JP2016188158A - Laminate and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is more excellent in balance between adhesiveness and transparency than the conventional one, can be used as an intermediate film of laminated glass or a sealing material of a solar cell module, and contains a resin sheet layer mainly composed of an ethylene-based ionomer and a glass layer.SOLUTION: There are provided a laminate and laminated glass which contain: a resin sheet layer (A) formed of a resin composition containing zinc ionomer of an ethylene-unsaturated carboxylic acid copolymer and a silane coupling agent, having a content of the unsaturated carboxylic acid of the ethylene-unsaturated carboxylic acid copolymer of 16 mass% or more, and having a neutralization degree by zinc ions of the ethylene-unsaturated carboxylic acid copolymer of 10-40%; and a glass layer (B), and have a haze of 5.0 or less.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a laminated glass.

  A resin obtained by neutralizing a copolymer of ethylene and an unsaturated carboxylic acid with a metal ion and crosslinking the copolymer molecules via the metal ion is known as a typical ionomer. An ionomer obtained by neutralizing such an ethylene / unsaturated carboxylic acid copolymer with a metal ion (hereinafter referred to as “ethylene ionomer”) is easy to process into a sheet or a film, and is relatively Excellent transparency and relatively high tack. For this reason, ethylene ionomers are widely used in products that require light transmittance and laminates with other materials such as paper, glass, and resin. Typical applications of such ethylene-based ionomers include laminated films of laminated glass interlayer films, solar cell sealing materials in solar cell modules, and other resin layers.

  Laminated glass is a multi-layer glass in which two or more plate glasses are bonded via an intermediate 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 cracking of the glass. There is an advantage that the plate is not easily detached from the frame. Such laminated glass is used as a windshield for automobiles, a monitor glass for instruments, and a glass for construction. Laminated glass and its processed products that emphasize safety in particular are sometimes referred to as safety glass, tempered glass, security glass, disaster prevention glass, and the like. Moreover, since laminated glass is excellent also in sound insulation, it is used also as soundproof glass.

  Laminated glass using an ethylene ionomer as an intermediate 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 of a binary copolymer of ethylene and (mea) acrylic acid or (mea) acrylate is particularly suitable for an interlayer film of laminated glass. Patent Document 1 describes that such an interlayer film of laminated glass has sufficient adhesion to a glass plate and is excellent in transparency.

  Patent Document 2 describes that a thermosetting resin in which an organic peroxide and a silane coupling are blended with an ionomer resin of an ethylene-methacrylic acid copolymer is used as an interlayer film of laminated glass. Patent Document 2 describes that when such an interlayer film of laminated glass is used, the adhesiveness associated with thermosetting is improved, and the obtained laminated glass is excellent in impact resistance and transparency. Yes.

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

  Patent Document 3 (Japanese Translation of PCT International Publication No. 2008-503366) also describes that a multilayer laminated film including different types of ethylene-based ionomer films is used as a sealing material for solar cell modules. Patent Document 3 describes that a glass plate as a light receiving layer and a power generation element are bonded through such a sealing material.

  Thus, both the high transparency and the high adhesiveness with respect to glass are calculated | required by the intermediate film of the laminated glass using an ethylene-type ionomer, or the sealing material of a solar cell module.

JP 2013-28486 A Japanese Patent Laid-Open No. 9-30846 Special table 2008-503366

  Here, the glass used for the above-mentioned laminated glass or solar cell module is mentioned. Many of these glasses belong to a class called float glass. The float glass is a flat glass produced by a method called a float method. In the float process, molten glass is poured onto molten metal tin, and the glass is cooled and solidified on the molten tin to obtain a plate glass with high smoothness. The solidified glass sheet is separated from the molten tin without being turned over and supports the side where the molten tin is in contact (the lower side), and applies the cutter from the side where the molten tin is not in contact (the upper side). And cut into a predetermined size. Although tin always adheres to the lower surface of the float glass manufactured by such a float method, tin does not adhere to the upper surface. Thus, the float glass inevitably has a surface to which tin is adhered (tin surface) and a surface to which tin is not adhered (non-tin surface).

  It is expected that surface properties such as affinity for other substances are different between such a tin surface and a non-tin surface. Therefore, the adhesion of the interlayer film of laminated glass containing the ethylene ionomer as described above or the sealing material of the solar cell module to the glass 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.

  However, until now, when investigating the adhesion of laminated glass interlayers containing ethylene ionomers or the sealing material of solar cell modules to glass, the difference between the adhesion of glass to the tin surface and the adhesion to the non-tin surface. In addition, there is no example that considers the balance of both adhesive forces. In fact, in the inventions described in the above-mentioned Patent Documents 1 to 4, when evaluating the adhesion between the layer containing the ethylene ionomer and the glass plate, the adhesion surface is a tin surface of glass, or a non-tin surface. Not considering what is. Thus, in the prior art, 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 intermediate film or the sealing material is a new viewpoint that has not been considered so far in the approach of improving the performance of the interlayer film of laminated glass containing an ethylene ionomer or the sealing material of a solar cell module. The adhesion force between the glass and the tin surface of the glass, the adhesion force between the intermediate film or the sealing material and the non-tin surface of the glass, and the balance between these two adhesion forces were added. By such an approach, in the present invention, the balance between adhesion to glass and transparency is superior to that of the prior art, and it is used for a laminated glass interlayer film or a solar cell module sealing material having higher practicality. An object of the present invention is to obtain a laminate including a resin sheet layer mainly composed of an 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 excellent balance of transparency, adhesion to glass tin surface, adhesion to glass non-tin surface, and excellent workability. I found.

That is, the present invention is as follows.
(Invention 1) An ethylene / unsaturated carboxylic acid copolymer zinc ionomer and a silane coupling agent are contained, and the ethylene / unsaturated carboxylic acid copolymer has an unsaturated carboxylic acid content of 16% by mass or more. A resin sheet layer (A) made of a resin composition, wherein the ethylene / unsaturated carboxylic acid copolymer has a neutralization degree with zinc ions of 10 to 40%, and a glass layer (B), and a haze The laminate is characterized by having a value of 5.0 or less.
(Invention 2) The laminate according to Invention 1, wherein the resin composition exhibits an adhesive strength of 10 N / 15 mm or more when measured by the following measurement method (c) on a glass non-tin surface.
Measurement method (c): A resin sheet made of the resin composition and a non-tin surface of float glass 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 glass are separated at a tensile speed of 100 mm / min, and the maximum stress is obtained as the adhesive strength (N / mm).
(Invention 3) An ethylene / unsaturated carboxylic acid copolymer zinc ionomer and a silane coupling agent are contained, and the ethylene / unsaturated carboxylic acid copolymer has an unsaturated carboxylic acid content of 16% by mass or more. A resin sheet layer (A) made of a resin composition, wherein the ethylene / unsaturated carboxylic acid copolymer has a neutralization degree with zinc ions of 10 to 40%, and a glass layer (B), and a haze Laminated glass, characterized in that is 5.0 or less.
(Invention 4) The laminated glass of Invention 3, wherein the resin composition exhibits an adhesive strength of 10 N / 15 mm or more when measured by the following measurement method (c) on a glass non-tin surface.
Measurement method (c): A resin sheet made of the resin composition and a non-tin surface of float glass 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 glass are separated at a tensile speed of 100 mm / min, and the maximum stress is obtained as the adhesive strength (N / mm).

  The laminate of the present invention includes a resin sheet (A) composed of a resin composition containing a specific ethylene ionomer as a main component and a glass layer (B), and is characterized by excellent transparency. The laminate of the present invention is also characterized in that the resin composition exhibits a high balance of adhesion to both the glass tin surface and the glass non-tin surface. In such a laminate of the present invention, not only is it excellent in transparency, even if 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 force 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 higher quality than conventional products. Moreover, such a laminated body of the present invention has high utility value as a part of a solar cell sealing material 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 that is a comonomer of the ethylene / unsaturated carboxylic acid copolymer that is the base polymer of the zinc ionomer is at least one selected from acrylic acid, methacrylic acid, maleic anhydride, and maleic anhydride ester. . As such an unsaturated carboxylic acid, acrylic acid or methacrylic acid is preferred. In the ethylene / unsaturated carboxylic acid copolymer, the proportion of unsaturated carboxylic acid units (hereinafter referred to as “unsaturated carboxylic acid content”) is 16% by mass or more (total of ethylene units and unsaturated carboxylic acid units). 100 mass%), preferably 16-22 mass%, more preferably 16-20 mass%.

  The ethylene / unsaturated carboxylic acid copolymer may contain 30% by mass or less, preferably 25% by mass or less of other comonomer units based on a total of 100% by mass 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, methyl methacrylate, (Meth) acrylic acid esters such as isobutyl methacrylate can be used.

  The ethylene / unsaturated carboxylic acid copolymer is produced by polymerizing ethylene and an unsaturated carboxylic acid or, optionally, these and the other comonomers 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) at 190 ° C. and 2160 g load of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer used in the present invention is within a range suitable for processing into a resin sheet. Not limited. Such 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 provide the laminated body of the present invention with the heat resistance required for an interlayer film of laminated glass or a solar cell encapsulant for a solar cell module, the melting point of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer is It preferably has a melting point of 90 ° C. or higher, and more preferably has a melting point of 95 ° C. or higher.

[Silane coupling agent]
Any silane coupling agent used in the present invention can be used as long as it is conventionally blended with an interlayer film of laminated glass or a solar cell encapsulant together with an ethylene ionomer. Examples of such silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ- Glycidoxypropyltrimethoxysilane or the like can be used. "

  Further, 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-aminopropyl Pills ethyl diethyl Mexico silane well as N- phenyl-3-aminopropyl ethyl diethoxy silane can be used.

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

  The compounding quantity of the said silane coupling agent will not be limited if it is a range which contributes to the adhesive improvement of the resin sheet layer (A) and glass layer (B) of this invention. Usually, when 0.01 parts by weight or more of a silane coupling agent is added to 100 parts by weight of the zinc ionomer of the ethylene / unsaturated carboxylic acid copolymer, the function of the silane coupling agent is exhibited. When an economical viewpoint is also added, the blending amount of the silane coupling agent of the present invention is 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. Preferably it is 0.02-0.5 mass part, Most preferably, it is 0.05-0.4 mass part.

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

  Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone and 2-hydroxy-4-n-. Benzophenone series such as octoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole and 2- ( 2'-hydroxy-5-t-octylphenyl) benzotriazoles such as benzotriazole; salicylic acid esters such as phenylsalicylate and p-octylphenylsalicylate are used.

  As the light stabilizer, a hindered amine type is used. Examples of hindered amine light stabilizers include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 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-piperidi ) 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 (2,2,6,6-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, -Tetramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) propane-1,1,2,3-tetracarboxylate And tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate.

  As the antioxidant, various hindered phenols and phosphites are used. Specific examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 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-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis (4 -Sec-butyl-6-t-butylphenol), 2,2'-ethylidenebis (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-octadecyloxy Phenol, tetrakis [methylene-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-hydro) Roxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-t-butyl-4- And hydroxybenzylthio) -1,3,5-triazine. Specific examples of the phosphite antioxidant include 3,5-di-t-butyl-4-hydroxybenzyl phosphinate dimethyl ester and bis (3,5-di-t-butyl-4-hydroxy). Examples thereof include ethyl benzylphosphonate and tris (2,4-di-t-butylphenyl) phosphanate.

  There is no restriction | limiting in the mixing | blending of antioxidant, a light stabilizer, and a ultraviolet absorber, if it is the quantity by which each function is exhibited. Usually, it 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.

  You may mix | blend additives, such as a coloring agent, a light-diffusion agent, a flame retardant, and a metal deactivator, with the said resin composition further as needed.

  Known pigments, inorganic compounds, dyes, and the like can be used as the colorant. Various known colorants can be used. As the white colorant, titanium oxide, zinc oxide, calcium carbonate, or the like can be used. Examples of the pigment include inorganic pigments such as titanium oxide, zinc white, lead white, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, precipitated silica, and other white inorganic pigments, carbon black, lamp black, Black inorganic pigments such as titanium black and synthetic iron black, gray inorganic pigments such as zinc dust, lead oxide and slate powder, red inorganic pigments such as cadmium red, cadmium mercury red, silver vermilion, red rose, molybten red and red lead, amber Inorganic brown pigments such as iron oxide tea, cadmium yellow, zinc yellow, ocher, siena, synthetic ocher, yellow inorganic pigments such as yellow lead, titanium yellow, chromium oxide green, cobalt green, and chromium can be used. Further, examples of the pigment include organic red, such as permanent red 4R, para red, first yellow G, first yellow 10G, disazo yellow G, disazo yellow GR, disazo orange, pyrazolone orange, Brilliant Carmin 3B, Brilliant Carmine 6B, Brilliant Scarlet G, Brilliant Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmine FB, Risole Red R, Risole Red B, Rake Red C, Rake Red D, brilliant fast scarlet, pyrazolone red, bon maroon light, bon maroon medium, azo pigments such as fire red, nitroso pigments such as naphthol green B, naphtho・ Nitro pigments such as yellow S, basic dye lakes such as rhodamine B lake and rhodamine 6G lake, mordant dye lakes such as alizarin and lake, vat dye pigments such as indanthrene blue, phthalocyanine blue, Phthalocyanine pigments such as phthalocyanine green and fast 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, which are inorganic spherical substances, are used. Further, for example, plastic beads such as acrylic or vinyl benzene, which are organic spherical substances, are also used.

  Examples of the flame retardant include halogen flame retardants such as bromides, phosphorus flame retardants, silicone flame retardants, metal hydrates such as magnesium hydroxide and aluminum hydroxide, and the like.

  As a metal deactivator, a well-known thing can be used as a compound which suppresses the metal damage of a thermoplastic resin. Two or more metal deactivators may be used in combination. A preferred example of the metal deactivator is a hydrazide derivative or a triazole derivative. Preferred examples of hydrazide derivatives include decamethylene dicarboxyl-disalicyloyl hydrazide, 2 ′, 3-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide, isophthalic acid Bis (2-phenoxypropionyl-hydrazide). A preferred example of the triazole derivative is 3- (N-salicyloyl) amino-1,2,4-triazole. Besides hydrazide derivatives and triazole derivatives, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyl diphenylmethane, tris- (2-methyl-4-hydroxy-) 5-tert-butylphenyl) butane, a mixture of 2-mercaptobenzimidazole and a phenol condensate can be used.

  There is no restriction | limiting in the thickness of 1 layer of the resin sheet layer (A) of this invention. The thickness of the resin sheet layer (A) can be set in any manner according to 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 to 10 mm.

[Glass layer (B)]
In the glass layer of the present invention, plate-like or sheet-like glass can be used without limitation. For example, normal float glass, a processed product of float glass, or glass with a specific function added can be used. That is, in addition to float glass, design glass such as heat-resistant glass, fire-resistant glass, frosted glass, polished glass, and template glass, high-functional glass such as colored glass, non-reflective glass, and heat-resistant glass, chemically tempered glass, and heat-tempered glass A wide range of glass such as tempered glass, high transmission glass and the like can be used. The material of the glass layer (B) can be selected in any manner according to the use of the laminate of the present invention. In particular, when the laminate of the present invention is used for a product requiring high transparency such as an interlayer film of laminated glass or a solar cell encapsulant, highly transparent glass with high transparency is particularly 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 requiring 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 It is 10 mm or less, preferably 5 mm or less.

[Laminate]
The laminate of the present invention is a multilayer molded article including at least the above-described resin sheet (A) and the above-described 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. Corresponds to the resin composition, wherein 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, each composition 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 adjacent to each other as shown in (A1)-(A2), (A1)-(A2)-(A1 ) In the order of (A2)-(A1)-(A2). In the case of three or more layers, the intermediate layer may not contain a silane coupling agent. There is no restriction | limiting also in the thickness of each resin sheet layer (A) (for example, resin sheet layer (A1) or 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), the respective glass layers (B) may be the same glass or different glasses.

  In the laminate of the present invention, as long as the condition that haze is 5.0 or less is satisfied, the resin sheet layer (A) or the glass layer (B) is not in contact with the glass layer (B). Can have no other layers. Such other layers can be selected in any manner according to the use of the laminate of the present invention. For example, a printed layer, a colored layer, a reinforcing layer made of metal or resin, and the like are used as such other layers.

  The laminate of the present invention is prepared by heating a resin sheet layer (A) previously produced by a known film / sheet molding method such as a T-die extrusion method, a calendar molding method, an inflation method, and the glass layer (B). It is manufactured by adhering to the bottom and cooling after both have been sufficiently adhered.

[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 a glass layer (B), one or two or more resin sheet layers (A), and a glass layer (B) laminated in this order. As a glass layer (B), a highly transmissive glass is preferable. 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. Corresponds to the resin composition, wherein 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, each composition may be the same or different. For example, a resin sheet (A1) and a resin sheet (A2) that correspond to the above resin composition but have different compositions are placed adjacent to each other as shown in (A1)-(A2), (A1)-(A2)-(A1 ) In the order of (A2)-(A1)-(A2). There is no restriction | limiting also in the thickness of each resin sheet layer (A) (for example, resin sheet layer (A1) or resin sheet layer (A2)). Moreover, there is no restriction | limiting also in the thickness of each resin sheet layer (A) (for example, resin sheet layer (A1) or resin sheet layer (A2)), unless the function of laminated glass, such as architectural glass and disaster prevention glass, is 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 not in contact with the glass layer (B). Such other layers can be selected in any manner according to the function required for the laminated glass of the present invention. For example, a printed layer, a colored layer, a reinforcing layer made of metal or resin, and the like are used as such other layers.

  The laminated glass of the present invention typically has one or two or more resin sheet layers (A) produced 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) using a vacuum laminator, a vacuum bag, a nip roll, an autoclave, or the like, or by combining these methods under heating, and after the two have 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 laminated body of this invention can be used also as a structural member of a solar cell module. If the resin sheet (A) of the present invention is used as a solar cell encapsulant and the cover glass is bonded to the glass layer (B) with the glass layer (B), the transparency on the light receiving side is high, and the cover glass and solar cell encapsulant are sealed. A high-quality solar cell module excellent in adhesiveness with a stopper can be manufactured. Such a solar cell module has a transparent cover glass, one or two or more resin sheet layers (A), a solar cell element, one or two or more resin sheet layers (in order from the light receiving side to the back surface). A) A lower protective material is laminated and bonded.

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

[Haze of laminate and laminated glass]
The laminate and the laminated glass of the present invention are characterized in that the haze is 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 laminate and the 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, the laminate and the laminated glass of the present invention have a resin sheet layer (A) of 10 N / 15 mm or more, preferably 10 to 150 N / 15 mm, more preferably 15 when the resin sheet layer (A) is measured by the following measurement method (c). It consists of a resin composition exhibiting adhesive strength to a glass non-tin surface of -100 N / 15 mm. In addition, when measuring the adhesive strength of the resin layer sheet | seat (A) and the tin surface of a glass layer (B), an opposing surface is changed and other conditions can be measured by the same method.

  Measurement method (c): A laminate is obtained by bonding a resin sheet made of the resin composition and a non-tin surface of a float plate glass under vacuum heating. This laminate is installed in a tensile tester, the resin sheet and the float glass are separated at a tensile speed of 100 mm / min, and the maximum stress is obtained as the adhesive strength (N / mm).

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.
[Example of zinc ionomer of ethylene / unsaturated carboxylic acid copolymer and its control]
“Content (%)” indicates a ratio (mass%) of the monomer unit in which the total of ethylene units and unsaturated carboxylic acid units is 100 mass%. “MFR” indicates a melt flow rate at 190 ° C. under a load of 2160 g (according to JIS K7210-1999, unit: g / 10 minutes).
Ethylene ionomer 1 (IO-1):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, degree of neutralization: 20%, MFR: 9)
Ethylene ionomer 2 (IO-2):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, degree of neutralization: 25%, MFR: 6)
-Ethylene ionomer 3 (IO-3):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, degree of neutralization: 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%, degree of neutralization: 23%, MFR: 5)
Control ethylene ionomer 5 (IO-5):
Mg ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 15%, degree of neutralization: 54%, MFR: 1)
Control ethylene ionomer 6 (IO-6):
Zinc ionomer of ethylene / methacrylic acid copolymer (ethylene content: 82%, methacrylic acid content: 18%, degree of neutralization: 45%, MFR: 1)

The following were used as a silane coupling agent and glass.
[Silane coupling agent] N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane was used.
[Glass]
A 3.2 mm thick Asahi Glass float plate glass 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 screw extruder at the blending ratio shown in Table 1. The obtained resin composition was molded into a sheet shape 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 resin sheet was evaluated. In the production of the above-described resin sheet, when a resin sheet having a predetermined thickness can be produced without any problem, “◯” is displayed in Table 1. If there is a problem, x is displayed in Table 1.

[Production example of laminate]
The resin sheet and the glass were bonded together under the conditions of a heating temperature of 140 ° C. and a heating time of 8 minutes using a vacuum heating bonding machine (double vacuum tank bonding machine LM-50 × 50S manufactured by NPC). Thereafter, the bonded material was left in the atmosphere and gradually cooled by natural cooling. In this way, the laminate of the present invention or the laminate of the control product thereof comprising the resin sheet layer (A) of the present invention comprising the above resin sheet or its control layer and the glass layer (B) was obtained.

[Haze measurement of laminate]
The haze (cloudiness, unit:%) of the obtained laminate was measured using a haze meter manufactured by Suga Test Instruments Co., Ltd. according to JIS-K7105. Table 1 shows the haze value of each laminate.

[Adhesive strength of laminate (non-tin surface)]
Using a vacuum heat bonding machine (NPC double vacuum tank bonding machine LM-50x50S), the resin sheet and the non-tin surface of the glass are bonded under conditions of a heating temperature of 140 ° C. and a heating time of 8 minutes. Combined. Thereafter, the bonded material was left in the atmosphere and gradually cooled by natural cooling. A slit having a width of 15 mm was formed in a sheet portion of the completed laminate to obtain a test piece, which was installed in a tensile tester. The resin sheet and glass were pulled apart at a pulling speed of 100 mm / min, and the maximum stress was determined as the adhesive strength (N / mm). The obtained adhesive strength is shown in Table 1 as the adhesive strength of the glass non-tin surface in each laminate.

[Adhesive strength of laminate (tin surface)]
Using a vacuum heating bonding machine (NPC double vacuum tank bonding machine LM-50x50S), the resin sheet and the tin surface of the glass are bonded together under the conditions of a heating temperature of 140 ° C. and a heating time of 8 minutes. It was. Thereafter, the bonded material was left in the atmosphere and gradually cooled by natural cooling. A slit having a width of 15 mm was formed in a sheet portion of the completed laminate to obtain a test piece, which was installed in a tensile tester. The resin sheet and glass were pulled apart at a pulling speed of 100 mm / min, and the maximum stress was determined as the adhesive strength (N / 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 laminate of the present invention, the resin sheet and the glass layer are firmly adhered to the glass, and the transparency is high. Can understand. In Examples 1, 2, and 3, it can also be seen that the adhesive strength of the glass non-tin surface is high.

  Comparative Example 1 is a rejected product of the present invention. In Comparative Example 1, a resin sheet made of a resin composition not containing an ionomer is used. In Comparative Example 1, the glass adhesive strength is excellent, but the transparency is poor.

  Comparative Example 2 is a rejected product of the present invention. Comparative Example 2 uses a resin sheet made of a resin composition that does not contain a 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 glass non-tin surface is inferior.

  Comparative Example 3 is a rejected product of the present invention as in Comparative Example 2. Comparative Example 3 uses a resin sheet made of a resin composition that does not contain a 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 glass non-tin surface is inferior.

  Comparative Example 4 is a rejected product of the present invention. In Comparative Example 4, a resin sheet made of a resin composition containing an ethylene ionomer having a methacrylic acid content lower than the specified range is used. In Comparative Example 4, good glass adhesion strength is obtained, but transparency is extremely poor.

  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 cross-linked 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 poor.

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

  From the results of Examples and Comparative Examples, the laminate of the present invention comprising a resin sheet composed of a resin composition containing a specific ethylene ionomer as a main component and blended with silane coupling, and a glass layer is transparent. It can be seen that the glass sheet has excellent properties and high glass adhesive strength, in particular, excellent adhesive strength on the glass non-tin surface, and also excellent in processability of the resin sheet of the laminate.

  If such a laminate of the present invention is used as an interlayer film for laminated glass, it is expected that a laminated glass having excellent transparency and having both glass plates adhered to the interlayer film with uniform high adhesive strength can be obtained. . Such a laminated glass can be expected as a safer and more beautiful glass. Such laminated glass has high utility value as automotive glass or architectural glass.

Claims (4)

Containing an ethylene / unsaturated carboxylic acid copolymer zinc ionomer and a silane coupling agent, wherein the ethylene / unsaturated carboxylic acid copolymer has an unsaturated carboxylic acid content of 16% by mass or more; A resin sheet layer (A) comprising a resin composition, wherein the degree of neutralization of the unsaturated carboxylic acid copolymer by zinc ions is 10 to 40%;
A glass layer (B),
A laminate having a haze of 5.0 or less. The laminate according to claim 1, wherein the resin composition exhibits an adhesive strength of 10 N / 15 mm or more when measured by the following measurement method (c) on a glass non-tin surface.
Measurement method (c): A laminate is obtained by bonding a resin sheet made of the resin composition and a non-tin surface of a float plate glass under vacuum heating. This laminate is installed in a tensile tester, the resin sheet and the float glass are separated at a tensile speed of 100 mm / min, and the maximum stress is obtained as the adhesive strength (N / mm). Containing an ethylene / unsaturated carboxylic acid copolymer zinc ionomer and a silane coupling agent, wherein the ethylene / unsaturated carboxylic acid copolymer has an unsaturated carboxylic acid content of 16% by mass or more; A resin sheet layer (A) comprising a resin composition, wherein the degree of neutralization of the unsaturated carboxylic acid copolymer by zinc ions is 10 to 40%;
A glass layer (B),
A laminated glass having a haze of 5.0 or less. The laminated glass according to claim 3, wherein the resin composition exhibits an adhesive strength of 10 N / 15 mm or more when measured by the following measurement method (c) with respect to a glass non-tin surface.
Measurement method (c): A laminate is obtained by bonding a resin sheet made of the resin composition and a non-tin surface of a float plate glass under vacuum heating. This laminate is installed in a tensile tester, the resin sheet and the float glass are separated at a tensile speed of 100 mm / min, and the maximum stress is obtained as the adhesive strength (N / mm).