent, and the unsaturated carboxylic acid content of the ethylene / unsaturated carboxylic acid copolymer is 16% by mass or more, and the above ethylene. A resin sheet layer (A) made of a resin composition having a degree of neutralization of the unsaturated carboxylic acid copolymer by zinc ions of 10 to 40%, and a resin sheet layer (A).
Including the glass layer (B)
Haze is 5.0 or less and
The difference between the adhesive strength to the glass tin surface and the adhesive strength to the non-glass tin surface of the resin sheet layer (A) measured by the following measuring method (c) is 17 N / 15 mm or less, and the resin sheet layer (A) Adhesive strength to the non-tin surface of glass is 15 to 100 N / 15 mm .
Laminated body.
Measuring method (c): A resin sheet made of the resin composition and a tin surface of a float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the glass tin surface. Further, the resin sheet made of the resin composition and the non-tin surface of the float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the non-tin surface of the glass. It contains a zinc ionomer of an ethylene / unsaturated carboxylic acid copolymer and a silane coupling agent, and the unsaturated carboxylic acid content of the ethylene / unsaturated carboxylic acid copolymer is 16% by mass or more, and the above ethylene. A resin sheet layer (A) made of a resin composition having a degree of neutralization of the unsaturated carboxylic acid copolymer by zinc ions of 10 to 40%, and a resin sheet layer (A).
Including the glass layer (B)
Haze is 5.0 or less and
The difference between the adhesive strength to the glass tin surface and the adhesive strength to the non-glass tin surface of the resin sheet layer (A) measured by the following measuring method (c) is 17 N / 15 mm or less, and the resin sheet layer (A) Adhesive strength to the non-tin surface of glass is 15 to 100 N / 15 mm .
Laminated glass.
Measuring method (c): A resin sheet made of the resin composition and a tin surface of a float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the glass tin surface. Further, the resin sheet made of the resin composition and the non-tin surface of the float plate glass are bonded together under vacuum heating to obtain a laminate. This laminate is installed in a tensile tester, the resin sheet and the float plate glass are separated from each other at a tensile speed of 100 mm / min, and the maximum stress is determined as the adhesive strength (N / 15 mm) with respect to the non-tin surface of the glass.