JP5385640B2 - Laminated sheet and solar cell module including the same - Google Patents

Description

  The present invention has a dark appearance and absorbs visible light when irradiated with light, but transmits infrared light and suppresses heat storage, and has heat resistance, flexibility, weather resistance and adhesiveness. The present invention relates to an excellent laminated sheet and a solar cell module including the same.

In recent years, solar cells have received more attention as energy supply means in place of petroleum, which is an energy source that forms carbon dioxide, which causes global warming. The demand for solar cells is also increasing, and stable supply and cost reduction of various members constituting solar cell modules included in solar cells have been required. In addition, the demand for improving the power generation efficiency of solar cells has increased.
In the solar cell module, a large number of plate-like solar cell elements are arranged, and these are wired in series and in parallel, and packaged to protect the elements and unitized. And this solar cell module usually uses a composition containing an ethylene / vinyl acetate copolymer having a high transparency and excellent moisture resistance by covering the surface of the solar cell element that is exposed to sunlight with a glass plate. Thus, the gap between the solar cell elements is filled to form a filler portion, and the back surface (the lower surface of the filler portion) is sealed with a member called a solar cell backsheet.

As a back sheet for a solar cell, a laminated sheet in which a white thermoplastic resin sheet is laminated on both sides of a polyester sheet is known in order to increase the reflectance of sunlight and increase the power generation efficiency of the solar cell (Patent Document). 1 and 2).
When arranging solar cells on the roof of a house, etc., it is preferred to be colored in a dark color such as black from the viewpoint of appearance, and for that reason, it is colored in a dark color A sheet is sought.

As a sheet colored in a dark color, a sheet made of carbon black is generally used. However, in this embodiment, the carbon black absorbs sunlight and the temperature rises, so that not only the power generation efficiency of the solar cell is lowered, but also the durability may be lowered.
Moreover, the sheet | seat which consists of a low heat storage thermoplastic resin composition containing a thermoplastic resin and the inorganic pigment which has an infrared reflective characteristic is known (refer patent document 3).
Furthermore, a sheet is known which has a black resin layer containing a perylene pigment on the surface and prevents heat accumulation by reflecting near infrared rays with a reflectance of light having a wavelength of 800 to 1,100 nm of 30% or more. (See Patent Document 4).

JP 2006-270025 A JP 2007-177136 A JP 2007-103813 A JP 2007-128943 A

  The present invention has a dark-colored appearance, is excellent in low heat storage when receiving sunlight or the like on the surface on the first resin layer side, excellent in heat resistance, flexibility, and weather resistance. An object of the present invention is to provide a laminated sheet excellent in adhesiveness with a member containing a polymer and having good workability and handleability, and a solar cell module including the same and providing a solar cell with improved photoelectric conversion efficiency. And

The present invention is shown below.
1. A laminated sheet comprising a first resin layer, a water vapor barrier layer, and a second resin layer in sequence ,
The first resin layer includes an aromatic vinyl resin and a first thermoplastic resin having a maximum glass transition temperature of 140 ° C. to 220 ° C. measured with a differential scanning calorimeter, an infrared transmitting colorant, An infrared transparent colored resin layer having a thickness of 10 to 100 μm, comprising a first thermoplastic resin composition containing
A rubber-reinforced aromatic vinyl resin obtained by polymerizing a monomer containing an aromatic vinyl compound in the presence of a rubbery polymer, and an aromatic vinyl compound and a maleimide compound. A vinyl monomer copolymer containing
The second resin layer is made of a second thermoplastic resin composition containing a second thermoplastic resin and white colorants, Ri white resin layer der having a thickness of 10 to 500 [mu] m,
The second thermoplastic resin is a saturated polyester resin;
Laminated sheet the water vapor barrier layer, on the surface of the polyester film, consisting of the deposition film formed by forming the film containing metal and / or metal oxide, the thickness is characterized by layers der Rukoto of 10~200μm .
2. 2. The laminated sheet according to 1 above, wherein when light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the laminated sheet, the light absorptance is 60% or more.
3. 3. The laminated sheet according to 1 or 2 above, wherein when light having a wavelength of 800 to 1,400 nm is emitted to the surface of the first resin layer in the laminated sheet, the reflectance with respect to the light is 50% or more.
4. The laminated sheet according to any one of 1 to 3 above, which has a dimensional change rate of ± 1% or less when left at 135 ° C. for 30 minutes.
5 . The first thermoplastic resin includes a structural unit (s1) derived from an aromatic vinyl compound and a structural unit (s2) derived from a maleimide compound, and the content of the structural unit (s2) is The laminated sheet according to any one of 1 to 4 above, which is 10 to 50% by mass with respect to 100% by mass of the total amount of structural units constituting one thermoplastic resin.
6 . The laminated sheet according to any one of 1 to 5 above, wherein the thickness of the laminated sheet is 30 to 600 μm.
7 . A solar cell module comprising the laminated sheet according to any one of 1 to 6 above.

According to the laminated sheet of the present invention, the surface on the first resin layer side is excellent in low heat storage when receiving sunlight or the like, the thermal deformation is suppressed, the heat resistance is excellent, flexibility, weather resistance, ethylene -Excellent adhesion to members containing vinyl acetate copolymer, and good workability and handleability.
When light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the laminated sheet and the light absorption rate is 60% or more, the infrared rays blended in the first resin layer According to the color of the transmissive colorant, it is possible to provide a solar cell module having an excellent dark color appearance, and when the solar cell module including the laminated sheet is disposed on a roof of a house, an excellent appearance and design Sex etc. can be obtained.
When light having a wavelength of 800 to 1,400 nm is radiated to the surface of the first resin layer in the laminated sheet, when the reflectance with respect to the light is 50% or more, sunlight is adjacent to the solar cell. When leaking from the gap between the elements toward the laminated sheet, heat storage in the laminated sheet is suppressed. And reflected light can be made incident on a solar cell element, and electric power generation efficiency can be improved.
When the dimensional change rate when the laminated sheet of the present invention is allowed to stand at 135 ° C. for 30 minutes is ± 1% or less, the heat resistance is excellent.
The first thermoplastic resin includes a structural unit (s1) derived from an aromatic vinyl compound and a structural unit (s2) derived from a maleimide compound, and the content of the structural unit (s2) is When it is 10-50 mass% with respect to 100 mass% of 1 thermoplastic resin, it is excellent in heat resistance especially.
Between the first resin layer and the second resin layer, so it comprises a water vapor barrier layer, the surface of the first resin layer side, and, laminated with excellent water vapor barrier property from the surface of the second resin layer side It can be a sheet.
The water vapor barrier layer, on its surface, since a deposition film layer containing a metal and / or metal oxide is formed, reducing the balance of heat resistance (dimensional stability) and flexibility in the laminated sheet Without having an excellent water vapor barrier property.
When the thickness of the laminated sheet of the present invention is 30 to 600 μm, the flexibility is excellent.

  Since the solar cell module of the present invention includes the laminated sheet of the present invention, the solar cell module is excellent in appearance, design, low heat storage, heat resistance and weather resistance, and forms a solar cell with improved photoelectric conversion efficiency. Can do. This solar cell is suitable for outdoor use exposed to sunlight or wind and rain for a long time.

It is a schematic sectional drawing which shows an example of the lamination sheet which is not included in this invention. It is a schematic sectional drawing which shows an example of the lamination sheet of this invention. It is a schematic sectional drawing which shows an example of the solar cell module of this invention.

  The present invention will be described in detail below. In this specification, “(co) polymerization” means homopolymerization and copolymerization. Further, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

The laminated sheet of the present invention is a laminated sheet comprising a first resin layer (infrared transparent colored resin layer), a water vapor barrier layer, and a second resin layer (white resin layer) in sequence, and its schematic cross section. It is illustrated in Figure 2. That is, the laminated sheet 1 ′ in FIG. 2 is a laminated sheet that includes the first resin layer 11, the water vapor barrier layer 13, and the second resin layer 12 in order.

Hereinafter, each layer will be described in order.
The first resin layer is an infrared transparent colored resin layer having a thickness of 10 to 100 μm, which is composed of a first thermoplastic resin composition containing a first thermoplastic resin and an infrared transparent colorant. It is a layer that has a property of absorbing visible light and transmitting infrared light and imparting flexibility to the laminated sheet of the present invention. The first thermoplastic resin composition is preferably a resin composition having film formability.

The first thermoplastic resin contained in the first thermoplastic resin composition contains an aromatic vinyl-based resin, and has a glass transition temperature (hereinafter referred to as “DSC”) measured using a differential scanning calorimeter (hereinafter referred to as “DSC”). Hereinafter, the maximum temperature of “Tg” is 140 ° C. to 220 ° C. Hereinafter, this property is referred to as “Tg requirement”. This Tg is preferably 145 ° C to 210 ° C, more preferably 150 ° C to 200 ° C. The Tg measurement conditions are as described in [Example].
When the first thermoplastic resin contains an aromatic vinyl resin, the member containing the ethylene / vinyl acetate copolymer composition and the first resin layer can be efficiently bonded.

  The first thermoplastic resin may be a single resin (aromatic vinyl resin) or a combination of two or more (aromatic vinyl resin and other resins). In addition, an aromatic vinyl-type resin may be used independently and may be used in combination of 2 or more type.

When the first thermoplastic resin is composed only of an aromatic vinyl resin, the DSC measurement of the aromatic vinyl resin has a Tg within a temperature range of 140 ° C to 220 ° C.
Moreover, when the said 1st thermoplastic resin consists of an aromatic vinyl-type resin and another resin, it originates in any one or both, and Tg is detected within the temperature range of 140 to 220 degreeC.
When the first thermoplastic resin composition contains the first thermoplastic resin having Tg in the above range, heat resistance can be imparted to the laminated sheet of the present invention.

The aromatic vinyl resin is a thermoplastic resin having a structural unit derived from an aromatic vinyl compound, and in the presence of a rubbery polymer (hereinafter referred to as “rubbery polymer (a1)”). Rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound (hereinafter referred to as “vinyl monomer (b11)”) (hereinafter referred to as “rubber-reinforced aromatic vinyl-based resin”). Resin (I-1) ") and a vinyl monomer containing an aromatic vinyl compound and a maleimide compound (hereinafter referred to as" vinyl monomer (b12) "). polymer (hereinafter, referred to as "copolymer (I-2)".) Ru Tona. The aromatic vinyl-based resin, because it contains rubber-reinforced aromatic vinyl resin (I-1), it is possible to form the first resin layer excellent in impact resistance.

  The rubber-reinforced aromatic vinyl resin (I-1) is a resin obtained by polymerizing a vinyl monomer (b11) containing an aromatic vinyl compound in the presence of the rubbery polymer (a1). In general, a copolymer resin in which a vinyl monomer (b11) containing an aromatic vinyl compound is graft-copolymerized on the rubber polymer (a1), and an ungrafted structure on which the rubber polymer (a1) is not grafted Ingredients, that is, (co) polymers with the remaining vinyl monomer (b11) are included.

  The rubbery polymer (a1) used for forming the rubber-reinforced aromatic vinyl resin (I-1) is not particularly limited as long as it is rubbery at room temperature, and any of a homopolymer and a copolymer may be used. Good. Further, the rubbery polymer (a1) may be either a crosslinked polymer or a non-crosslinked polymer.

  The rubbery polymer (a1) is not particularly limited, but is conjugated diene rubber, hydrogenated conjugated diene rubber, ethylene / α-olefin copolymer rubber, acrylic rubber, silicone rubber, silicone / acrylic composite. Rubber etc. are mentioned. These can be used alone or in combination of two or more. From the viewpoint of weather resistance, acrylic rubber, silicone rubber, silicone / acrylic composite rubber, ethylene / α-olefin copolymer rubber, hydrogenated conjugated diene rubber, and the like are preferable.

  The shape of the rubber polymer (a1) is not particularly limited, and may be particulate (spherical or substantially spherical), linear, curved or the like. When it is particulate, the volume average particle diameter is preferably 5 to 2,000 nm, more preferably 10 to 1,800 nm, and still more preferably 50 to 1,500 nm. If the volume average particle diameter is in the above range, the processability of the first thermoplastic resin composition and the impact resistance of the obtained first resin layer are excellent. The volume average particle diameter can be measured by image analysis using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

Examples of the conjugated diene rubber include polybutadiene, butadiene / styrene random copolymer, butadiene / styrene block copolymer, butadiene / acrylonitrile copolymer, and the like. These can be used alone or in combination of two or more.
In the present invention, the conjugated diene rubber preferably has a glass transition temperature of −20 ° C. or lower from the viewpoints of flexibility, low temperature impact property and the like.

  As said acrylic rubber, 80 mass% or more is included with respect to the whole quantity of the structural unit which comprises the said acrylic rubber for the structural unit derived from the alkyl group C2-C8 acrylic acid alkyl ester (co). Polymers are preferred.

  Examples of the alkyl acrylate having 2 to 8 carbon atoms in the alkyl group include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. Etc. These may be used alone or in combination of two or more. Preferred alkyl acrylates are n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.

  When the acrylic rubber contains a structural unit derived from another monomer, other monomers include vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ester, methacrylic acid alkyl ester, (meth) acrylic acid, Monofunctional monomers such as styrene; mono- or polyethylene glycol di (such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate ( Di- or triallyl compounds such as (meth) acrylate, divinylbenzene, diallyl phthalate, diallyl maleate, diallyl succinate, triallyl triazine, allyl compounds such as allyl (meth) acrylate, conjugated diene-based compounds such as 1,3-butadiene Crosslinkable monomer such as things like.

In the present invention, the acrylic rubber preferably has a glass transition temperature of −10 ° C. or lower from the viewpoints of flexibility, low temperature impact property and the like. The acrylic rubber having the glass transition temperature is usually a copolymer containing a structural unit derived from the crosslinkable monomer.
The content of the structural unit derived from the crosslinkable monomer constituting the preferred acrylic rubber is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass with respect to the total amount of the structural unit. %, More preferably 0.1 to 5% by mass.

  The volume average particle diameter of the acrylic rubber is preferably 5 to 500 nm, more preferably 10 to 450 nm, and still more preferably 20 to 400 nm from the viewpoints of flexibility, low temperature impact property and the like.

  The acrylic rubber is produced by a known method, but a preferred production method is an emulsion polymerization method.

  The silicone rubber is preferably a rubber contained in a latex in order to facilitate emulsion polymerization, which is a suitable method for producing a rubber-reinforced aromatic vinyl resin. Therefore, the silicone rubber is, for example, a polyorganosiloxane rubber produced by the method described in US Pat. Nos. 2,891,920, 3,294,725, etc. Can do.

  The polyorganosiloxane rubber is obtained by, for example, shear-mixing organosiloxane and water in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid using a homomixer or an ultrasonic mixer. The silicone rubber contained in the latex obtained by the condensation method is preferable. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also as a polymerization initiator. In this case, it is preferable to use an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt, or the like in combination because it has an effect of stably maintaining the silicone rubber when producing a rubber-reinforced aromatic vinyl resin. The polymer end of the polyorganosiloxane rubber may be sealed with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a methyldiphenylsilyl group, or the like. Further, if necessary, a graft crossing agent and / or a crosslinking agent may be co-condensed within a range not impairing the target performance of the present invention. By using these, impact resistance can be improved.

The organosiloxane used in the above reaction is, for example, the general formula [R ¹ _m SiO _{(4-m) / 2} ] (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and m is 0 to 0. 3 represents an integer of 3.). The structure of this compound is linear, branched or cyclic, but is preferably an organosiloxane having a cyclic structure. R ¹ possessed by the organosiloxane, that is, monovalent hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; aryl groups such as phenyl group and tolyl group; vinyl groups and allyl groups An alkenyl group such as: a group in which a part of hydrogen atoms bonded to carbon atoms in these hydrocarbon groups is substituted with a halogen atom, a cyano group, or the like; and at least one hydrogen atom in an alkyl group is substituted with a mercapto group Group and the like.

Examples of the organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. In addition to a cyclic compound such as a linear or branched organosiloxane. These can be used alone or in combination of two or more.
The organosiloxane may be a polyorganosiloxane condensed in advance, for example, having an Mw of about 500 to 10,000. When the organosiloxane is a polyorganosiloxane, the molecular chain terminal may be sealed with a hydroxyl group, an alkoxy group, a trimethylsilyl group, a methyldiphenylsilyl group, or the like.

  The graft crossing agent is usually a compound having a carbon-carbon unsaturated bond and an alkoxysilyl group. For example, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (P-Vinylbenzoyloxy) propylmethyldimethoxysilane and the like.

  The amount of the grafting agent used is usually 10 parts by mass or less, preferably 0.2 to 10 parts by mass, and more preferably 0.000 parts by mass when the total of the organosiloxane, the grafting agent and the crosslinking agent is 100% by mass. 5 to 5 parts by mass. If the amount of the graft crossing agent used is too large, the molecular weight of the graft copolymer is lowered, and as a result, sufficient impact resistance may not be obtained. Moreover, the oxidative deterioration is more likely to proceed than the double bond of the polyorganosiloxane rubber after grafting, and the rubber-reinforced aromatic vinyl resin (I-1) having good weather resistance may not be obtained.

  Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. A crosslinkable prepolymer obtained by condensation polymerization of these compounds in advance may be used. These may be used alone or in combination of two or more.

  The amount of the crosslinking agent used is usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 0.01 to 5 parts by mass, when the total of the organosiloxane, the grafting agent and the crosslinking agent is 100% by mass. Part. When there is too much usage-amount of the said crosslinking agent, the softness | flexibility of the polyorganosiloxane type rubber | gum obtained will be impaired and the flexibility of a film may fall.

  The volume average particle diameter of the silicone rubber is usually 5 to 500 nm, preferably 10 to 400 nm, and more preferably 50 to 400 nm. This volume average particle diameter can be easily controlled by the amount of emulsifier and water used during production, the degree of dispersion when mixed using a homomixer or an ultrasonic mixer, or the method of charging the organosiloxane. If the volume average particle diameter exceeds 500 nm, the appearance may be inferior, such as a decrease in gloss.

  The silicone / acrylic composite rubber is a rubbery polymer containing a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber. A preferable silicone-acrylic composite rubber is a composite rubber having a structure in which polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber are intertwined with each other so that they cannot be separated.

As the polyorganosiloxane rubber, a copolymer obtained by copolymerizing an organosiloxane can be preferably used. Examples of the organosiloxane include various reduced products having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, Tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane are preferred. These organosiloxanes can be used alone or in combination of two or more.
The content of the structural unit derived from the organosiloxane constituting the polyorganosiloxane rubber is preferably 50% by mass or more, more preferably 70% by mass or more based on the total amount of the structural unit.

The acrylic rubber is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate. A rubber obtained by (co) polymerizing a monomer containing a (meth) acrylic acid alkyl ester compound such as stearyl methacrylate. These (meth) acrylic acid alkyl ester compounds can be used alone or in combination of two or more.
In addition to (meth) acrylic acid alkyl ester compounds, the above monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid modified Various vinyl monomers such as silicone and fluorine-containing vinyl compounds may be included as a copolymerization component in the range of 30% by mass or less.

  The acrylic rubber is preferably a copolymer having two or more glass transition temperatures since it can impart sufficient flexibility to the film.

  As the silicone-acrylic composite rubber, for example, those manufactured by the methods described in JP-A-4-239010, JP-A-4-100812, and the like can be used.

  The volume average particle diameter of the silicone / acrylic composite rubber is preferably 5 to 500 nm, more preferably 10 to 450 nm, and still more preferably 20 to 400 nm from the viewpoints of flexibility, low temperature impact property and the like.

The ethylene / α-olefin copolymer rubber is a copolymer containing an ethylene unit and a structural unit composed of an α-olefin having 3 or more carbon atoms, and the ethylene / α-olefin copolymer, ethylene / α -An olefin and a nonconjugated diene copolymer etc. are mentioned.
Examples of the ethylene / α-olefin copolymer include an ethylene / propylene copolymer and an ethylene / butene-1 copolymer. Examples of the ethylene / α-olefin / non-conjugated diene copolymer include an ethylene / propylene / non-conjugated diene copolymer and an ethylene / butene-1 / non-conjugated diene copolymer.

  The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicocene and the like. In the α-olefin, a more preferable carbon number is 3 to 12, and further preferably 3 to 8.

  The proportion of ethylene units and α-olefin units constituting the ethylene / α-olefin copolymer rubber is preferably 5 to 95% by mass and 5 to 95%, respectively, when the total of these is 100% by mass. More preferably, they are 50-90 mass% and 10-50 mass%, More preferably, they are 60-88 mass% and 12-40 mass%, Most preferably, they are 70-85 mass% and 15-30 mass%. When there is too much content rate of the said alpha olefin unit, flexibility may fall.

When the ethylene / α-olefin copolymer rubber is an ethylene / α-olefin / non-conjugated diene copolymer, examples of the non-conjugated diene include alkenyl norbornene such as 5-ethylidene-2-norbornene; dicyclopentadiene Cyclic dienes such as aliphatic diene and the like. These compounds can be used alone or in combination of two or more.
The content of the structural unit derived from the non-conjugated diene is preferably 1 to 30% by mass, more preferably 2 with respect to the total amount of the structural unit constituting the ethylene / α-olefin / non-conjugated diene copolymer. ˜20 mass%. When there is too much content rate of a nonconjugated diene unit, shaping | molding external appearance property and weather resistance may fall.

The amount of unsaturated groups in the ethylene / α-olefin copolymer rubber is preferably 4 to 40 in terms of iodine value.
The Mooney viscosity (ML _{1 + 4} , 100 ° C .; conforming to JIS K6300) of the ethylene / α-olefin copolymer rubber is preferably 5 to 80, more preferably 10 to 65, and still more preferably 15 to 45. is there. When the Mooney viscosity is in the above range, the impact resistance and flexibility are excellent.

The hydrogenated conjugated diene rubber is not particularly limited as long as it is a (co) polymer obtained by hydrogenating a (co) polymer containing a structural unit derived from a conjugated diene compound.
Examples of the hydrogenated conjugated diene rubber include hydrogenated conjugated diene block copolymers having the following structure. That is, a polymer block A composed of a structural unit derived from an aromatic vinyl compound; a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content exceeding 25 mol%. Polymer block B formed by hydrogenation of 95 mol% or more; 95 mol% or more of a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content of 25 mol% or less Hydrogenated polymer block C formed by hydrogenation; and 95 mol% or more of a double bond portion of a copolymer composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. It is a block copolymer which consists of what combined 2 or more types among the polymer blocks D formed.

The molecular structure of the block copolymer may be branched, radial, or a combination thereof. The block structure may be a diblock, triblock, multiblock, or a combination thereof.
As the structure of the block copolymer, A- (BA) n, (AB) n, A- (BC) n, C- (BC) n, (BC) n , A- (DA) n, (AD) n, A- (DC) n, C- (DC) n, (DC) n, A- (BCD) ) N, (A-B-C-D) n [n is an integer of 1 or more. Etc., preferably AB-A, A-B-A-B, A-B-C, A-D-C, and C-B-C.

The aromatic vinyl compound used for forming the polymer blocks A and D constituting the block copolymer is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. . Examples thereof include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and the like. . These compounds can be used alone or in combination of two or more. Of these, styrene is preferred.
The content ratio of the polymer block A constituting the block copolymer is preferably 0 to 65% by mass, more preferably 10 to 40% by mass with respect to the whole polymer. When there is too much content of the polymer block A, impact resistance may not be enough.

  The polymer blocks B, C and D are formed by hydrogenating a pre-hydrogenation block copolymer obtained using a conjugated diene compound and an aromatic vinyl compound. Examples of the conjugated diene compound used for forming the polymer blocks B, C, and D include 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, and the like. These compounds can be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred because they can be utilized industrially and have excellent physical properties.

The hydrogenation rates of the polymer blocks B, C and D are all 95 mol% or more, preferably 96 mol% or more.
The 1,2-vinyl bond content in the polymer block B is preferably more than 25 mol% and 90 mol% or less, more preferably 30 to 80 mol%. When the 1,2-vinyl bond content is 25 mol% or less, rubbery properties are lost and impact resistance may not be sufficient. On the other hand, when it exceeds 90 mol%, chemical resistance may not be sufficient.
The 1,2-vinyl bond content in the polymer block C is preferably 25% mol or less, more preferably 20 mol% or less.

The 1,2-vinyl bond content in the polymer block D is preferably 25 to 90 mol%, more preferably 30 to 80 mol%. When the 1,2-vinyl bond content is less than 25 mol%, rubbery properties are lost and impact resistance may not be sufficient. On the other hand, when it exceeds 90 mol%, chemical resistance may not be sufficient.
The amount of the aromatic vinyl compound unit in the polymer block D is preferably 25% by mass or less, more preferably 20% by mass or less. If the amount of the aromatic vinyl compound unit exceeds 25% by mass, rubber properties may be lost and impact resistance may not be sufficient.

  Examples of the hydrogenated conjugated diene rubber include hydrogenated polybutadiene, hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer. And a hydrogenated product of a butadiene / acrylonitrile copolymer.

  The weight average molecular weight (Mw) of the hydrogenated conjugated diene rubber is preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000, and still more preferably 50,000 to 500,000. When Mw is in the above range, the flexibility is excellent.

  Next, the vinyl monomer (b11) used for forming the rubber-reinforced aromatic vinyl resin (I-1) contains an aromatic vinyl compound. That is, this vinyl monomer (b11) may be composed only of an aromatic vinyl compound, or composed of an aromatic vinyl compound and another monomer copolymerizable with this compound. Also good. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These can be used alone or in combination of two or more.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) ) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. Of these, N-phenylmaleimide is preferred. Moreover, these compounds can be used individually or in combination of 2 or more. As another method for introducing a structural unit derived from a maleimide compound into the rubber-reinforced aromatic vinyl resin, for example, an unsaturated dicarboxylic anhydride of maleic anhydride is copolymerized and then imidized. The method may be used.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester having a hydroxyl group such as a compound obtained by adding ε-caprolactone to 2-hydroxyethyl acid; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α -Methylstyrene M-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4 -Hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy- 2-butene, 3-hydroxy-2-me Examples include til-1-propene. These compounds can be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These compounds can be used alone or in combination of two or more.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.

  In the present invention, the vinyl monomer (b11) preferably contains an aromatic vinyl compound and a vinyl cyanide compound, and the total amount used thereof is molding processability, chemical resistance, hydrolysis resistance, dimensions. From the viewpoints of stability, molded appearance, etc., the content is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b11). The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 50 to 95% by mass and 5 to 50% by mass, still more preferably 60 to 95% by mass and 5 to 40% by mass, respectively.

  Moreover, when the said vinyl-type monomer (b11) contains a maleimide-type compound, heat resistance can be provided to a 1st resin layer. The preferable content of the structural unit derived from the maleimide compound contained in the first thermoplastic resin will be described later.

As the rubber-reinforced aromatic vinyl resin (I-1), preferred resins are as follows.
[1-1] A rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer (b11) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer (a1). (I-1-1)
[1-2] Rubber-reinforced aroma obtained by polymerizing vinyl monomer (b11) comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of rubber polymer (a1). Group vinyl resin (I-1-2)
[1-3] A rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer (b11) composed of an aromatic vinyl compound and a maleimide compound in the presence of the rubbery polymer (a1) ( I-1-3)
[1-4] Rubber reinforcement obtained by polymerizing a vinyl monomer (b11) comprising an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic ester compound in the presence of the rubbery polymer (a1). Aromatic vinyl resin (I-1-4)

  The rubber-reinforced aromatic vinyl resin (I-1) can be produced by polymerizing the vinyl monomer (b11) in the presence of the rubber polymer (a1). As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used.

  In the production of the rubber-reinforced aromatic vinyl resin (I-1), the rubber polymer (a1) and the vinyl monomer (b11) are reacted with each other in the reaction system. (A1) In the presence of the total amount, the above-mentioned vinyl monomer (b11) may be added all at once to initiate the polymerization, or the polymerization may be carried out while being divided or continuously added. Further, in the presence or absence of a part of the rubber polymer (a1), the vinyl monomer (b11) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, the remainder of the rubber-like polymer (a1) may be added all at once during the reaction, divided or continuously.

  In the case of producing a rubber-reinforced aromatic vinyl resin by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b11) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0 mass% with respect to the total amount of the vinyl monomer (b11).
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b11) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (b11), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
In the case where two or more kinds of rubber-reinforced aromatic vinyl resins are contained in the aromatic vinyl resin, the resins may be mixed after being isolated from each latex. There are methods such as coagulating a mixture of latexes each containing a resin.

  Known methods can be applied to the method for producing a rubber-reinforced aromatic vinyl resin by solution polymerization, bulk polymerization, and bulk-suspension polymerization.

  The rubber-reinforced aromatic vinyl resin (I-1) may be a commercially available product having a configuration such as a silicone rubber-reinforced styrene resin or a silicone / acrylic composite rubber-reinforced styrene resin. For example, a rubber-reinforced aromatic vinyl resin (I-1) using a silicone / acrylic composite rubber as the rubber polymer (a1) is, for example, a commercial product obtained by the method described in JP-A-4-239010. Examples thereof include “Metablene SX-006” (trade name) manufactured by Mitsubishi Rayon Co., Ltd.

  The graft ratio of the rubber-reinforced aromatic vinyl resin (I-1) is preferably 20 to 170%, more preferably 30 to 170%, and still more preferably 40 to 150%. If this graft ratio is too low, the flexibility of the first resin layer may not be sufficient. On the other hand, if the graft ratio is too high, the viscosity of the rubber-reinforced aromatic vinyl resin (I-1) tends to increase, and it may be difficult to reduce the thickness with the first thermoplastic resin composition.

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the above formula, S represents 1 gram of rubber-reinforced aromatic vinyl resin (I-1) in 20 ml of acetone (acetonitrile when rubbery polymer (a1) is an acrylic rubber), and the temperature is 25 ° C. Then, after shaking with a shaker for 2 hours, centrifuge for 60 minutes under a temperature condition of 5 ° C. with a centrifuge (rotation speed: 23,000 rpm) to separate insoluble and soluble components. It is the mass (g) of the insoluble matter obtained, and T is the mass (g) of the rubber-like polymer (a1) contained in 1 gram of the rubber-reinforced aromatic vinyl resin (I-1). The mass of the rubber-like polymer (a1) can be obtained by a method of calculating from the polymerization prescription and the polymerization conversion rate, a method of obtaining from the infrared absorption spectrum (IR), and the like.

  The rubber-reinforced aromatic vinyl resin (I-1) can be used alone or in combination of two or more.

The copolymer (I-2) is a homopolymer and copolymers obtained by using a vinyl-based monomer containing an aromatic vinyl compound and maleimide compound (b12).

The vinyl monomer (b12) may be only an aromatic vinyl compound and a maleimide compound, or may be a combination of this aromatic vinyl compound, a maleimide compound and another monomer. Good. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, oxazoline groups Examples thereof include unsaturated compounds. These can be used alone or in combination of two or more. The compound illustrated in the said vinyl monomer (b11) is applied to each said compound.

The other monomer is preferably a vinyl cyanide compound.
When the vinyl monomer (b12) contains an aromatic vinyl compound and a vinyl cyanide compound, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is determined by molding processability, chemical resistance, and hydrolysis resistance. From the viewpoints of dimensional stability, molded appearance, etc., when these totals are 100% by mass, preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 40 to 95% by mass and 5%, respectively. It is -60 mass%, More preferably, it is 50-90 mass% and 10-50 mass%.

The copolymer as (I-2), preferred polymers are as follows.
[1-5] A structural unit derived from an aromatic vinyl compound (hereinafter referred to as “structural unit (s1)”) and a structural unit derived from a maleimide compound (hereinafter referred to as “structural unit (hereinafter referred to as“ structural unit ”). a structural unit (s1) derived from a copolymer [1-6] aromatic vinyl compound, a structural unit (s2) derived from a maleimide compound, and cyanide A copolymer comprising a structural unit derived from a vinyl compound (hereinafter referred to as “structural unit (s3)”).

When the copolymer (I-2) is the above embodiment [1-5], the content ratios of the structural unit (s1) and the structural unit (s2) are the molding processability, heat resistance, chemical resistance, and water resistance. From the viewpoints of degradability, dimensional stability, flexibility, etc., when these totals are 100% by mass, preferably 10 to 90% by mass and 90 to 10% by mass, more preferably 20 to 80% by mass, respectively. And 80 to 20% by mass, more preferably 30 to 70% by mass and 70 to 30% by mass.
As said aspect [1-5], a styrene N-phenylmaleimide copolymer etc. are mentioned.

When the copolymer (I-2) is the above embodiment [1-6], the content ratios of the structural unit (s1), the structural unit (s2), and the structural unit (s3) are molding processability, heat resistance, From the viewpoints of chemical resistance, hydrolysis resistance, dimensional stability, flexibility and the like, when these are 100% by mass, preferably 10 to 90% by mass, 10 to 70% by mass and 1 to 1%, respectively. It is 45 mass%, More preferably, it is 20-80 mass%, 15-60 mass%, and 3-40 mass%, More preferably, it is 30-70 mass%, 20-50 mass%, and 5-35 mass%.
As said aspect [1-6], an acrylonitrile * styrene * N-phenylmaleimide copolymer etc. are mentioned.

The copolymer (I-2) can be produced by polymerizing a vinyl monomer (b12) containing an aromatic vinyl compound and a maleimide compound in the presence or absence of a polymerization initiator. it can. When a polymerization initiator is used as the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. Moreover, when not using a polymerization initiator, it can be set as thermal polymerization.

As said polymerization initiator, the compound illustrated by description of the manufacturing method of the said rubber reinforced aromatic vinyl-type resin (I-1) can be used individually by 1 type or in combination of 2 or more types. The usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b12) whole quantity.
In addition, the chain transfer agent, emulsifier, etc. which can be used at the time of manufacture of the said rubber reinforced aromatic vinyl-type resin (I-1) can be used as needed.

  In the production of the copolymer (I-2), the polymerization may be started in a state where the entire amount of the vinyl monomer (b12) is accommodated in the reaction system, and an arbitrarily selected monomer component. The polymerization may be carried out by adding in portions or continuously. Furthermore, when using the said polymerization initiator, it can add to a reaction system collectively or continuously.

  The said copolymer (I-2) can be used individually by 1 type or in combination of 2 or more types.

  When the first thermoplastic resin is an aromatic vinyl resin, usually at least one of the rubber-reinforced aromatic vinyl resin (I-1) and the copolymer (I-2) satisfies the Tg requirement. Satisfies.

  In the aromatic vinyl resin, the content of the rubber polymer (a1) derived from the rubber-reinforced aromatic vinyl resin (I-1) is preferably based on 100% by mass of the first thermoplastic resin. Is 5 to 40% by mass, more preferably 8 to 30% by mass, still more preferably 10 to 20% by mass, and particularly preferably 12 to 18% by mass. If the content exceeds 40% by mass, the heat resistance may not be sufficient and the formation of the first resin layer may be difficult. On the other hand, when the content is less than 5% by mass, the impact resistance may not be sufficient.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of a component soluble in acetone of the aromatic vinyl resin (but acetonitrile if the rubbery polymer is an acrylic rubber) is preferably Is 0.1 to 2.5 dl / g, more preferably 0.2 to 1.5 dl / g, still more preferably 0.25 to 1.2 dl / g. When the intrinsic viscosity [η] is within the above range, the moldability of the first thermoplastic resin composition is excellent, and the thickness accuracy of the first resin layer is also excellent.

Here, the intrinsic viscosity [η] can be obtained in the following manner.
When the graft ratio in the above aromatic vinyl resin (including rubber-reinforced aromatic vinyl resin (I-1)) is determined, acetone-soluble matter recovered after centrifugation (the rubbery polymer is an acrylic rubber). In this case, acetonitrile soluble component) is dissolved in methyl ethyl ketone, 5 different concentrations are prepared, and the reduced viscosity of each concentration is measured at 30 ° C. using an Ubbelohde viscosity tube, and the intrinsic viscosity [η] is obtained. .

The graft ratio and the intrinsic viscosity [η] are a polymerization initiator, a chain transfer agent used when the rubber-reinforced aromatic vinyl resin (I-1) and the copolymer (I-2) are produced, It can be easily controlled by adjusting the type and amount of the emulsifier, the solvent, etc., as well as the polymerization time and polymerization temperature.
Further, the intrinsic viscosity [η] of the aromatic vinyl resin is appropriately selected from rubber-reinforced aromatic vinyl resins (I-1) and copolymers (I-2) having different intrinsic viscosities [η]. It can also be adjusted by doing.

The aromatic vinyl resin includes a structural unit (s2) derived from a maleimide compound. This structural unit (s2) may be derived from the rubber-reinforced aromatic vinyl resin (I-1) and the copolymer (I-2).

  When the first thermoplastic resin is composed of an aromatic vinyl resin and another resin, the other resin includes an acrylic resin containing a structural unit derived from an alkyl (meth) acrylate; polyethylene terephthalate, polyethylene naphthalate And saturated polyester resins such as polybutylene terephthalate, polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polycarbonate resins, fluororesins, and ethylene / vinyl acetate resins. These can be used alone or in combination of two or more.

When the first thermoplastic resin is composed of an aromatic vinyl resin and another resin, the lower limit of the content of the aromatic vinyl resin is preferably 50% by mass with respect to the first thermoplastic resin. Preferably it is 60 mass%, More preferably, it is 70 mass%. If the content is too low, the impact resistance and the like in the first resin layer may not be sufficient.
When the first thermoplastic resin is composed of an aromatic vinyl resin and another resin, any resin that satisfies the Tg requirement may be used, but the aromatic vinyl resin satisfies the Tg requirement. Preferably it is.

In the present invention, as an aspect of the first thermoplastic resin that imparts excellent heat resistance to the first resin layer, the aromatic vinyl resin is the rubber-reinforced aromatic vinyl resin (I-1), and A resin comprising the copolymer (I-2), wherein the resin comprises at least a structural unit (s1) derived from an aromatic vinyl compound and a structural unit (s2) derived from a maleimide compound. In addition, the content of the latter structural unit (s2) is preferably 10 to 50% by mass, more preferably 12 to 45% by mass, with respect to 100% by mass of the total amount of the structural units constituting the first thermoplastic resin. More preferably, it has a configuration of 15 to 40% by mass.
In a particularly preferred embodiment, the aromatic vinyl resin is a resin comprising the rubber-reinforced aromatic vinyl resin (I-1) and the copolymer (I-2), and the rubber-reinforced aromatic vinyl resin. (I-1) may be any of the rubber-reinforced aromatic vinyl resins (I-1-1) to (I-1-4) exemplified above, and the copolymer (I-2) is an aromatic vinyl. The structural unit (s1) derived from the compound and the structural unit (s2) derived from the maleimide compound, and the content of the structural unit (s2) is 100 based on the total amount of the structural units constituting the first thermoplastic resin. The composition is preferably 10 to 50 mass%, more preferably 12 to 45 mass%, and still more preferably 15 to 40 mass% with respect to mass%.
When there is too much content of the structural unit (s2) which comprises the said 1st thermoplastic resin, the flexibility of a 1st resin layer may fall.

  The infrared transmissive colorant contained in the first thermoplastic resin composition is a colorant having a property of absorbing visible light and transmitting infrared light. This infrared transmissive colorant usually has a color other than white, and is preferably a dark color system such as black, brown, dark blue, or dark green.

〔式中、Ｒ^２及びＲ^３は、互いに同一又は異なって、ブチル基、フェニルエチル基、メトキシエチル基又は４−メトキシフェニルメチル基である。〕

〔式中、Ｒ^４及びＲ^５は、互いに同一又は異なって、フェニレン基、３−メトキシフェニレン基、４−メトキシフェニレン基、４−エトキシフェニレン基、炭素数１〜３のアルキルフェニレン基、ヒドロキシフェニレン基、４，６−ジメチルフェニレン基、３，５−ジメチルフェニレン基、３−クロロフェニレン基、４−クロロフェニレン基、５−クロロフェニレン基、３−ブロモフェニレン基、４−ブロモフェニレン基、５−ブロモフェニレン基、３−フルオロフェニレン基、４−フルオロフェニレン基、５−フルオロフェニレン基、ナフチレン基、ナフタレンジイル基、ピリジレン基、２，３−ピリジンジイル基、３，４−ピリジンジイル基、４−メチル−２，３−ピリジンジイル基、５−メチル−２，３−ピリジンジイル基、６−メチル−２，３−ピリジンジイル基、５−メチル−３，４−ピリジンジイル基、４−メトキシ−２，３−ピリジンジイル基又は４−クロロ−２，３−ピリジンジイル基である。〕

〔式中、Ｒ^６及びＲ^７は、互いに同一又は異なって、フェニレン基、３−メトキシフェニレン基、４−メトキシフェニレン基、４−エトキシフェニレン基、炭素数１〜３のアルキルフェニレン基、ヒドロキシフェニレン基、４，６−ジメチルフェニレン基、３，５−ジメチルフェニレン基、３−クロロフェニレン基、４−クロロフェニレン基、５−クロロフェニレン基、３−ブロモフェニレン基、４−ブロモフェニレン基、５−ブロモフェニレン基、３−フルオロフェニレン基、４−フルオロフェニレン基、５−フルオロフェニレン基、ナフチレン基、ナフタレンジイル基、ピリジレン基、２，３−ピリジンジイル基、３，４−ピリジンジイル基、４−メチル−２，３−ピリジンジイル基、５−メチル−２，３−ピリジンジイル基、６−メチル−２，３−ピリジンジイル基、５−メチル−３，４−ピリジンジイル基、４−メトキシ−２，３−ピリジンジイル基又は４−クロロ−２，３−ピリジンジイル基である。〕 Examples of the infrared transmitting colorant include perylene pigments. As the perylene pigment, compounds represented by the following general formulas (I) to (III) can be used.

[Wherein, R ² and R ³ are the same or different from each other, and are a butyl group, a phenylethyl group, a methoxyethyl group, or a 4-methoxyphenylmethyl group. ]

[Wherein, R ⁴ and R ⁵ are the same as or different from each other, and include a phenylene group, a 3-methoxyphenylene group, a 4-methoxyphenylene group, a 4-ethoxyphenylene group, an alkylphenylene group having 1 to 3 carbon atoms, and a hydroxyphenylene. Group, 4,6-dimethylphenylene group, 3,5-dimethylphenylene group, 3-chlorophenylene group, 4-chlorophenylene group, 5-chlorophenylene group, 3-bromophenylene group, 4-bromophenylene group, 5- Bromophenylene group, 3-fluorophenylene group, 4-fluorophenylene group, 5-fluorophenylene group, naphthylene group, naphthalenediyl group, pyridylene group, 2,3-pyridinediyl group, 3,4-pyridinediyl group, 4- Methyl-2,3-pyridinediyl group, 5-methyl-2,3-pyridinediyl group, 6- Le-2,3-pyridinediyl group, 5-methyl 3,4-pyridinediyl group, 4-methoxy-2,3-pyridinediyl group, or a 4-chloro-2,3-pyridinediyl group. ]

[Wherein, R ⁶ and R ⁷ are the same or different from each other, and include a phenylene group, a 3-methoxyphenylene group, a 4-methoxyphenylene group, a 4-ethoxyphenylene group, an alkylphenylene group having 1 to 3 carbon atoms, and a hydroxyphenylene. Group, 4,6-dimethylphenylene group, 3,5-dimethylphenylene group, 3-chlorophenylene group, 4-chlorophenylene group, 5-chlorophenylene group, 3-bromophenylene group, 4-bromophenylene group, 5- Bromophenylene group, 3-fluorophenylene group, 4-fluorophenylene group, 5-fluorophenylene group, naphthylene group, naphthalenediyl group, pyridylene group, 2,3-pyridinediyl group, 3,4-pyridinediyl group, 4- Methyl-2,3-pyridinediyl group, 5-methyl-2,3-pyridinediyl group, 6- Le-2,3-pyridinediyl group, 5-methyl-3,4-pyridinediyl group, 4-methoxy-2,3-pyridinediyl group, or a 4-chloro-2,3-pyridinediyl group. ]

In addition, as the perylene-based pigment, commercially available products such as “Paligen Black S 0084”, “Palogen Black L 0086”, “Lumogen Black FK4280”, “Lumogen Black FK4281” (all of which are trade names manufactured by BASF) are used. Can be used.
The infrared transmissive colorant can be used alone or in combination of two or more.

  The content ratio of the infrared transmitting colorant in the first thermoplastic resin composition is preferably 10% by mass with respect to the first thermoplastic resin composition from the viewpoints of infrared transmission and visible light absorption. Hereinafter, it is more preferably 0.01 to 6% by mass, and still more preferably 0.05 to 5% by mass.

In the present invention, the first thermoplastic resin composition can contain other colorants depending on the purpose, application, etc., unless the infrared transmittance of the first resin layer is reduced.
Examples of other colorants include a cyan colorant (blue color material), a magenta colorant (red color material), and a yellow colorant (yellow color material).

For example, as other colorants, yellow pigments, blue pigments, and the like are used, and an article provided with variously colored laminated sheets can be obtained by the following combinations.
[1] Brown coloration by combination of black-based infrared transmitting colorant and yellow pigment [2] Dark blue coloration by combination of black-based infrared transmitting colorant and blue pigment When other colorant is used, The content in the thermoplastic resin composition is usually 60 parts by mass or less, preferably 0.01 to 55 parts by mass with respect to 100 parts by mass of the infrared transmitting colorant.

  As a dark colorant, carbon black that absorbs light having a wavelength in the infrared region is known. In the case where sunlight is received on the surface of the first resin layer with respect to the laminated sheet formed with the composition using carbon black instead of the infrared transmitting colorant, the first resin layer receives the first resin layer. Heat storage in the resin layer becomes significant. Therefore, this laminated sheet is used as a solar battery back sheet, and the surface on the first resin layer side and the filler part containing the ethylene / vinyl acetate copolymer composition and the like embedding the solar battery element are joined. When the solar cell module is used, when sunlight leaks to the first resin layer containing carbon black, from the stored solar cell backsheet, the temperature of the filler part including the solar cell element will be increased, There is a problem that reduces power generation efficiency. Therefore, in the present invention, by setting the first resin layer to include an infrared transmitting colorant, it is possible to maintain low heat storage and suppress the above-described problems in solar cell applications and the like.

  The said 1st thermoplastic resin composition shall contain an additive according to the objective, a use, etc. This additive includes antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, fluorescent brighteners, weathering agents, fillers, antistatic agents, flame retardants, antifogging agents, antibacterial agents, antifungal agents, Antifouling agents, tackifiers, silane coupling agents and the like can be mentioned. Specific compounds in these additives and their blending amounts will be described later.

  In order to contain the additive, a melt-kneading method is usually used. Examples of the apparatus used for melt kneading include a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a continuous kneader.

The thickness of the first resin layer is 10 to 100 μm, preferably 15 to 95 μm, more preferably 20 to 90 μm. When the said thickness is too thin, the intensity | strength of the lamination sheet of this invention is inadequate, and flexibility is inadequate when it is too thick.

  The second resin layer is a white resin layer having a thickness of 10 to 500 μm made of a second thermoplastic resin composition containing a second thermoplastic resin and a white colorant. Is a layer having an action of reflecting the light and maintaining the balance of flexibility of the laminated sheet of the present invention. And this 2nd thermoplastic resin composition, Preferably, it is a resin composition which has film forming property.

Second thermoplastic resin contained in the second thermoplastic resin composition, Ru saturated polyester resin der. A saturated polyester resin is used from the viewpoints of toughness, flame retardancy, heat resistance, and the like.

The saturated polyester resin is preferably a resin obtained by polycondensation reaction of a dicarboxylic acid component and a glycol component.
Dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfoisophthalic acid and other aromatic dicarboxylic acids Alicyclic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid and fumaric acid; alicyclic dicarboxylic acids such as cyclohexyne dicarboxylic acid; oxycarboxylic acids such as p-oxybenzoic acid; Etc.
Examples of the glycol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-butanediol, and 1,6-hexane. Aliphatic glycols such as diol and neopentyl glycol; polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; alicyclic glycols such as 1,4-cyclohexanedimethanol; bisphenol A, bisphenol S and the like Aromatic glycols, and the like. Each of these dicarboxylic acid components and glycol components may be used alone or in combination of two or more.

As the saturated polyester resin, a polyester resin containing ethylene terephthalate as a main constituent unit obtained by a polycondensation reaction using terephthalic acid or dimethyl terephthalate and ethylene glycol using an esterification reaction or an ester exchange reaction is preferable. By using this polyester resin, it is excellent in mechanical strength, workability, thermal characteristics and the like. The “main structural unit” means that the content of ethylene terephthalate constituting the polyester resin is 30 mol% or more.
As the saturated polyester resin, polyethylene-2,6-naphthalate resin is also preferably used from the viewpoint of strength and heat stability.

Examples of the white colorant include titanium oxide, zinc oxide, calcium carbonate, barium sulfate, calcium sulfate, alumina, silica, 2PbCO ₃ .Pb (OH) ₂ , [ZnS + BaSO ₄ ], talc, and gypsum. These may be used alone or in combination of two or more.
The content of the white colorant is preferably 1 to 45% by mass, more preferably 3 to 3% with respect to the second thermoplastic resin composition, from the viewpoint of reflectivity with respect to light having a wavelength of 800 to 1,400 nm. It is 40 mass%, More preferably, it is 5-30 mass%. When there is too much content of this white type coloring agent, the flexibility of the lamination sheet of the present invention may fall.

  The second resin layer is a white resin layer, and the L value (brightness) on the surface of the film composed of the single layer is preferably 60 or more, more preferably 65 or more, and particularly preferably 70 or more.

  The second thermoplastic resin composition may contain other colorants (for example, a yellow colorant, a blue colorant, etc.) other than the white colorant as long as the L value is not lowered. When using other colorants, the content thereof is usually 10% by mass or less with respect to the second thermoplastic resin composition.

  The said 2nd thermoplastic resin composition shall contain an additive according to the objective, a use, etc. This additive includes antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, fluorescent brighteners, weathering agents, fillers, antistatic agents, flame retardants, antifogging agents, antibacterial agents, antifungal agents, Antifouling agents, tackifiers, silane coupling agents and the like can be mentioned. Specific compounds in these additives and their blending amounts will be described later.

  In order to contain the additive, a melt-kneading method is usually used. Examples of the apparatus used for melt kneading include a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a continuous kneader.

  In forming the second resin layer, a commercially available white resin film can also be used. For example, “Lumirror E20” (trade name) manufactured by Toray Industries, Inc., “PET film U2” (trade name) manufactured by Teijin DuPont Films, Inc. can be used. In the case of using a commercially available resin film, it is preferable to use a flame retardant resin film in order to increase the fire resistance from the second resin layer side surface of the laminated sheet. In addition, it is preferable that the flame retardance of the resin film which has a flame retardance is a UL94VTM-2 class or a class beyond it.

  The thickness of the second resin layer is 10 to 500 μm, preferably 15 to 400 μm, more preferably 20 to 300 μm. If it is the said thickness, it is excellent in the flexibility and heat resistance of the lamination sheet of this invention. If the thickness is too thin, the protective effect on the second resin layer side surface of the laminated sheet of the present invention is insufficient, and when the first resin layer in the laminated sheet emits light, the first resin layer May not be sufficiently reflected by the second resin layer. On the other hand, when the thickness is too thick, the flexibility of the laminated sheet is insufficient.

  Next, the additive contained in the first resin layer (first thermoplastic resin composition) and the second resin layer (second thermoplastic resin composition) will be described.

Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.
The content of the antioxidant is preferably 0.05 to 10% by mass with respect to the first thermoplastic resin composition and / or the second thermoplastic resin composition.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.
The content of the ultraviolet absorber is preferably 0.05 to 10% by mass with respect to the first thermoplastic resin composition and / or the second thermoplastic resin composition.

Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.
The content of the anti-aging agent is preferably 0.05 to 10% by mass with respect to the first thermoplastic resin composition and / or the second thermoplastic resin composition.

Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; dimethyl adipate , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octy Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate, Examples include tri- (2-ethylhexyl) phosphate and epoxidized soybean oil. These can be used alone or in combination of two or more.
The content of the plasticizer is preferably 0.05 to 10% by mass with respect to the first thermoplastic resin composition and / or the second thermoplastic resin composition.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.
Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toki Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus flame retardants such as phosphazene derivatives containing phosphorus elements and nitrogen elements; polytetrafluoroethylene, guanidine salts, silicone compounds, phosphazene compounds, and the like. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate. These can be used alone or in combination of two or more.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used alone or in combination of two or more.

The content of the flame retardant is preferably 10% by mass or less with respect to the first thermoplastic resin composition and / or the second thermoplastic resin composition.
In addition, when making a thermoplastic resin composition contain a flame retardant, it is preferable to use a flame retardant aid. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples include ammonium polyphosphate and tin oxide. These may be used alone or in combination of two or more.

In the present invention, the degree of coloring of the first resin layer, which is an infrared transmissive colored resin layer, is not particularly limited as long as the infrared transparency of the first resin layer is satisfied. Colored so that the L value of the surface on the first resin layer side of the laminated sheet (hereinafter referred to as “L value as a laminated sheet”) is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. Has been.
The first resin layer may contain a white colorant as long as the L value as the laminated sheet (the L value of the surface on the first resin layer side) has the above value. It is preferable that no white colorant is contained. When the white colorant is contained in the first resin layer and the L value is satisfied, the upper limit of the content is usually 3 parts by mass, preferably 1 with respect to 100 parts by mass of the first thermoplastic resin. Part by mass.

  As described above, the laminated sheet of the present invention includes the water vapor barrier layer 13 between the first resin layer 11 and the second resin layer 12 (see FIG. 2).

The water vapor barrier layer has a moisture permeability (also referred to as “water vapor permeability”) measured under conditions of a temperature of 40 ° C. and a humidity of 90% RH in accordance with JIS K7129, preferably 3 g / (m ² · day) or less. More preferably, the layer has a performance of 1 g / (m ² · day) or less, and further preferably 0.7 g / (m ² · day) or less.
The water vapor barrier layer is preferably a layer made of an electrically insulating material.

The water vapor barrier layer, Ru multilayer structure der made of two kinds of materials. In this invention, it is a vapor deposition film by which the film | membrane which consists of a metal and / or a metal oxide is formed in the surface of a polyester film . Both the metal and the metal oxide may be a single substance or two or more kinds.

Examples of the metal include aluminum.
Examples of the metal compound include oxides of elements such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. Of these, silicon oxide, aluminum oxide, and the like are particularly preferable from the viewpoint of water vapor barrier properties.
The film made of the metal and / or metal oxide may be formed by a method such as plating, vacuum deposition, ion plating, sputtering, plasma CVD, or microwave CVD. Two or more of these methods may be combined.

  Examples of the resin layer in the deposited film include polyester films such as polyethylene terephthalate film and polyethylene naphthalate. The thickness of this resin film is preferably 5 to 50 μm, more preferably 8 to 20 μm.

  The said water vapor | steam barrier layer shall be formed using the commercial item. For example, “Tech Barrier AX” manufactured by Mitsubishi Plastics, “GX Film” manufactured by Toppan Printing Co., Ltd., “Ecosia VE500” manufactured by Toyobo Co., Ltd. (hereinafter referred to as “trade name”), and the like are used as the water vapor barrier layer forming sheet (or film). Can do.

  The arrangement of the water vapor barrier layer between the first resin layer and the second resin layer is not particularly limited, and a film made of a metal and / or a metal oxide is placed on either the first resin layer or the second resin layer. You may face.

  The thickness of the water vapor barrier layer is preferably 5 to 300 μm, more preferably 8 to 250 μm, and still more preferably 10 to 200 μm. If the water vapor barrier layer is too thin, the water vapor barrier property may be insufficient. If it is too thick, the flexibility as a sheet may not be sufficient.

In the laminated sheet of the present invention, an adhesive layer can be provided between the first resin layer and / or the second resin layer and the water vapor barrier layer. The configuration of the adhesive layer can be a polyurethane resin composition, an epoxy resin composition, an acrylic resin composition, or the like.

The thickness of the laminated sheet of the present invention is preferably 30 to 600 μm, more preferably 50 to 500 μm, and still more preferably, from the viewpoints of flexibility, shape followability when disposed on other articles, workability, and the like. 60-400 μm.
In addition, between the 1st resin layer and the 2nd resin layer in the lamination sheet of this invention, in the range which does not impair the effect of this invention, if desired, a layer which consists of a decorative resin, a coating layer, and the recycled resin produced at the time of manufacture It is also possible to stack other layers.

The method for producing the laminated sheet of the present invention is not particularly limited, and is selected depending on the constituent material of each layer, that is, each thermoplastic resin composition.
For example, the first resin layer is formed by bonding one surface side of the first resin layer sheet (or film) and one surface side of the water vapor barrier layer forming sheet (or film) by heat fusion, dry lamination, or an adhesive. And a laminate comprising a water vapor barrier layer, and then a method of bonding the second resin layer sheet (or film) to the surface of the water vapor barrier layer in the laminate with an adhesive, and the like.

  In the laminated sheet of the present invention, when light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the laminated sheet, the light absorption rate is preferably 60% or more, more preferably 70% or more, and further Preferably it is 80% or more. The higher the absorptance, the lower the brightness of the laminated sheet as viewed from the first resin layer side, and the dark colored laminated sheet is formed. Thereby, when a transparent member or a semi-transparent member and the surface of the 1st resin layer are joined, and a composite member is produced, it is excellent in the external appearance and design nature seen from the transparent member side. For example, when a laminated sheet is used as a back sheet for a solar cell to produce a solar cell module and then used as a solar cell, the appearance and design of the solar cell disposed on the roof of a house are excellent. “Absorptivity with respect to light having a wavelength of 400 to 700 nm is 60% or more” means that the absorptance of light in the wavelength region from 400 nm to 700 nm is measured every 400 nm or from 700 nm to 20 nm, and each absorptivity is used. It means that the calculated average value is 60% or more, and it does not require that the light absorption rate in the wavelength range is 60% or more.

  In the laminated sheet of the present invention, when light having a wavelength of 800 to 1,400 nm is radiated to the surface of the first resin layer in the laminated sheet, the reflectance with respect to this light is preferably 50% or more, more preferably 60. % Or more, more preferably 70% or more. The higher the reflectance, the more light having at least the wavelength can be reflected toward the first resin layer side. For example, when a laminated sheet is used as a back sheet for a solar cell to produce a solar cell module, at least light having the above wavelength can be reflected toward the solar cell element, thereby improving the photoelectric conversion efficiency. it can. “Reflectance for light with a wavelength of 800 to 1,400 nm is 50% or more” means that the reflectance of light in the wavelength range from 800 nm to 1,400 nm is measured every 800 nm or every 1,400 nm to 20 nm. In addition, it means that the average value calculated using each reflectance is 50% or more, and it does not require that all the reflectances of light in the wavelength range are 50% or more.

  By providing these preferable performances, in the laminated sheet of the present invention, preferably, 60% or more of light having a wavelength of 400 to 700 nm emitted to the surface of the first resin layer is absorbed, and a wavelength of 800 to 1, When light of 400 nm is transmitted and this light reaches the second resin layer, at least the second resin layer can sufficiently reflect this light, and the occurrence of thermal deformation due to light can be suppressed. The laminated sheet is used as a solar cell backsheet, and the first resin layer side surface is bonded to a filling portion made of an ethylene / vinyl acetate copolymer composition embedding the solar cell element. In the case of a battery module, the reflected light can be used for photoelectric conversion to improve power generation efficiency.

Further, the laminated sheet of the present invention, since comprise a water vapor barrier layer between the first resin layer and second resin layer, excellent in water vapor barrier property of the first resin layer side and the second resin layer side, the laminated sheet When the water vapor transmission rate is measured in accordance with JIS K7129 under conditions of a temperature of 40 ° C. and a humidity of 90% RH, it is preferably 3 g / (m ² · day) or less, more preferably 1 g / (m ² · day) or less. It can be. Because of having the above performance, when the laminated sheet of the present invention is used as a back sheet for a solar cell and a solar cell module is produced, deterioration of the solar cell element due to intrusion of water, water vapor, etc. The decrease can be suppressed, and the durability is excellent.

  The laminated sheet of the present invention is excellent in heat resistance, and the dimensional change rate when the laminated sheet is left at 135 ° C. for 30 minutes is preferably ± 1% or less.

The solar cell module of the present invention includes the above-described laminated sheet of the present invention. A schematic diagram of the solar cell module of the present invention is shown in FIG.
The solar cell module 2 in FIG. 3 includes, from the sunlight receiving surface side (upper side in the drawing), the front surface side transparent protective member 21, the front surface side sealing film (front surface side filler portion) 23, the solar cell element 25, the back surface side The sealing film (back surface side filler part) 27 and the laminated sheet 1 (1 ′) of the present invention may be arranged in this order. In addition, the solar cell module of this invention can also be equipped with various members as needed other than the said component as needed as needed (not shown).

As the said surface side transparent protection member 21, what consists of a material excellent in water vapor | steam barrier property is preferable, and the transparent substrate which consists of glass, resin, etc. is used normally. In addition, although glass is excellent in transparency and weather resistance, since impact resistance is not enough and it is heavy, when it is set as the solar cell mounted on the roof of a house, it is preferable to use a weather resistant transparent resin. Examples of the transparent resin include a fluorine-based resin.
The thickness of the surface side transparent protective member 21 is usually about 1 to 5 mm when glass is used, and is usually about 0.1 to 5 mm when transparent resin is used.

  The solar cell element 25 has a power generation function by receiving sunlight. As such a solar cell element, if it has a function as a photovoltaic power, it will not be specifically limited, A well-known thing can be used. For example, a crystalline silicon solar cell element such as a single crystal silicon type solar cell element or a polycrystalline silicon type solar cell element; an amorphous silicon solar cell element composed of a single bond type or a tandem structure type; gallium arsenide (GaAs) or indium phosphorus ( III-V compound semiconductor solar cell elements such as InP); II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe) and copper indium selenide (CuInSe2). Of these, a crystalline silicon solar cell element is preferable, and a polycrystalline silicon solar cell element is particularly preferable. A thin film polycrystalline silicon solar cell element, a thin film microcrystalline silicon solar cell element, a hybrid element of a thin film crystalline silicon solar cell element and an amorphous silicon solar cell element, or the like can be used.

  Although not shown in FIG. 3, the solar cell element 25 usually includes a wiring electrode and a take-out electrode. The wiring electrode has an action of collecting electrons generated in the plurality of solar cell elements by receiving sunlight, for example, a solar cell element on the surface side sealing film (surface side filler part) 21 side, It connects so that the solar cell element by the side of the back surface side sealing film (back surface side filler material part) 27 side may be connected. The take-out electrode has an action of taking out electrons collected by the wiring electrode or the like as a current.

The front-side sealing film (front-side filler part) 21 and the back-side sealing film (back-side filler part) 27 (hereinafter collectively referred to as “sealing film”) are usually the same as each other. Alternatively, after using a different sealing film forming material to form a sheet-shaped or film-shaped sealing film in advance, the solar cell element 25 or the like is thermocompression bonded between the surface-side transparent protective member 21 and the laminated sheet 1. Formed.
The thickness of each sealing film (filler part) is usually about 100 μm to 4 mm, preferably about 200 μm to 3 mm, more preferably about 300 μm to 2 mm. If the thickness is too thin, the solar cell element 25 may be damaged. On the other hand, if the thickness is too thick, the manufacturing cost increases, which is not preferable.

  The sealing film forming material is usually a resin composition or a rubber composition. Examples of the resin include an olefin resin, an epoxy resin, a polyvinyl butyral resin, and the like. Examples of the rubber include silicone rubber and hydrogenated conjugated diene rubber. Of these, olefin resins and hydrogenated conjugated diene rubbers are preferred.

  Examples of olefin resins include olefins such as ethylene, propylene, butadiene, and isoprene, or polymers obtained by polymerizing diolefins, and ethylene and other monomers such as vinyl acetate and acrylate esters. Copolymers, ionomers and the like can be used. Specific examples include polyethylene, polypropylene, polymethylpentene, ethylene / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / vinyl alcohol copolymer, chlorine. Examples thereof include chlorinated polyethylene and chlorinated polypropylene. Among these, an ethylene / vinyl acetate copolymer and an ethylene / (meth) acrylic acid ester copolymer are preferable, and an ethylene / vinyl acetate copolymer is particularly preferable.

  Examples of hydrogenated conjugated diene rubber include hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer, and the like. It is done. Preferably, a hydrogenated conjugated diene block copolymer having the following structure, that is, a polymer block A containing an aromatic vinyl compound unit; a conjugated diene compound having a 1,2-vinyl bond content exceeding 25 mol% Polymer block B formed by hydrogenating 80 mol% or more of a double bond portion of a polymer containing a unit; Double of a polymer containing a conjugated diene compound unit having a 1,2-vinyl bond content of 25 mol% or less Polymer block C obtained by hydrogenating 80 mol% or more of the bonded portion; and a polymer block C obtained by hydrogenating 80 mol% or more of the double bond portion of the copolymer containing the aromatic vinyl compound unit and the conjugated diene compound unit. It is a block copolymer having at least two selected from the combined block D.

The sealing film-forming material may contain a crosslinking agent, a crosslinking aid, a silane coupling agent, an ultraviolet absorber, a hindered phenol-based or phosphite-based antioxidant, a hindered amine-based light stabilizer, a light as necessary. Additives such as diffusing agents, flame retardants, and anti-discoloring agents can be contained.
As described above, the material forming the front surface side sealing film (front surface side filler part) 23 and the material forming the back surface side sealing film (back surface side filler part) 27 are the same or different. However, the same is preferable from the viewpoint of adhesiveness.

In the solar cell module of the present invention, for example, after arranging the surface side transparent protective member, the surface side sealing film, the solar cell element, the back surface side sealing film and the laminated sheet of the present invention in this order, these are integrated. Further, it can be manufactured by a lamination method or the like in which heat-pressure bonding is performed while vacuum suction is performed.
The lamination temperature in this lamination method is usually about 100 ° C. to 250 ° C. from the viewpoint of adhesiveness of the laminated sheet of the present invention. The laminating time is usually about 3 to 30 minutes.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Evaluation method Measurement methods for various evaluation items are shown below.
1-1. Rubber content in the first thermoplastic resin composition Calculated from the composition at the time of raw material charging.
1-2. N-phenylmaleimide unit content in 1st thermoplastic resin composition It computed from the composition at the time of raw material preparation.
1-3. Glass transition temperature (Tg)
Measurement was performed according to JIS K 7121 using a differential scanning calorimeter “DSC2910” (model name) manufactured by TA Instruments, using the thermoplastic resin contained in the first thermoplastic resin composition as a measurement sample. In addition, when two or more types of thermoplastic resins were included and a plurality of Tg values were obtained by the DSC curve, the higher Tg was adopted.

1-4. Absorptivity (%) for light having a wavelength of 400 to 700 nm
Using a laminated sheet (50 mm × 50 mm, thickness shown in the table) as a measurement sample, transmittance and reflectance were measured with an ultraviolet-visible near-infrared spectrophotometer “V-670” (model name) manufactured by JASCO Corporation. . That is, light was emitted to the surface of the first resin layer of the measurement sample, and the transmittance and reflectance in the wavelength region from 400 nm to 700 nm were measured every 20 nm, and the average value thereof was calculated. The absorptance was calculated by the following formula using the average value of transmittance and the average value of reflectance.
Absorptivity (%) = 100− {transmittance (%) + reflectance (%)}

1-5. Reflectance (%) for light with a wavelength of 800 to 1,400 nm
Using a laminated sheet (50 mm × 50 mm, thickness shown in the table) as a measurement sample, the reflectance was measured with an ultraviolet-visible near-infrared spectrophotometer “V-670” (model name) manufactured by JASCO Corporation. That is, light was emitted to the surface of the first resin layer of the measurement sample, the reflectance in the wavelength range from 800 nm to 1,400 nm was measured every 20 nm, and the average value of these was calculated.

1-6. L value A test piece (50 mm × 50 mm × 100 μm) obtained by cutting a laminated sheet was used as a measurement sample, and the L values of the first resin layer side surface and the second resin layer side surface were respectively manufactured by Toyo Seiki Co., Ltd. It was measured with a spectrophotometer “TCS-II” (model name).

また、処理後の試験片の形状を目視観察し、下記基準で判定した。
○：変形がなかった。
△：ごくわずかに変形していた。
×：変形があった。 1-7. Heat resistance A laminated sheet (thickness is described in the table) was cut to prepare a test piece having a size of 120 mm (MD; resin extrusion direction) × 120 mm (TD; direction orthogonal to MD). Next, a square mark of 100 mm (MD) × 100 mm (TD) was drawn at the center of the test piece, and left at 135 ° C. for 30 minutes in a thermostatic bath. Then, it cooled, the length in the said marked line was measured, and the dimensional change rate was computed from the following formula.

Moreover, the shape of the test piece after a process was observed visually, and the following reference | standard determined.
○: There was no deformation.
(Triangle | delta): It deform | transformed very slightly.
X: Deformation occurred.

1-8. A flexible laminated sheet (thickness is listed in the table) was cut to prepare a test piece having a size of 100 mm (MD) × 100 mm (TD). Next, after bending along the symmetry axis in the MD direction, bending was performed along the symmetry axis in the TD direction. The folded test piece was reciprocated twice on each crease at a speed of 5 mm / sec using a manual crimping roll (2,000 g) according to JIS Z0237. Thereafter, the folds were widened to return to the original state, the test piece was visually observed, and judged according to the following criteria. Those in which the folds are not broken are excellent in flexibility.
◯: The crease was not cracked, and the crease did not break even if it was folded or expanded again.
(Triangle | delta): Although the crease | fold is not cracked, when it was folded again and spread, the crease | fold was cracked.
X: The crease was broken.

1-9. Adhesiveness with EVA film As described above, when the laminated sheet is used as a member constituting the solar cell module (solar cell backsheet), the laminated sheet is applied to the surface of the first resin layer and the solar cell module. It is used for adhering a back surface side sealing film formed by embedding a solar cell element included. Since the ethylene / vinyl acetate copolymer composition is widely used as a material for forming the back side sealing film, the adhesion between the surface of the first resin layer in the laminated sheet and the following EVA film was evaluated.
The laminated sheet was cut into a strip shape (length 200 mm, width 15 mm, thickness described in the table), and two evaluation sheets were obtained. An EVA film “Ultra Pearl” (trade name; manufactured by Sanvic Co., Ltd.) having a length of 100 mm, a width of 15 mm and a thickness of 400 μm made of an ethylene / vinyl acetate copolymer is located between the first resin layers in two evaluation samples. And placed in a laminator in a laminated state. Thereafter, the upper and lower portions of the laminator were evacuated and preheated at 150 ° C. for 5 minutes. Next, the upper part was returned to atmospheric pressure and pressed for 15 minutes to obtain a sample for measuring peel strength. In the obtained peel strength measurement sample, the peel strength was measured by peeling the T-shape from the portion where the evaluation sheet was not adhered to the EVA film. Further, the peeled state was visually evaluated.
○: EVA film was broken.
X: Peeled at the interface between the EVA film and the evaluation film.

1-10. Weather resistance A laminated sheet (thickness is described in the table) was cut to prepare a test piece having a size of 500 mm (MD) × 30 mm (TD). Next, the conditions of Steps 1 to 4 shown below were repeated on the surface of the test piece on the first resin layer side to be subjected to an exposure test, and a color tone change value ΔE before exposure and after 100 hours of exposure was calculated. The processing apparatus is a metering weather meter “MV3000” (model name) manufactured by Suga Test Instruments Co., Ltd.
Step 1: Irradiation 0.53 kW / m ² , 63 ° C., 50% RH, 4 hours Step 2: Irradiation + rainfall 0.53 kW / m ² , 63 ° C., 95% RH, 1 minute Step 3: Dark 0 kW / m ² , 30 ° C., 98% RH, 4 hours Step 4: Irradiation + rainfall 0.53 kW / m ² , 63 ° C., 95% RH, 1 minute

ΔE was calculated from Lab (L: brightness, a: redness, b: yellowness) data using a spectrophotometer “V670” (model name) manufactured by JASCO Corporation according to the following equation.
ΔE = √ {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² }
(In the formula, L ₁ , a ₁ and b ₁ are values after exposure, and L ₀ , a ₀ and b ₀ are values before exposure.)
The smaller the value of ΔE, the smaller the change in color and the better the weather resistance. The weather resistance was determined according to the following criteria.
○: ΔE was 10 or less.
X: ΔE exceeded 10

1-11. Flame retardant Laminated sheet (20 mm x 100 mm, thickness is listed in the table) is used as a test piece. This test piece is suspended vertically, and a UL94 V test burner is used to separate the test piece from the burner tip to the lower end of the test piece by 10 mm. In this state, the lower end of the test piece was indirectly flamed for 5 seconds. After the completion of flame contact, the combustion state of the flame contact portion of the test piece was visually observed and judged according to the following criteria.
○: Not ignited.
X: Ignition occurred.

1-12. Thermal storage laminate sheet (80 mm x 80 mm, thickness is listed in the table) as a measurement sample, in a chamber adjusted to a temperature of 25 ° C ± 2 ° C and humidity of 50 ± 5% RH, the first resin layer in the measurement sample The side surface was irradiated with an infrared lamp (output: 100 W) from a height of 200 mm. The surface temperature after 60 minutes of irradiation was measured using a surface thermometer. The unit is ° C.

1-13. Photoelectric conversion efficiency improvement rate In a room adjusted to a temperature of 25 ° C. ± 2 ° C. and a humidity of 50 ± 5% RH, a cell is previously used by using Solar Simulator “PEC-11” (model name) manufactured by Pexel Technologies. 3mm thick glass is placed on the surface of a 1/4 polycrystalline silicon cell where the photoelectric conversion efficiency of a single unit is measured, a laminated sheet is placed on the back side, the silicon cell is sandwiched, and EVA is placed between the glass and the laminated sheet. The silicon cell was sealed by introducing and a solar cell module was produced. Then, in order to reduce the influence of temperature, the photoelectric conversion efficiency was measured immediately after the light irradiation. The photoelectric conversion efficiency improvement rate was calculated | required using the obtained photoelectric conversion efficiency and the photoelectric conversion efficiency of the cell single-piece | unit.
Photoelectric conversion efficiency improvement rate (%) = {(photoelectric conversion efficiency of module−photoelectric conversion efficiency of single cell) ÷ (photoelectric conversion efficiency of single cell)} × 100

1-14. Water vapor barrier property Water vapor permeability is measured according to JIS K7129B using MOPER's water vapor permeability measuring device “PERMATRAN W3 / 31” (model name) under conditions of a temperature of 40 ° C. and a humidity of 90% RH. did. In addition, the surface on the second resin layer side was disposed on the water vapor side as the transmission surface.

2. 2. Raw material for producing laminated sheet 2-1. Silicone / acrylic composite rubber reinforced styrene resin (rubber reinforced resin (A1))
“Metablene SX-006” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used. This is a resin obtained by grafting an acrylonitrile / styrene copolymer onto a silicone / acrylic composite rubber. The content of the silicone / acrylic composite rubber is 50%, the grafting rate is 80%, the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C) 0.38 dl / g, glass transition temperature (Tg) 135 ° C).

2-2. Silicone rubber reinforced styrene resin (rubber reinforced resin (A2))
1.3 parts of p-vinylphenylmethyldimethoxysilane and 98.7 parts of octamethylcyclotetrasiloxane are mixed, and this is put into 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid is dissolved, and 3 parts by a homogenizer. The mixture was stirred and dispersed for emulsification. This emulsified dispersion was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and heated at 90 ° C. for 6 hours while stirring. Subsequently, it was kept at 5 ° C. for 24 hours to complete the condensation, and a latex containing a polyorganosiloxane rubber was obtained. The condensation rate was 93%. Thereafter, the latex was neutralized to pH 7 using an aqueous sodium carbonate solution. The obtained polyorganosiloxane rubber had a volume average particle size of 300 nm.
Next, in a 7-liter glass flask equipped with a stirrer, 100 parts of ion exchange water, 1.5 parts of potassium oleate, 0.01 parts of potassium hydroxide, 0.1 part of tert-dodecyl mercaptan, A batch polymerization component consisting of a latex adjusted to pH 7 containing 40 parts of an organosiloxane rubber, 15 parts of styrene and 5 parts of acrylonitrile was added, and the temperature was raised while stirring. When the temperature reaches 45 ° C., the activity comprises 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and 15 parts of ion-exchanged water. Aqueous agent aqueous solution and 0.1 part of diisopropylbenzene hydroperoxide were added and polymerization was carried out for 1 hour.
Thereafter, 50 parts of ion exchange water, 1 part of potassium oleate, 0.02 part of potassium hydroxide, 0.1 part of tert-dodecyl mercaptan, 0.2 part of diisopropylbenzene hydroperoxide, 30 parts of styrene and An incremental polymerization component consisting of 10 parts of acrylonitrile was added continuously over 3 hours to continue the polymerization. After completion of the addition, stirring was further continued. One hour later, 0.2 part of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was added to terminate the polymerization, and a latex containing a silicone rubber reinforced styrene resin (rubber reinforced resin A2) was added. Obtained. Next, 1.5 parts of sulfuric acid is added to the latex to coagulate the resin component at 90 ° C., and then the resin component is washed with water, dehydrated and dried to obtain a silicone rubber reinforced styrene resin (rubber reinforced resin A2). Got. The glass transition temperature (Tg) was 108 ° C., the polyorganosiloxane rubber content was 40%, the graft ratio was 84%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) was 0.60 dl / g.

2-3. Acrylic rubber reinforced aromatic vinyl resin (rubber reinforced resin (A3))
The reactor contains an acrylic rubbery polymer (volume average particle size: 100 nm, gel content: 90%) obtained by emulsion polymerization of 99 parts of n-butyl acrylate and 1 part of allyl methacrylate. 50 parts of latex having a solid content concentration of 40% (in terms of solid content) was added, and further diluted with 1 part of sodium dodecylbenzenesulfonate and 150 parts of ion-exchanged water. Thereafter, the inside of the reactor was replaced with nitrogen gas, and 0.02 part of disodium ethylenediaminetetraacetate, 0.005 part of ferrous sulfate and 0.3 part of sodium formaldehydesulfoxylate were added, and the mixture was stirred up to 60 ° C. The temperature rose.
On the other hand, 50 parts of a mixture of 37.5 parts of styrene and 12.5 parts of acrylonitrile, 1.0 part of terpinolene and 0.2 part of cumene hydroperoxide are placed in a container, and the inside of the container is replaced with nitrogen gas. A mass composition was obtained.
Next, the monomer composition was added to the reactor at a constant flow rate over 5 hours, and polymerization was performed at 70 ° C. to obtain a latex. Magnesium sulfate was added to this latex to coagulate the resin component. Then, acrylic rubber reinforced aromatic vinyl resin (rubber reinforced resin A3) was obtained by washing with water and drying. The acrylic rubbery polymer content was 50%, the graft ratio was 93%, the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) was 0.30 dl / g, and the glass transition temperature (Tg) was 108 ° C.

2-4. Acrylonitrile / styrene copolymer AS resin “SAN-H” (trade name) manufactured by Technopolymer Co., Ltd. was used. The glass transition temperature (Tg) is 108 ° C.

2-5. Acrylonitrile / styrene / N-phenylmaleimide copolymer Acrylonitrile / styrene / N-phenylmaleimide copolymer “Polyimilex PAS1460” (trade name) manufactured by Nippon Shokubai Co., Ltd. was used. The amount of N-phenylmaleimide units is 40%, the amount of acrylonitrile units is 9%, the amount of styrene units is 51%, and the Mw in terms of polystyrene by GPC is 120,000. The glass transition temperature (Tg) is 173 ° C.

2-6. Styrene / N-phenylmaleimide copolymer A styrene / N-phenylmaleimide copolymer “Denki IP” (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. was used. The N-phenylmaleimide unit amount is 55%, and the styrene unit amount is 45%. The glass transition temperature (Tg) is 209 ° C.

2-7. Infrared transmitting colorant A perylene-based black pigment “Lumogen BLACK FK4280” (trade name) manufactured by BASF was used.

2-8. Yellow colorant A quinophthalone yellow pigment “Pariotol Yellow K0961HD” (trade name) manufactured by BASF was used.

2-9. Carbon black “Carbon black # 45” (trade name) manufactured by Mitsubishi Chemical Corporation was used.

2-10. Second resin layer film (II-1)
A white highly concealed PET film “Lumirror E20” (trade name) manufactured by Toray Industries, Inc. was used. The thickness is 50 μm. The glass transition temperature (Tg) is 70 ° C.
2-11. Second resin layer film (II-2)
A white highly concealed PET film “Lumirror E20” (trade name) manufactured by Toray Industries, Inc. was used. The thickness is 100 μm. The glass transition temperature (Tg) is 70 ° C.
2-12. Second resin layer film (II-3)
A transparent PET film “Lumirror S10” (trade name) manufactured by Toray Industries, Inc. was used. The thickness is 100 μm. The glass transition temperature (Tg) is 70 ° C.

2-13. Water vapor barrier layer forming film (R-1)
A transparent vapor deposition film “Tech Barrier AX” (trade name) manufactured by Mitsubishi Plastics, Inc. was used. It is a transparent film having a silica vapor deposition film on one side of a PET film, and has a thickness of 12 μm and a water vapor transmission rate (JIS K7129) of 0.15 g / (m ² · day).
2-14. Water vapor barrier layer forming film (R-2)
An inorganic binary vapor barrier film “Ecosia VE500” (trade name) manufactured by Toyobo Co., Ltd. was used. This is a transparent film obtained by vapor-depositing (silica / alumina) on one side of a PET film, and has a thickness of 12 μm and a water vapor permeability of 0.5 g / (m ² · day).

3. Preparation of first thermoplastic resin composition Production Example 1
Henschel is a rubber-reinforced resin (A1), an acrylonitrile / styrene copolymer, an acrylonitrile / styrene / N-phenylmaleimide copolymer, an infrared transmitting colorant, and a yellow colorant in the proportions shown in Table 1. Mix with a mixer. Then, it melt-kneaded at the barrel temperature of 270 degreeC using the Nippon Steel Works twin screw extruder "TEX44" (model name), and obtained the pellet-shaped 1st thermoplastic resin composition (I-1) (Table | Table) 1).

Production Examples 2-8
Except having used each raw material shown in Table 1 in the ratio shown in Table 1, it carried out similarly to manufacture example 1, and obtained pellet-shaped 1st thermoplastic resin composition (I-2)-(I-8). (See Table 1).

Production Example 9
The pellet-like thermoplastic resin for the first resin layer, except that polyethylene terephthalate “Novapex GM700Z” (trade name) manufactured by Mitsubishi Chemical Corporation and the colorant were used in the proportions shown in Table 1, were used. A resin composition (I-9) was obtained (see Table 1).

4). Manufacture and evaluation of laminated sheets (1)
Reference example 1
The first thermoplastic resin composition (I-1) for forming the first resin layer is melt-kneaded at 270 ° C., and a T die having a die width of 1,400 mm and a lip interval of 0.4 mm and an extruder having a screw of 65 mm are provided. Using a film forming machine provided, a thin-walled body was obtained, and the surface was brought into close contact with a cast roll whose surface temperature was controlled at 95 ° C. with an air knife to cool and solidify to obtain a black film having a thickness of 15 μm. Thickness gauge "ID-C1112C" (model name) manufactured by Mitutoyo Co., Ltd. was used to cut the film after 1 hour from the start of film production. Then, the thickness was measured at intervals of 10 mm (n = 107), and the average value was obtained. Measurement point values in the range of 20 mm from the edge of the film were removed from the average calculation.
Next, the film (II-1) for 2nd resin layers of Table 2 was adhere | attached on the surface of the said black film using the polyurethane-type adhesive agent, and the lamination sheet was obtained. And about this laminated sheet, various evaluation was performed and the result was written together in Table 2.

Reference Examples 2-6 and Comparative Examples 1-6
A laminated sheet was obtained in the same manner as in Reference Example 1 using the first thermoplastic resin composition shown in Tables 2 to 5. And about this laminated sheet, various evaluation was performed and the result was written together in Table 2-Table 5. FIG.

5. Manufacture and evaluation of laminated sheets (2)
Example 1
The first thermoplastic resin composition (I-1) for forming the first resin layer is melt-kneaded at 270 ° C., and a T die having a die width of 1,400 mm and a lip interval of 0.4 mm and an extruder having a screw of 65 mm are provided. Using a film forming machine, a thin-walled body was made, and with an air knife, the film was brought into close contact with a cast roll whose surface temperature was controlled to 95 ° C. and cooled and solidified to obtain a black film having a thickness of 50 μm.
Next, the water vapor barrier layer-forming film (R-1) was adhered to the surface of the black film using a polyurethane-based adhesive so that the deposited film became the outer surface. Furthermore, the film (II-1) for 2nd resin layers was adhere | attached on the surface of the vapor deposition film in a water vapor | steam barrier layer using the polyurethane-type adhesive agent, and the laminated sheet was obtained. And about this laminated sheet, various evaluation was performed and the result was written together in Table 6.

Example 2
After obtaining a black film in the same manner as in Example 1 using the first thermoplastic resin composition (I-1) for forming the first resin layer, this black film, the second resin layer film (II -2) and a water vapor barrier layer forming film (R-2) were used in the same manner as in Example 1 to obtain a laminated sheet. And about this laminated sheet, various evaluation was performed and the result was written together in Table 6.

In the laminated sheet comprising the first resin layer and the second resin layer, which is one embodiment of the present invention, when light is radiated to the first resin layer, infrared rays are easily transmitted, and thus low heat storage in the first resin layer It is excellent in the property, and it is excellent in the reflectivity in the 2nd resin layer of the light which permeate | transmitted the 1st resin layer. In a high-temperature environment, thermal deformation due to light reception or the like is suppressed, and heat resistance is excellent, and designability and weather resistance can be maintained over a long period of time. Moreover, it is excellent in the adhesiveness between the surface of the first resin layer and a member containing an ethylene / vinyl acetate copolymer, and the processability and the handleability thereof are good. Therefore, as an article having a support part on the second resin layer side, a member containing an ethylene / vinyl acetate copolymer joined to the first resin layer side surface, for example, for a long time in sunlight or wind and rain It is suitable for applications that are exposed and require shape stability over a long period of time. Especially, it is useful as a structural member of the solar cell module which comprises the solar cell arrange | positioned on roofs, such as a house and a building, ie, a solar cell backsheet. Since this laminated sheet is excellent in flexibility, it is not dependent on the shape of the solar cell module, that is, arranged according to the surface shape of the filler portion filling the gaps of the solar cell elements included in the solar cell module. This is suitable for protecting solar cell elements.
In addition, in a laminated sheet sequentially including the first resin layer, the water vapor barrier layer, and the second resin layer, which is another aspect of the present invention, infrared light is easily transmitted when light is emitted to the first resin layer. Thus, the low heat storage property in the first resin layer is excellent, and the light transmitted through the first resin layer and the water vapor barrier layer is excellent in reflectivity in the second resin layer. In a high-temperature environment, thermal deformation due to light reception or the like is suppressed, and heat resistance is excellent, and designability and weather resistance can be maintained over a long period of time. Moreover, it is excellent in adhesiveness between the surface of the first resin layer and the member containing the ethylene / vinyl acetate copolymer, and the water vapor barrier is present on both the surface on the first resin layer side and the surface on the second resin layer side. Excellent in workability and workability and handleability. Therefore, as an article having a support part on the second resin layer side, a member containing an ethylene / vinyl acetate copolymer joined to the first resin layer side surface, for example, for a long time in sunlight or wind and rain It is suitable for applications that are exposed and require shape stability over a long period of time. Especially, it is useful as a structural member of the solar cell module which comprises the solar cell arrange | positioned on roofs, such as a house and a building, ie, a solar cell backsheet. Since this laminated sheet is excellent in flexibility, it is not dependent on the shape of the solar cell module, that is, arranged according to the surface shape of the filler portion filling the gaps of the solar cell elements included in the solar cell module. This is suitable for protecting solar cell elements.

1 and 1 ′: laminated sheet 11: first resin layer 12: second resin layer 13: water vapor barrier layer 2: solar cell module 21: surface side transparent protective member 23: surface side sealing film 25: solar cell element 27: Back side sealing film

Claims (7)

A laminated sheet comprising a first resin layer, a water vapor barrier layer, and a second resin layer in sequence ,
The first resin layer includes an aromatic vinyl resin and a first thermoplastic resin having a maximum glass transition temperature of 140 ° C. to 220 ° C. measured with a differential scanning calorimeter, an infrared transmitting colorant, An infrared transparent colored resin layer having a thickness of 10 to 100 μm, comprising a first thermoplastic resin composition containing
A rubber-reinforced aromatic vinyl resin obtained by polymerizing a monomer containing an aromatic vinyl compound in the presence of a rubbery polymer, and an aromatic vinyl compound and a maleimide compound. A vinyl monomer copolymer containing
The second resin layer is made of a second thermoplastic resin composition containing a second thermoplastic resin and white colorants, Ri white resin layer der having a thickness of 10 to 500 [mu] m,
The second thermoplastic resin is a saturated polyester resin;
Laminated sheet the water vapor barrier layer, on the surface of the polyester film, consisting of the deposition film formed by forming the film containing metal and / or metal oxide, the thickness is characterized by layers der Rukoto of 10~200μm .   The laminated sheet according to claim 1, wherein when light having a wavelength of 400 to 700 nm is emitted to the surface of the first resin layer in the laminated sheet, the light absorptance is 60% or more.   The laminated sheet according to claim 1 or 2, wherein when light having a wavelength of 800 to 1,400 nm is radiated to the surface of the first resin layer in the laminated sheet, the reflectance with respect to the light is 50% or more.   The laminated sheet according to any one of claims 1 to 3, which has a dimensional change rate of ± 1% or less when left at 135 ° C for 30 minutes. The first thermoplastic resin includes a structural unit (s1) derived from an aromatic vinyl compound and a structural unit (s2) derived from a maleimide compound, and the content of the structural unit (s2) is It is 10-50 mass% with respect to 100 mass% of whole quantity of the structural unit which comprises 1 thermoplastic resin, The laminated sheet as described in any one of Claims 1-4 . Laminated sheet according to any one of claims 1 to 5 the thickness of the laminated sheet is 30～600Myuemu. A solar cell module comprising the laminated sheet according to any one of claims 1 to 6 .

Images