WO2014021003A1

WO2014021003A1 - Laminate sheet and method for manufacturing same

Info

Publication number: WO2014021003A1
Application number: PCT/JP2013/066551
Authority: WO
Inventors: 堀江将人; 巽規行; 塩見篤史; 高橋弘造
Original assignee: 東レ株式会社
Priority date: 2012-07-30
Filing date: 2013-06-17
Publication date: 2014-02-06
Also published as: TW201404591A; JPWO2014021003A1

Abstract

Provided is a laminate sheet having a layer (P1 layer) having a polyamide-based resin as a main component thereof, and a layer (P3 layer) having an olefin-based resin as a main component thereof, the P3 layer containing inorganic particles, the P1 layer being positioned on a surface layer, the P3 layer being positioned on a reverse layer from the P1 layer, and the expressions (1) through (3) all being satisfied, where Ta (µm) is the total thickness of the laminate sheet, T1 (µm) is the thickness of the P1 layer, T3 (µm) is the thickness of the P3 layer, and M (mass%) is the content of inorganic particles in the P3 layer. This laminate sheet is capable of superior durability, nonflammability, and water vapor barrier properties relative to a conventional laminate sheet that uses a polyamide-based resin, and is particularly suitable for use as a backing sheet for a solar cell. (1): 0.05 ≤ M/T3 ≤ 0.5; (2): 200 ≤ Ta ≤ 500; (3): 0.3 ≤ T1/Ta ≤ 0.5

Description

Laminated sheet and method for producing the same

The present invention relates to a laminated sheet capable of achieving both durability, flame retardancy, and water vapor barrier properties. In particular, the present invention relates to a laminated sheet that can be suitably used as a back sheet for a solar cell, and a method for producing the laminated sheet.

In recent years, photovoltaic power generation has attracted attention as a semi-permanent and pollution-free next-generation energy source, and solar cells are rapidly spreading. A solar cell is composed of a power generation element sealed with a transparent sealing material such as ethylene-vinyl acetate copolymer (EVA), and a transparent substrate such as glass and a resin sheet called a back sheet bonded together. The Sunlight is introduced into the solar cell through the transparent substrate. Sunlight introduced into the solar cell is absorbed by the power generation element, and the absorbed light energy is converted into electrical energy. The converted electric energy is taken out by a lead wire connected to the power generation element and used for various electric devices. Here, the structure which provides barrier property and an electrical property by pasting together various raw materials to the biaxially-stretched polyethylene terephthalate (PET) which is a low-cost and high-performance is studied. In addition to the barrier property, the olefin resin is a material generally used as a back sheet because it has good adhesion to the sealing material.

On the other hand, in order to improve the durability and productivity of the back sheet, application of resin materials other than PET has been studied, and a back sheet based on a durable polyamide-based resin has been developed (Patent Document 1). 2).

Special table 2010-528454 gazette Special table 2010-527142 gazette

However, polyamide-based resins generally have a drawback that the water vapor barrier property is lower than that of biaxially stretched PET. Furthermore, there is a problem in that it is easily deteriorated by heat and the color tone is easily changed to yellow. Moreover, in the sheet | seat which laminated | stacked biaxially stretched PET on the polyamide-type resin of patent document 2, although a water vapor | steam barrier property is obtained, in order to obtain high wet heat resistance and interlayer adhesion, a biaxial stretch process is essential. There is a problem with productivity. Therefore, in the present invention, in view of the conventional problems, a laminated sheet that is highly productive, hardly yellowed, and can be suitably used for a solar cell backsheet having durability, interlayer adhesion, and water vapor barrier properties. I will provide a.

In order to solve the above problems, the present invention has the following configuration. That is:

A laminated sheet having a layer (P1 layer) mainly comprising a polyamide-based resin and a layer (P3 layer) mainly comprising an olefin-based resin,
P3 layer contains inorganic particles,
Furthermore, the P1 layer is located on the surface layer, and the P3 layer is located on the surface opposite to the P1 layer,
When the thickness of the entire laminated sheet is Ta (μm), the thickness of the P1 layer is T1 (μm), the thickness of the P3 layer is T3 (μm), and the content of inorganic particles in the P3 layer is M (mass%), A laminated sheet characterized by satisfying all of the following formulas (1) to (3).
0.05 ≦ M / T3 ≦ 0.5 (1)
200 ≦ Ta ≦ 500 (2)
0.3 ≦ T1 / Ta ≦ 0.5 (3)

According to the present invention, there is provided a laminated sheet having excellent durability, interlayer adhesion, water vapor barrier properties, sealant adhesion, flame retardancy, and yellowing that can be suitably used for a solar cell backsheet. Can do. Such a laminated sheet can be suitably used for a solar cell backsheet, and a high-performance solar cell can be provided by using the backsheet.

It is sectional drawing which shows typically an example of a structure of the solar cell using the lamination sheet of this invention.

The laminated sheet of the present invention has a layer (P1 layer) mainly composed of a polyamide-based resin and a layer (P3 layer) mainly composed of a polyolefin-based resin.

The polyamide resin which is the main constituent of the P1 layer in the present invention is 1) ring-opening polymerization of a compound having a lactam skeleton, and 2) polycondensation of an amino acid compound having an amino group and a carboxyl group in one molecule. And 3) those obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, and those obtained by copolymerizing 1) to 3). And as for the polyamide-type resin which is a main structural component of P1 layer, these can be used individually or can be mixed and used.

Examples of the compound having a lactam skeleton used in 1) include ε-caprolactam (nylon 6 is obtained by ring-opening polymerization), ω-undecanlactam (nylon 11 is obtained by ring-opening polymerization), ω-laurolactam ( And lactam compounds such as nylon 12 can be obtained by ring-opening polymerization.

Examples of amino acid compounds having an amino group and a carboxyl group in one molecule used in 2) include amino acid compounds such as ε-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

Examples of the diamine compound used in 3) include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 1,2,2,4-tetramethylhexamethylene diamine, 2,4,4-trimethyl. Hexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, Examples include 2,2-bis-p-aminocyclohexylpropane and isophoronediamine. Examples of the dicarboxylic acid compound used in 3) include adipic acid, peric acid, azelaic acid, sepacic acid, dodecanoic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, Examples thereof include dicarboxylic acid compounds such as naphthalenedicarboxylic acid and dimer acid.

About these compounds, 1) a compound having a lactam skeleton, 2) an amino acid compound, alone or in a mixture, or 3) a mixture of diamine and dicarboxylic acid, etc. Either a single polymer or a copolymer can be used in the present invention. That is, for example, if 1) a compound having a lactam skeleton is used, a compound having one or more lactam skeletons is polymerized to obtain a polyamide-based resin (note that two or more compounds are When used, the resulting polyamide resin is a copolymer). Similarly, if 2) an amino acid compound is used, one or more amino acid compounds are polymerized to obtain a polyamide resin. 3) When a diamine compound and a dicarboxylic acid compound are used, one or more diamine compounds and one or more dicarboxylic acid compounds are polymerized to obtain a polyamide resin. Among these, as the polyamide-based resin, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), Polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polyundecanamide (nylon 11), and polydodecanamide (nylon 12) are preferable.

Here, in the laminated sheet of the present invention, the polyamide-based resin that is the main constituent of the P1 layer is nylon 6, nylon 66, nylon 610, nylon 11, and the like in terms of crystallinity, strength, heat resistance, and rigidity. More preferably, it is at least one resin selected from the group consisting of nylon 12.

In addition, about P1 layer, making a polyamide-type resin a main structural component means that the polyamide-type resin is contained more than 50 mass% and 100 mass% or less in 100 mass% of all the components of this layer.

The P1 layer constituting the laminated sheet of the present invention preferably contains inorganic particles in the range of 0.1% by mass to 30% by mass. The content of inorganic particles in the P1 layer is more preferably 2% by mass or more and 25% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. These inorganic particles are used for imparting necessary functions to the sheet depending on the purpose. When the content of the inorganic particles in the P1 layer is more than 30% by mass, handling properties may be lowered or durability may be lowered. When the content of the inorganic particles in the P1 layer is less than 0.1% by mass, the effect due to the inclusion of the inorganic particles is difficult to obtain, and yellowing may occur.

Examples of the inorganic particles suitably used for the P1 layer include inorganic particles having an ultraviolet absorbing ability, particles having a large refractive index difference from the polyamide resin, conductive particles, pigments, and the like. In addition, optical properties such as light reflectivity and whiteness, antistatic properties and the like can be imparted. The particle means a particle having a primary particle diameter of 5 nm or more based on the diameter of a projected equivalent equivalent circle. Unless otherwise specified, in the present invention, the particle size means a primary particle size, and the particle means a primary particle.

More specifically, the inorganic particles suitably used for the P1 layer of the present invention include, for example, gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, praseodymium, chromium, Metals such as nickel, aluminum, tin, zinc, titanium, tantalum, zirconium, antimony, indium, yttrium, lanthanum, zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, oxidation Metal oxides such as lanthanum soot, zirconium oxide, aluminum oxide, silicon oxide, lithium fluoride, magnesium fluoride soot, aluminum fluoride soot, metal fluorides such as cryolite, metal phosphates such as calcium phosphate, carbonates such as calcium carbonate Salt, barium sulfate And sulfates such as talc, talc and kaolin.

In the present invention, in view of the fact that it is often used outdoors, as the inorganic particles in the P1 layer, metal oxides such as titanium oxide, zinc oxide, and cerium oxide, which are inorganic particles having ultraviolet absorbing ability, are used. preferable. When inorganic particles having ultraviolet absorbing ability are used, it is preferable in that the effect of reducing coloring due to deterioration of the sheet over a long period of time can be exhibited by utilizing the ultraviolet resistance by the inorganic particles. Furthermore, it is more preferable to use titanium oxide as the inorganic particles in the P1 layer in that high reflection characteristics can be imparted, and it is more preferable to use rutile type titanium oxide in terms of higher ultraviolet resistance. That is, in the present invention, the P1 layer particularly preferably contains titanium oxide, and particularly preferably contains rutile-type titanium oxide.

The method in which the polyamide-based resin and the inorganic particles are contained in the P1 layer is preferably a method in which the polyamide-based resin and the inorganic particles are previously melt-kneaded using a vent type biaxial kneading extruder or a tandem type extruder. Here, since the thermal history is received when the inorganic particles are contained, the polyamide-based resin may be deteriorated. Therefore, a high-concentration master pellet having a large amount of inorganic particles compared to the amount of inorganic particles to be contained in the P1 layer is prepared, mixed with a polyamide-based resin and diluted to obtain a predetermined P1 layer of inorganic particles. The content is preferably from the viewpoint of durability.

In addition, the P1 layer and the P3 layer of the laminated sheet of the present invention may have other additives (for example, a heat stabilizer, an ultraviolet absorber, a weather stabilizer, an organic lubricant, as long as the effects of the present invention are not impaired). Pigments, dyes, fillers, antistatic agents, nucleating agents, etc. However, the inorganic particles referred to in the present invention may not be included in the additives herein. For example, when an ultraviolet absorber is selected as an additive and contained in the P1 layer and / or the P3 layer, the ultraviolet resistance of the laminated sheet of the present invention can be further improved. Further, when an antistatic agent or the like is contained in the P1 layer and / or the P3 layer, an improvement in withstand voltage can be expected.

Further, it is important that the P1 layer in the present invention is located on the surface layer of the laminated sheet from the viewpoint of flame retardancy. Here, the phrase “P1 layer is located on the surface layer” means that the P1 layer is located on one outermost layer of the laminated sheet of the present invention.

In the present invention, it is preferable to provide a P2 layer between the P1 layer and a P3 layer described later. Here, the P2 layer is a layer mainly composed of one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer. In addition, regarding the P2 layer, the main constituent component is one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer. It means that one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene vinyl acetate copolymer exceeds 50% by mass and is equal to or less than 100% by mass.

The P2 layer is preferably between the P1 layer and the P3 layer. That the P2 layer is between the P1 layer and the P3 layer means that the P1 layer that is the surface layer of the laminated sheet of the present invention and the P3 layer that is the reverse surface layer, that is, the P2 layer is in the inner layer. . That is, as long as the P2 layer is between the P1 layer and the P3 layer, the P2 layer may be in contact with the P1 layer or the P3 layer, or may be disposed so as not to contact these. For example, the P2 layer may be in contact with the P1 layer / P2 layer / P3 layer, the P1 layer and the P3 layer, or may be in contact with other layers such as the P1 layer / P2 layer / P5 layer / P2 layer / P3 layer. It doesn't matter.

The P2 layer preferably has a function of adhering to both the P1 layer and the P3 layer. Examples of the low crystalline soft polymer that is one of the main components of the P2 layer include acid-modified polyolefins and unsaturated polyolefins. The acrylic adhesive, which is one of the main constituents of the P2 layer, refers to those using acrylic ester and methacrylic ester as raw materials, and the acrylic adhesive is ethylene-acrylic ester-maleic anhydride. An acid terpolymer can be used. Among these, from the viewpoint of adhering to both the P1 layer and the P3 layer, the P2 layer is preferably made of acid-modified polyolefin as a main constituent. Examples of the acid-modified polyolefin include “Admer” manufactured by Mitsui Chemicals, Inc. and “Modic” manufactured by Mitsubishi Chemical Corporation as commercially available products.

The acid-modified polyolefin is a copolymer of an acid compound and a polyolefin (excluding those in which acrylic acid ester and methacrylic acid ester are used as raw materials). The acid compound is not particularly limited as long as it does not significantly depart from the object of the present invention, but is preferably a saturated or unsaturated carboxylic acid and carboxylic anhydride having at least one carboxyl group. More preferred are carboxylic acids and carboxylic anhydrides having two or more carboxyl groups. Specifically, for example, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, aconitic acid, crotonic acid, succinic acid, oxalic acid, malonic acid, malic acid, thiomarinic acid, tartaric acid, adipic acid, citric acid, Examples include carboxylic acids such as pimelic acid, suberic acid, azelaic acid, and sebacic acid, and carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and succinic anhydride. Maleic acid and maleic anhydride are preferable, and maleic anhydride is particularly preferable. Examples of polyolefins include polyethylene, polypropylene, polybutene, polymethylpentene, polycycloolefin, polyhexene, polyoctene, polydecene, and polydodecene. Among these, various propylene polymers are used because they are easy to process and relatively inexpensive. Is preferred. For example, propylene homopolymer (polypropylene homopolymer), copolymer of ethylene and propylene, propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene , And a copolymer with an α-olefin comonomer having 2 or more carbon atoms such as norbornene, or two or more kinds of copolymers of these comonomers can be used. The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 6 carbon atoms. It may be a random copolymer or a block copolymer.

The P2 layer preferably contains a polyolefin-based elastomer. The polyolefin-based elastomer generally refers to one obtained by finely dispersing ethylene-propylene rubber in polypropylene or one obtained by copolymerizing polypropylene with another α-olefin. These polyolefin-based elastomers are preferably contained in a proportion of 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of all components of the P2 layer. By including the polyolefin-based elastomer, it is possible to impart adhesiveness to the P2 layer, and the adhesion between the P1 layer and the P2 layer and the adhesion between the P3 layer and the P2 layer are improved. The content of the polyolefin elastomer in the P2 layer is preferably 10% by mass or more and 20% by mass or less. The polyolefin-based elastomer may be a commercially available product, for example, “Thermolan”, “Zeras” manufactured by Mitsubishi Chemical Corporation, “Excellen”, “Tough Selenium”, “Esplen”, “Hibler” manufactured by Kuraray, Preferred examples include “Septon” and “Notio” manufactured by Mitsui Chemicals.

The P3 layer in the present invention is mainly composed of an olefin resin. Examples of the polyolefin resin in the present invention include polyethylene, polypropylene, polybutene, polymethylpentene, polycycloolefin, polyhexene, polyoctene, polydecene, and polydodecene. Among these, polyethylene and polypropylene are preferable as the olefin resin of the P3 layer because it is easy to process and relatively inexpensive. These olefin-based resins may be mixed and copolymerized with other olefin compounds. For example, when an ethylene-propylene copolymer or an ethylene-propylene-butene copolymer is used, the melting point of the resin can be lowered.

In addition, about P3 layer, making an olefin resin into a main structural component means containing 100 mass% or less of olefin resin exceeding 50 mass% in 100 mass% of all the components of this layer.

The melting point (hereinafter also referred to as melting endothermic peak temperature) of the olefin resin in the P3 layer in the present invention is preferably 120 ° C. or higher and 155 ° C. or lower. If the melting point of the olefin resin in the P3 layer is less than 120 ° C, the heat resistance may be inferior. On the other hand, if the melting point of the olefin resin in the P3 layer is higher than 155 ° C., the adhesiveness with the sealing material may be lowered.

In the present invention, the thickness of the entire laminated sheet is Ta (μm), the thickness of the P1 layer is T1 (μm), the thickness of the P3 layer is T3 (μm), and the content of inorganic particles in the P3 layer is M (mass%). It is important to satisfy all of the expressions (1) to (3).
0.05 ≦ M / T3 ≦ 0.5 (1)
200 ≦ Ta ≦ 500 (2)
0.3 ≦ T1 / Ta ≦ 0.5 (3)
By satisfying the expressions (1) to (3) at the same time, a laminated sheet having durability, interlayer adhesion, water vapor barrier properties, and electrical characteristics can be obtained.

In addition, when the laminated sheet of the present invention has a plurality of P1 layers and P3 layers, T1 is obtained using the P1 layer of the surface layer, T3 and M are obtained using the P3 layer of the reverse surface layer, and this is expressed by the formula It is important to satisfy (1) to (3) simultaneously.

Formula (1) formulates the amount of inorganic particles per thickness, and shows that it is important to increase the amount of inorganic particles as the thickness increases in order to develop the effect of inorganic particles. .

From the conventional knowledge, the present inventors considered that the change in color tone due to thermal deterioration mainly depends on the concentration of inorganic particles.

However, as a result of investigations by the present inventors, it has been found that the change in color tone due to thermal degradation does not simply depend on the concentration of inorganic particles but also on the thickness of the P1 layer. . The reason for this is that the amount of change in color tone (absorption amount of visible light) caused by deterioration is obtained by integration in the thickness direction. Therefore, it is assumed that the greater the thickness, the greater the change in color tone. In order to efficiently suppress the above, the inventors conceived of controlling the amount of inorganic particles according to the thickness.

Therefore, the formula (1) is expressed using the concentration and thickness of the inorganic particles, and in the present invention, it is important that the relationship of the formula (1) is satisfied.

In the formula (1), if M / T3 is smaller than 0.05, the P3 layer tends to yellow due to deterioration, which is a problem. When M / T3 is larger than 0.5, there is a problem that adhesion with EVA is lowered.

It is important that the P3 layer contains inorganic particles, and these inorganic particles are used for imparting necessary functions to the sheet depending on the purpose. As the inorganic particles in the P3 layer, the same inorganic particles as those mentioned above as the inorganic particles in the P1 layer can be used. In the present invention, in view of the fact that they are often used outdoors, the inorganic particles in the P3 layer are preferably metal oxides such as titanium oxide, zinc oxide, and cerium oxide having ultraviolet absorbing ability. When inorganic particles having ultraviolet absorbing ability are used, it is preferable in that the effect of reducing coloring due to deterioration of the sheet over a long period of time can be exhibited by utilizing the ultraviolet resistance by the inorganic particles. Furthermore, it is more preferable to use titanium oxide as inorganic particles in the P3 layer in that high reflection characteristics can be imparted, and it is more preferable to use rutile type titanium oxide in terms of higher ultraviolet resistance. That is, in the present invention, the P3 layer particularly preferably contains titanium oxide, and particularly preferably contains rutile titanium oxide.

Formula (2) represents the thickness range of the entire laminated sheet. When Ta is smaller than 200 μm, durability, flame retardancy, and water vapor barrier are inferior. If Ta is larger than 500 μm, the processability is poor and the conveyance is difficult, so that there are problems such as poor process suitability and heavy weight. Furthermore, when using the laminated sheet of this invention as a solar cell backsheet, there exists a problem that the solar cell module in which weight reduction and space saving are calculated | required becomes too thick.

Formula (3) shows the thickness ratio of the P1 layer with respect to the total thickness, and the durability is greatly affected by the polyamide-based resin. If the value of T1 / Ta is smaller than 0.3, the durability is lowered. There is a problem to do. The greater the T1 / Ta value, the better the durability. However, the polyamide-based resin has a high hygroscopic property, which adversely affects the electrical characteristics. If the T1 / Ta value exceeds 0.5, the electrical characteristics become a problem. .

The thickness T2 (μm) of the P2 layer is preferably 15 to 50 μm. When there are a plurality of P2 layers, the thickness T2 (μm) of each P2 layer is preferably 15 to 50 μm. When T2 is smaller than 15 μm, the adhesion with the P1 layer and the P3 layer is lowered, and delamination is likely to occur. When T2 is larger than 50 μm, the flame retardancy tends to deteriorate. T2 is more preferably 20 μm or more and 40 μm or less. Here, delamination refers to what peels at the interface, such as between the P1 layer and the P2 layer and between the P2 layer and the P3 layer.

The laminated structure of the laminated sheet in the present invention is a structure in which at least the P1 layer is located on the surface layer and the P3 layer is located on the opposite surface layer to the P1 layer. Here, the P3 layer being located on the reverse surface layer of the P1 layer means that the P1 layer is located on one outermost layer of the laminated sheet, and therefore the P3 layer is located on the other outermost layer. From such a viewpoint, the layer configuration (layer order) of the laminated sheet of the present invention is preferably P1 layer / P2 layer / P3 layer. Furthermore, the laminated sheet of the present invention has other layers between the P1 layer and the P3 layer, such as (i) P1 layer / P2 layer / P5 layer / P2 layer / P3 layer, which has a four-layer five-layer configuration. A layer having the above function may be included. Further, the laminated sheet of the present invention has (ii) a plurality of P1 layers and P3 layers through the P2 layer, such as (1) P1 layer / P2 layer / P3 layer / P2 layer / P1 layer / P2 layer / P3 layer. A multi-layered laminated structure is also a preferred embodiment.

Also, the laminated sheet of the present invention can be a laminated body laminated with another film or the like. Also in such a laminated body, it is preferable that the P1 layer has a laminated structure provided on any one of the surface layers. Examples of other films include polyester layers for increasing mechanical strength, antistatic layers, adhesion layers with other materials, UV resistant layers for further improving UV resistance, and flame resistance for imparting flame resistance A layer, a hard coat layer for improving impact resistance and scratch resistance, and the like can be arbitrarily selected and used depending on applications. As a specific example when the laminated sheet of the present invention is a laminated body laminated with another film or the like, when the laminated sheet of the present invention is used as a solar battery backsheet, other sheet materials or power generation elements are embedded. In order to further improve the adhesion to the sealing material (for example, ethylene vinyl acetate), in addition to the easy adhesion layer, UV-resistant layer, flame retardant layer, the voltage at which partial discharge phenomenon, which is an index of insulation, is generated is improved. For example, a conductive layer to be formed may be formed.

Next, an example is given and demonstrated about the manufacturing method of the lamination sheet of the present invention. Examples of the method for laminating the P1, P2, and P3 layers in the laminated sheet of the present invention include, for example, a raw material mainly comprising a polyamide-based resin for the P1 layer, a low crystalline soft polymer for the P2 layer, acrylic Extruders each comprising a raw material mainly comprising one selected from the group consisting of an adhesive based on ethylene and an ethylene vinyl acetate copolymer and a raw material mainly comprising an olefin resin for the P3 layer , P1 layer, P2 layer, P3 layer are joined together in this order after being melted, laminated, and processed into a sheet including the process of extruding into a sheet form from a T die (coextrusion method), produced as a single film A method in which the raw material of the coating layer is put into an extruder and melt extruded and laminated while extruding from the die (melt laminating method), and each film is produced separately and heated. A method of thermocompression bonding (thermal laminating method), a method of bonding via an adhesive (adhesion method), a method of applying and drying a solution dissolved in a solvent (coating method), and a method of combining these Etc. can be used. Of these, the coextrusion method is preferred in that the production process is short and the adhesion between the layers is good. Hereinafter, the manufacturing method by the co-extrusion method will be described in detail (however, the manufacturing method described in detail below is an example).

When the laminated sheet of the present invention is produced by a coextrusion method, first, a raw material mainly comprising a dried polyamide resin for the P1 layer, a low crystalline soft polymer for the P2 layer, an acrylic adhesive, and ethylene A raw material mainly composed of one selected from the group consisting of vinyl acetate copolymers and a raw material mainly composed of an olefin resin for the P3 layer under a nitrogen stream, the P1 layer is 240 ° C. or higher. The P2 layer and the P3 layer at 300 ° C. or lower are respectively supplied to three extruders heated to 180 ° C. or higher and 250 ° C. or lower and melted. Next, using a multi-manifold die, a feed block, a static mixer, a pinol, etc., the P1 layer, the P2 layer and the P3 layer are joined and laminated in this order, and are coextruded from the T die into a sheet. When the difference in melt viscosity of each layer is large, it is preferable to use a multi-manifold die from the viewpoint of suppressing lamination unevenness.

The laminated sheet of the present invention can be obtained by extruding the laminated sheet discharged from the T die by the above-described method onto a cooling body such as a casting drum and cooling and solidifying it.

The laminated sheet of the present invention obtained by the above-described method may be subjected to processing such as heat treatment or aging as necessary within the range where the effects of the present invention are not impaired. By heat-treating, the thermal dimensional stability of the laminated sheet of the present invention can be improved. Moreover, in order to improve the adhesiveness of the laminated sheet of the present invention obtained by the above method, corona treatment or plasma treatment may be performed.

The solar cell backsheet of the present invention is composed of the laminated sheet of the present invention. That is, the laminated sheet of the present invention can be suitably used as a solar battery back sheet. The solar cell of the present invention is characterized by using the solar cell backsheet of the present invention. By using the laminated sheet of the present invention in a solar cell, it becomes possible to increase the durability or reduce the thickness as compared with a conventional solar cell. A structural example of the solar cell of the present invention is shown in FIG. In FIG. 1, a power generating element 3 connected with a lead wire (not shown in FIG. 1) for extracting electricity is sealed with a transparent sealing material 2 such as EVA resin, and a transparent substrate 4 such as glass. And the laminated sheet of this invention is bonded together as the solar cell backsheet 1, but the structural example of the solar cell of this invention is not limited to this, It can use for arbitrary structures. In addition, although the example by the lamination sheet single-piece | unit of this invention was shown in FIG. 1, it is also possible to use the composite sheet of the lamination sheet of this invention and another film according to the other required required characteristic.

Further, the solar cell member of the present invention is a member used for a solar cell and having the laminated sheet of the present invention. Moreover, the above-mentioned solar cell backsheet is also included in the solar cell member of the present invention. Since the laminated sheet of the present invention has characteristics suitable for the solar battery backsheet as described above, the solar cell member using the laminated sheet of the present invention is suitably used for solar cell applications.

In the laminated sheet of the present invention, as a method of laminating with other films, etc., for example, a method of co-extrusion and processing into a sheet (co-extrusion method), a coating layer raw material is put into an extruder into a sheet made of a single film Then, melt extrusion and laminating while extruding from the die (melt laminating method), making each film separately, thermocompression bonding with heated rolls etc. (thermal laminating method), pasting through adhesive A method of bonding (adhesion method), a method of applying and drying a solution dissolved in a solvent (coating method), a method of combining these, and the like can be used.

In the solar cell of the present invention, the above-described solar cell backsheet 1 is installed on the back surface of the sealing material 2 in which the power generating element is sealed. Here, the solar cell backsheet of the present invention has an asymmetric configuration, and the P3 layer is disposed so as to be positioned on the sealing material 2 side, so that the adhesion with the sealing material can be further increased. This is preferable. Moreover, since it becomes the structure arrange | positioned so that P1 layer of the lamination sheet of this invention may be located in the opposite side to the sealing material 2, it becomes possible to improve the tolerance with respect to the ultraviolet rays etc. of the reflection from the ground, and high durability. It can be a solar cell or the thickness can be reduced.

Moreover, the laminated sheet of the present invention can be suitably used as a member of a solar cell comprising a laminated sheet and a sealing material.

Therefore, the solar cell member having the laminated sheet and the sealing material of the present invention is particularly suitably used for solar cell applications. In particular, as described above, the sealing material is preferably located on the surface side of the P3 layer of the laminated sheet.

Furthermore, in the present invention, it is preferable to previously laminate the sealing material with the laminated sheet, and in particular, a method in which the sealing material is simultaneously coextruded and processed into a sheet shape is preferable.

The power generating element 3 converts light energy of sunlight into electric energy, and is based on crystalline silicon, polycrystalline silicon, microcrystalline silicon, amorphous silicon, copper indium selenide, compound semiconductor, dye enhancement Arbitrary elements such as a sensitive system can be used in series or in parallel according to the desired voltage or current depending on the purpose. Since the transparent substrate 4 having translucency is located on the outermost surface layer of the solar cell, a transparent material having high weather resistance, high contamination resistance, and high mechanical strength characteristics in addition to high transmittance is used. In the solar cell of the present invention, the transparent substrate 4 having translucency can be made of any material as long as the above characteristics are satisfied. Examples thereof include glass, ethylene tetrafluoride-ethylene copolymer (ETFE), polyfluoride. Vinyl fluoride resin (PVF), polyvinylidene fluoride resin (PVDF), polytetrafluoroethylene resin (TFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polytrifluoroethylene chloride resin (CTFE) ), Fluorinated resins such as polyvinylidene fluoride resin, olefinic resins, acrylic resins, and mixtures thereof. In the case of glass, it is more preferable to use a tempered glass. Moreover, when using the resin-made translucent base material, what extended | stretched the said resin uniaxially or biaxially from a viewpoint of mechanical strength is used preferably.

In addition, in order to provide these substrates with adhesion to an EVA resin or the like that is a sealing material for power generation elements, it is preferable to subject the surface to corona treatment, plasma treatment, ozone treatment, and easy adhesion treatment. Is called.

The sealing material 2 for sealing the power generating element covers the surface of the power generating element with resin and fixes it, protects the power generating element from the external environment, and has a light-transmitting base material for the purpose of electrical insulation. In addition, a material having high transparency, high weather resistance, high adhesion, and high heat resistance is used to adhere to the backsheet and the power generation element. Examples thereof include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methacrylic acid copolymer (EMAA), Ionomer resins, polyvinyl butyral resins, and mixtures thereof are preferably used.

As described above, by incorporating the solar battery back sheet using the laminated sheet of the present invention into the solar battery, it becomes possible to obtain a highly durable and / or thin solar battery compared to the conventional solar battery. . The solar cell of the present invention can be suitably used for various applications without being limited to outdoor use and indoor use such as a solar power generation system and a power source for small electronic components.

[Characteristic evaluation method]
(1) Layer thickness T1, T2, T3, Ta, lamination ratio T1 / Ta
The layer thicknesses T1, T2, T3, Ta and the lamination ratio T1 / Ta of the laminated sheet were determined by the following procedures (A1) to (A4). The measurement was performed at 10 different locations, and the average values were P1 layer thickness T1 (μm), P2 layer thickness T2 (μm), P3 layer thickness T3 (μm), and overall sheet thickness Ta ( μm), the stacking ratio T1 / T3 was further determined using T1 and T3 obtained here.

(A1) Using a microtome, the laminate sheet is cut perpendicularly to the laminate sheet surface direction without crushing the laminate sheet section in the thickness direction.

(A2) Next, the cut section is observed using an electron microscope, and an image magnified 500 times is obtained. Although the observation location is determined at random, the vertical direction of the image is parallel to the thickness direction of the laminated sheet, and the horizontal direction of the image is parallel to the surface direction of the laminated sheet. When the entire thickness direction does not fit in one image, observation is performed by shifting the observation position in the thickness direction, and an image that can confirm the entire thickness is prepared by combining a plurality of images.

(A3) The thickness T1 of the P1 layer, the thickness T2 of the P2 layer, the thickness T3 of the P3 layer, and the thickness Ta of the entire sheet were determined in the image obtained in (A2).

(A4) T1 was divided by Ta to obtain a stacking ratio T1 / Ta.

(2) Content of inorganic particles (% by mass)
Each of the P1 layer and the P3 layer was scraped or peeled off from the laminated sheet to separate the P1 layer and the P3 layer, and the content of inorganic particles was calculated by the following method.

The mass wa (g) of the shaved material was measured, and then the P1 layer was dissolved in formic acid and the P3 layer was dissolved in ortho-dichlorobenzene (100 ° C.), and inorganic particles were separated from the insoluble materials by centrifugation. The obtained inorganic particles were washed with formic acid and ortho-dichlorobenzene and centrifuged. The washing operation was repeated until no white turbidity occurred even when ethanol was added to the washing solution after centrifugation. Mass wa ′ (g) of the obtained inorganic particles was obtained, and the content of the inorganic particles was calculated from the following formula (4).
Content (mass%) of inorganic particles Wa1 = (wa ′ / wa) × 100 (4).

(3) Adhesiveness with sealing material Based on JIS K 6854 (1994 edition), the adhesiveness of the sealing material was evaluated from the peel strength between the EVA sheet (sealing material) and the P3 layer. The measurement test piece is an example in which a 500 μm-thick EVA sheet manufactured by Sanvic Co., Ltd. on a semi-tempered glass with a thickness of 3 mm, and a corona treatment (20 W · min / m ² ) on the surface of the P3 layer or comparison The laminated sheet of the example was stacked so that the EVA sheet and the P3 layer were in contact with each other, and after being evacuated using a commercially available glass laminator, pressed at 135 ° C. under a heating condition of 29.4 N / cm ² for 15 minutes. Using. The width of the test piece for the peel strength test was 10 mm, two test pieces were prepared, and each test piece was measured at three locations with different locations, and the average value of the obtained measured values was taken as the peel strength value.

That is, two measurement specimens having a sufficient size (for example, a width of 100 mm or more and a length of 100 mm or more) were prepared. Then, three test pieces each having a width of 10 mm (length is 100 mm or more) were cut out from each measurement test piece. The peel strength of the six cut specimens was measured, and the average value of the measured values obtained was taken as the peel strength of the sheet.

From the obtained peel strength, the adhesiveness of the sealing material was determined as follows.
When peel strength is 50 N / 10 mm or more: S
When the peel strength is 40 N / 10 mm or more and less than 50 N / 10 mm: A
When peel strength is 30N / 10mm or more and less than 40N / 10mm: B
When the peel strength is 20 N / 10 mm or more and less than 30 N / 10 mm: C
When peel strength is less than 20 N / 10 mm: D
S to C pass, and S is the best among them.

(4) Interlayer adhesion The adhesion was evaluated from the delamination strength of the laminated sheet. Here, as the delamination strength, the strength at the time of peeling in the T shape measured according to JIS K6854-3 (1999 edition) was used. Here, the interlayer was defined as an interlayer capable of interfacial separation such as between the P1 layer and the P2 layer and between the P2 layer and the P3 layer. The test piece width of the delamination strength test was 15 mm, and two test pieces were prepared. The test piece was changed in place and measured at three locations, and the average value of the obtained measurement values was taken as the delamination strength. The interlayer adhesion was determined as follows.
When peel strength is 10N / 15mm or more: S
When the peel strength is 6 N / 15 mm or more and less than 10 N / 15 mm: A
When peel strength is 3N / 15mm or more and less than 6N / 15mm: B
When peel strength is 1N / 15mm or more and less than 3N / 15mm: C
When peel strength is less than 1 N / 15 mm: D
S to C pass, and S is the best among them.

(5) Flame retardance Based on the UL94HB test, the laminated sheet was cut into a size of 13 mm × 125 mm, the first marked line at 25.4 mm from the cut end in the longitudinal direction, and the second marked at 101.6 mm. Draw a marked line, hold it horizontally, and at the burning rate from the first marked line to the second marked line, N = 3 for the width direction and the longitudinal direction of the laminated sheet, and the average value It was. The obtained burning rate was determined as follows.
When the burning rate is less than 100 mm / min: S
When the burning rate is 100 mm / min or more and less than 110 mm / min: A
When the burning rate is 110 mm / min or more and less than 130 mm / min: B
When the burning rate is 130 mm / min or more and less than 150 mm / min: C
When the burning rate is 150 mm / min or more: D
As for flame retardancy, S to C pass, and S is the best among them.

(6) Gas barrier property Using PERMATRAN W-TWIN manufactured by MOCON, according to “Test method for water vapor permeability of plastic films and sheets (instrument measurement method) JIS-K7129B method (1992 version)” established on August 1, 1992 The measurement was performed at 40 ° C. and 90% RH. From the obtained water vapor transmission rate, the gas barrier properties of the laminated sheet were determined as follows.
When the water vapor transmission rate is less than ² g / m ² · day: S
When the water vapor transmission rate is 2 g / m ² · day or more and less than 3 g / m ² · day: A
When the water vapor transmission rate is 3 g / m ² · day or more and less than 5 g / m ² · day: B
When the water vapor transmission rate is 5 g / m ² · day or more and less than 10 g / m ² · day: C
When the water vapor transmission rate is 10 g / m ² · day or more: D
S to C pass, and S is the best among them.

(7) Partial discharge voltage The partial discharge voltage of the laminated sheet was determined using a partial discharge tester KPD2050 (manufactured by Kikusui Electronics Co., Ltd.). The test conditions are as follows.
The output voltage application pattern on the output sheet is a pattern in which the first stage simply increases the voltage from 0 V to a predetermined test voltage, the second stage is a pattern that maintains a predetermined test voltage, and the third stage is a predetermined test A pattern composed of three stages of patterns in which the voltage is simply dropped from 0 to 0 V is selected.
・ The frequency is 50 Hz. The test voltage is 1 kV.
The first stage time T1 is 10 sec, the second stage time T2 is 2 sec, and the third stage time T3 is 10 sec.
• The counting method on the pulse count sheet is “+” (plus), and the detection level is 50%.
-The charge amount in the range sheet is set to 1,000 pc.
・ In the protection sheet, enter 2 kV after checking the voltage check box. The pulse count is 100,000.
In the measurement mode, the start voltage is 1.0 pc and the extinction voltage is 1.0 pc.

In addition, the measurement was carried out at 10 arbitrary positions in the laminated sheet surface, and the average value was defined as the partial discharge voltage V0. Further, the measurement was performed using a measurement sample that was left overnight (12 hours) in a room at 23 ° C. and 65% Rh.
When partial discharge voltage is 1,050 V or more: S
When the partial discharge voltage is 950 V or more and less than 1,050 V: A
When partial discharge voltage is 700V or more and less than 950V: B
When the partial discharge voltage is 300V or more and less than 700V: C
When partial discharge voltage is less than 300V: D
S to C pass, and S is the best among them.

(8) Measurement of elongation at break Based on ASTM-D882 (1997), a sample was cut into a size of 1 cm × 20 cm, and the elongation at break was measured when the sample was pulled at 5 cm between chucks and at a pulling speed of 300 mm / min. In addition, about each of the longitudinal direction and the width direction of a lamination sheet, after measuring the number of samples by n = 5, those average values were made into elongation at break.

(9) Heat-resistant yellowing After the laminated sheet was cut into a measurement piece (sample) shape (3 cm × 3 cm), it was treated at 120 ° C. for 72 hours in a hot air oven PV (H) -212 manufactured by ESPEC CORP. . With respect to the samples before and after the treatment, the spectroscopic color difference meter SE-2000 type (manufactured by Nippon Denshoku Industries Co., Ltd.) was used with the number of samples n = 5, and in the reflection mode according to JIS Z-8722 (2000). The b value before and after the treatment was determined by measuring the b value with a sample measurement diameter of 30 mmφ and calculating the average value. Δb was obtained by subtracting the b value before the processing from the b value after the processing, and the following determination was performed.
When the color change Δb is less than 3: S
When the color change Δb is 3 or more and less than 5: A
When the color change Δb is 5 or more and less than 8: B
When color change Δb is 8 or more and 10 or less: C
When the color change Δb exceeds 10: D
S to C pass, and S is the best among them.

(10) Weather resistance (color tone change Δb after UV irradiation)
The laminated sheet was measured with an I-super ultraviolet tester S-W131 manufactured by Iwasaki Electric Co., Ltd. at a temperature of 60 ° C., a relative humidity of 50%, an intensity of 100 mW / cm ² (light source: metal halide lamp, wavelength range: 295 to 450 nm, peak wavelength: 365 nm). ) For 48 hours from the P1 side. For samples before and after irradiation, the number of samples is n = 5 and a spectroscopic color difference meter SE-2000 type (manufactured by Nippon Denshoku Industries Co., Ltd.) is used, and irradiation is performed in a reflection mode according to JIS Z-8722 (2000). The b values before and after the irradiation were determined by measuring the b values before and after the P1 layer and calculating the average value. The difference (b value after irradiation to b value before irradiation) was defined as a color tone change Δb after ultraviolet irradiation.
The obtained color tone change (Δb) was determined as follows.
When the color change Δb is 1 or less: S
When the color tone change Δb is greater than 1 and 3 or less: A
When the color change Δb is greater than 3 and less than or equal to 6: B
When the color change Δb is greater than 6 and 9 or less: C
When the color change Δb is greater than 9: D
S to C pass, and S is the best among them.

(11) Durability (Elongation retention after wet heat resistance test)
After cutting the laminated sheet into the shape of the measurement piece (sample) (1 cm × 20 cm), it is processed for 48 hours under the conditions of a temperature cooker manufactured by Hirayama Seisakusho Co., Ltd. at a temperature of 125 ° C. and a relative humidity of 100% RH. Thereafter, the elongation at break was measured according to the above item (8). In addition, after measuring about 5 samples of the longitudinal direction (longitudinal direction) and the width direction (lateral direction) of a lamination sheet, the measurement was made into n = 5, and the average value was made into elongation at break E1. Moreover, also about the lamination sheet before performing a process, breaking elongation E0 is measured according to the said (8) term, The elongation retention is calculated by following Formula (5) using the obtained breaking elongation E0 and E1. Calculated.
Elongation retention (%) = (E1 / E0) × 100 (5)
The obtained elongation retention was determined as follows.
When the elongation retention is 50% or more: S
When the elongation retention is 40% or more and less than 50%: A
When the elongation retention is 30% or more and less than 40%: B
When the elongation retention is 20% or more and less than 30%: C
When the elongation retention is less than 20%: D
S to C pass, and S is the best among them.

(12) Melting point (Tm)
In the present invention, the melting point is a value obtained by differential scanning calorimetry (hereinafter referred to as DSC), which is obtained in a temperature rising process (temperature rising rate: 20 ° C./min), and the object to be measured is JIS K-7121 (1999). ) At a rate of temperature increase from 25 ° C. to 300 ° C. at a rate of 20 ° C./min, held at 300 ° C. for 5 minutes, then rapidly cooled to 25 ° C. or lower, and again 25 The temperature is the peak top temperature in the crystal melting peak in the differential scanning calorimetry chart obtained by raising the temperature from 20 ° C. to 300 ° C. at a rate of temperature rise of 20 ° C./min.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not necessarily limited thereto.

(material)
Polyamide resin Examples 1 to 23, Examples 28 to 36, Comparative Example 1 and Comparative Examples 3 to 8 Nylon 6 resin “Amilan” (registered trademark) CM1021T (polyamide resin (PA6) constituting the P1 layer) Toray Industries, Inc., Tm; 225 ° C.) was used.
Nylon 66 resin “Amilan” CM3001 (PA66) per Example 24, Nylon 610 resin “Amilan” CM2001 (PA610) per Example 25, Nylon 11 resin “Rilsan” BESN-O-TL (PA11) per Example 26 For example 27, the nylon 12 resin “Rilsan” AESN-TL (PA12) was used.

-Olefin resin Examples 1 to 15, 20 to 23, 24 to 36, and Comparative Examples 2 to 8, "Noblen" WF345S (3.5% by mass of ethylene) manufactured by Sumitomo Chemical Co., Ltd., which is a copolymerized polypropylene Copolymerized polypropylene in which 4.0% by mass of butene was copolymerized was used as “EPBC1”.
For Example 16, “Evolue” SP2530 manufactured by Sumitomo Chemical Co., Ltd., which is a linear low density polyethylene, was used as “LLDPE1”.
For Example 17, “Evolue” SP2540 manufactured by Sumitomo Chemical Co., Ltd., which is a linear low density polyethylene, was used as “LLDPE2”.
For Example 18, 1% ethylene copolymer polypropylene was used as “EPC1”.
In Example 19, “Noblen” FLX80E4 manufactured by Sumitomo Chemical Co., Ltd., which is polypropylene, was used as “PP1”.

Acid-modified polyolefin “Modic” P553A (acid-modified polyolefin using polypropylene as polyolefin) as a resin constituting the P2 layer in Examples 1 to 23, 24 to 27 and Comparative Examples 3 to 8 Was used as “resin 1”.
For Example 28, “Modic” M545 manufactured by Mitsubishi Chemical Corporation (acid-modified polyolefin using linear low-density polyethylene as the polyolefin) was used as “Resin 2”.
In Example 29, “Modic” F535 (an acid-modified polyolefin using a copolymerized olefin as the polyolefin) manufactured by Mitsubishi Chemical Corporation was used as “Resin 3”.
In Example 30, “Modic” A515 (an acid-modified polyolefin using an ethylene-vinyl acetate copolymer as the polyolefin) manufactured by Mitsubishi Chemical Corporation was used as “Resin 4”.
In Example 31, “Modic” L504 (acid-modified polyolefin in which low-density polyethylene was used as the polyolefin) manufactured by Mitsubishi Chemical Corporation was used as “Resin 5”.
For Example 32, “Modic” H503 (acid-modified polyolefin using high-density polyethylene as the polyolefin) manufactured by Mitsubishi Chemical Corporation was used as “Resin 6”.
In Example 33, “Admer” SF731 (acid-modified polyolefin using polyethylene as the polyolefin) manufactured by Mitsui Chemicals, Inc. was used as “Resin 7”.
For Example 34, “Admer” QB550 (acid-modified polyolefin using a copolymerized olefin as the polyolefin) manufactured by Mitsui Chemicals, Inc. was used as “Resin 8”.
For Example 35, “Admer” QF500 (acid-modified polyolefin using polypropylene as the polyolefin) manufactured by Mitsui Chemicals, Inc. was used as “Resin 9”.

For the acrylic adhesive Example 36, “Bondaine” TX8030 (ethylene-ethyl acrylate-maleic anhydride terpolymer type) manufactured by Arkema Co., Ltd. was used as “Resin 10”.

Polyolefin-based elastomer For Examples 20 to 23, “Notio” PN2060 manufactured by Mitsui Chemicals, Inc. was used as “Elastomer 1” as the polyolefin-based elastomer.

Inorganic particles The inorganic particles used in Examples 1 to 7, 9 to 23 and 24 to 36, and P1 layers of Comparative Examples 1 and 3 to 8 and P3 layers of Examples 1 to 23 and Comparative Examples 2 to 8 are Rutile type titanium dioxide was used. Further, the titanium dioxide of the P1 layer has a desired concentration of the resin used as the main constituent component of the P1 layer for each example and comparative example and the resin obtained by mastering titanium dioxide at a ratio of 50% by mass / 50% by mass. Added. The titanium dioxide of the P3 layer was added so that the resin used as the main constituent component of the P3 layer and the titanium dioxide mastered at a ratio of 30% by mass / 70% by mass in each example and comparative example to a desired concentration. .

(Examples 1 to 27, Comparative Examples 3 to 8)
Using the extruder 1, the extruder 2 and the extruder 3, the raw materials shown in Table 1 are supplied to each extruder so as to have a desired blending ratio, and then the layer melt-extruded from the extruder 1 is the P1 layer, the extrusion The machine 2 is the P2 layer and the extruder 3 is the P3 layer. The layers are joined together in a multi-manifold so that the P1 layer / P2 layer / P3 layer are laminated in order, and the resin discharged from the die is cooled and solidified on the cast drum. Thus, a laminated sheet was obtained. The thicknesses shown in Table 2 were obtained for the P1, P2, and P3 layers. The evaluation shown in Table 2 was implemented about the obtained lamination sheet. As a result, as shown in Table 2, the examples were found to be excellent laminated sheets.

Furthermore, since Examples 20 to 23 contained an elastomer in the P2 layer, the interlayer adhesion was extremely excellent.

On the other hand, Comparative Example 3 was inferior in durability and flame retardancy because T1 / Ta in formula (1) was smaller than 0.3. Comparative Example 4 was inferior in electrical characteristics because T1 / Ta was larger than 0.5. In Comparative Example 5, since Ta in formula (2) was smaller than 200, the durability, flame retardancy, and gas barrier properties were inferior. Since the comparative example 7 had M / T3 of Formula (3) smaller than 0.05, the heat yellowing was inferior. Since the comparative example 8 had M / T3 larger than 0.5, the adhesiveness with a sealing material was inferior.

(Comparative Example 1)
Using the extruder 1, the raw materials shown in Table 1 are supplied to the extruder so as to have a desired mixing ratio, and then the resin melt-extruded from the extruder 1 and discharged from the die is cooled and solidified on a cast drum to form a single layer A sheet was obtained. Since there was no olefin resin layer, the electrical properties, barrier properties, and adhesion to the sealing material were poor.

(Comparative Example 2)
Using the extruder 3, the raw materials shown in Table 1 are supplied to the extruder so as to have a desired blending ratio, and then the resin melt-extruded from the extruder 3 and discharged from the die is cooled and solidified on a cast drum to form a single layer A sheet was obtained. Since there was no polyamide resin layer, the durability and flame retardancy were poor.

(Examples 28 to 36)
A laminated sheet was obtained in the same manner as in Example 1 except that the raw materials shown in Table 1 were supplied to each extruder so as to have a desired blending ratio. The evaluation shown in Table 2 was implemented about the obtained lamination sheet. As a result, as shown in Table 2, it was found to be an excellent laminated sheet.

It is possible to provide a laminated sheet that is less susceptible to yellowing than a laminated sheet using a conventional polyamide-based resin, and that can achieve both durability, flame retardancy, and water vapor barrier properties. Such laminated sheets are used for solar cell backsheets, liquid crystal display reflectors, automotive materials, building materials, and other applications where yellowing, wet heat resistance, resistance to ultraviolet rays, and light reflectivity are important. Can be suitably used. In particular, a laminated sheet that can be suitably used as a back sheet for a solar cell, and a method for producing the laminated sheet can be provided.

1: Solar cell back sheet (laminated sheet)
2: Sealing material 3: Power generation element 4: Transparent substrate 5: Surface on the sealing material 2 side of the solar cell backsheet 6: Surface on the opposite side of the sealing material 2 of the solar cell backsheet

Claims

A laminated sheet having a layer (P1 layer) mainly comprising a polyamide-based resin and a layer (P3 layer) mainly comprising an olefin-based resin,
P3 layer contains inorganic particles,
Furthermore, the P1 layer is located on the surface layer, and the P3 layer is located on the surface opposite to the P1 layer,
When the thickness of the entire laminated sheet is Ta (μm), the thickness of the P1 layer is T1 (μm), the thickness of the P3 layer is T3 (μm), and the content of inorganic particles in the P3 layer is M (mass%), A laminated sheet characterized by satisfying all of the following formulas (1) to (3).
0.05 ≦ M / T3 ≦ 0.5 (1)
200 ≦ Ta ≦ 500 (2)
0.3 ≦ T1 / Ta ≦ 0.5 (3)
The laminated sheet according to claim 1, wherein the P1 layer contains 0.1 to 30% by mass of inorganic particles.
When a layer mainly composed of one selected from the group consisting of a low crystalline soft polymer, an acrylic adhesive, and an ethylene-vinyl acetate copolymer is a P2 layer, it is between the P1 layer and the P3 layer. The laminated sheet according to claim 1 or 2, wherein the P2 layer has a P2 layer thickness of 15 to 50 µm.
The laminated sheet according to any one of claims 1 to 3, wherein the P3 layer olefin resin has a melting point of 120 to 155 ° C.
The laminated sheet according to claim 3, wherein the P2 layer contains 0.1 to 20% by mass of a polyolefin-based elastomer.
A solar battery back sheet comprising the laminated sheet according to any one of claims 1 to 5.
A solar cell member comprising the laminated sheet according to any one of claims 1 to 5.
A solar cell member comprising the laminated sheet according to any one of claims 1 to 5 and a sealing material, wherein the sealing material is located on the surface side of the P3 layer of the laminated sheet .
It is a manufacturing method of the lamination sheet according to claim 3 or 5,
Main composition comprising one selected from the group consisting of a raw material mainly comprising a polyamide resin for P1 layer, a low crystalline soft polymer for P2 layer, an acrylic adhesive, and an ethylene vinyl acetate copolymer The raw material used as the component and the raw material mainly comprising the olefin resin for the P3 layer are supplied to different extruders, and after melting, the P1 layer, the P2 layer, and the P3 layer are merged in this order and laminated. And the manufacturing method of a lamination sheet characterized by including the process extruded to a sheet form from T-die.
A solar cell using the laminated sheet according to any one of claims 1 to 5, the solar cell backsheet according to claim 6, or the solar cell member according to claim 7 or 8.