JP2013053250A - Olefinic resin composition, and molding made by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in thermal reversible crosslinkability, moldability and total light transmittance, and having good color tone and high peeling strength.SOLUTION: A molding is formed using the resin composition containing a modified olefinic polymer (component A) obtained by grafting at least one unsaturated carboxylic anhydride on an olefinic polymer in a component concentration of the unsaturated carboxylic anhydride group of 0.1 to 20 mass%, a non-modified olefinic polymer (component B), and a polyhydric alcohol compound (component C) having at least two hydroxyl groups in the molecule, wherein the component A and the component B are in a specific proportion.

Description

  The resin composition of the present invention relates to an olefin resin composition exhibiting good moldability, color tone, and total light transmittance, and a molded article formed by molding the composition.

  In recent years, interest in clean energy has increased, and development of solar cell products has been demanded from such a viewpoint. As such a solar cell product, for example, a solar cell module is known. A solar cell module is generally composed of a solar cell element and various layers such as a sealing material layer in close contact with the surface or both surfaces thereof and a protective layer in close contact with the sealing material layer. As a layer in such a solar cell module, a resin layer is usually used, and a thermoreversible cross-linkable olefin polymer composition is known as a resin composition suitable for such a resin layer ( For example, see Patent Document 1.)

  Further, as the olefin polymer composition, in addition to excellent mechanical properties and weather resistance, for example, a composition that can be reversibly shaped, or that can be rapidly crosslinked and molded, is also known, Application to various uses is expected (for example, see Patent Documents 2 to 4).

  On the other hand, for solar cell modules, from the viewpoint of versatility and further expansion of applications, not only improvement of performance as a solar cell but also improvement of various characteristics such as diversification of shape and improvement of productivity are required. Yes. For this reason, the further examination for responding to the further request | requirement with respect to a solar cell module is calculated | required also for the material of a solar cell module.

JP 2001-326374 A JP-A-11-106578 JP 2001-139759 A Japanese Patent Laid-Open No. 11-269321

  The present invention provides a resin composition that is excellent in thermoreversible crosslinkability, moldability, and total light transmittance, and has good color tone and high peel strength.

  The present inventors have found that the above-mentioned problems can be solved by using a thermoreversible crosslinkable olefin polymer and a specific olefin polymer in combination, and have completed the present invention.

  That is, the present invention relates to a modified olefinic polymer obtained by grafting component A: at least one unsaturated carboxylic acid anhydride onto an olefinic polymer at a component concentration of carboxylic acid anhydride groups of 0.1 to 20% by mass. A resin composition comprising a polymer, component B: an unmodified olefin polymer, and component C: a polyhydric alcohol compound having at least two hydroxyl groups in the molecule, wherein the crystal melting point (Tm) of component B is Provided is a resin composition having a weight content ratio of component A to component B (component A) / (component B) of 95/5 to 5/95 at 100 ° C. or lower.

  Moreover, this invention provides the said resin composition whose weight content ratio (component A) / (component B) of the component A and the component B is 70 / 30-5 / 95.

  Moreover, this invention provides the molded object formed by shape | molding the said resin composition.

  Moreover, this invention provides the said molded object which is a solar cell element sealing material.

  Moreover, this invention provides the solar cell module using the said solar cell element sealing material.

  Since the present invention contains the components A to C in the resin composition, the resin composition is excellent in thermoreversible crosslinkability, moldability, and total light transmittance, and has a good color tone and high peel strength. can do.

The resin composition of the present invention contains the following components A to C. Each of the components A to C may be one kind or two or more kinds.
Component A: Modified olefin polymer obtained by grafting at least one unsaturated carboxylic acid anhydride onto an olefin polymer at a component concentration of carboxylic acid anhydride group of 0.1 to 20% by mass Component B: Not yet Modified Olefin Polymer Component C: A polyhydric alcohol compound having at least two hydroxyl groups in the molecule.

  In the present invention, component A is a modified olefin polymer obtained by grafting at least one unsaturated carboxylic acid anhydride onto an olefin polymer, and the component concentration of the carboxylic acid anhydride group is 0.1 to 20% by mass. It is. In the resin composition of the present invention, excellent thermoreversible crosslinkability can be obtained by using Component A. In the modified olefin polymer, the carboxylic acid anhydride groups may be present evenly dispersed or may be unevenly distributed. The component concentration is preferably a value per molecule.

  As the olefin polymer, a polymer containing an olefin structure to which an unsaturated carboxylic acid anhydride can be grafted can be used. The olefin polymer may be one type or two or more types. Examples of such an olefin polymer include homopolymers of olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and two or more kinds of these olefins. Alternatively, block copolymers and binary or multi-component copolymers with vinyl acetate, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, and the like mainly composed of these olefins may be mentioned.

  The molecular weight of the olefin polymer is not particularly limited as long as it has a range in which good fluidity can be obtained, for example, a range in which a preferable value of MFR described later can be obtained.

  As the unsaturated carboxylic acid anhydride, a compound having an unsaturated bond group and a carboxylic acid anhydride group can be used. The unsaturated carboxylic acid anhydride may be one kind or two or more kinds. Examples of such unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic acid anhydride, 1-butene-3,4-dicarboxylic acid anhydride, and at most 18 carbon atoms. Alkenyl succinic anhydride having a double bond at the terminal and alkadienyl succinic anhydride having a carbon number of at most 18 and having a double bond at the terminal. Among these, maleic anhydride and itaconic anhydride are particularly preferable.

In Component A, the component concentration of the carboxylic acid anhydride group is 0 from the viewpoint of expressing a sufficient crosslinking density in the molded product of the resin composition of the present invention and expressing desired properties such as flexibility and mechanical strength. 0.1 to 20% by mass, and preferably 1 to 10% by mass. The component concentration can be confirmed by infrared absorption spectrum analysis, or may be a theoretical value by calculation.

  Component A is not necessarily clearly limited, but the melt flow rate (MFR) of component A is 0.1 from the viewpoint of developing sufficient heat resistance and good moldability (fluidity). It is preferably ~ 100 g / 10 min. The MFR of component A can be determined according to the measurement method defined in JIS K7210.

  Component A can be obtained by any known method. For example, component A is prepared by dissolving the olefin polymer in a solvent, mixing the resulting solution with an unsaturated carboxylic acid anhydride and a radical initiator, or by extruding in the absence of a solvent. It can be obtained by a melt graft method in which the olefin polymer is modified with an unsaturated carboxylic acid anhydride in a machine, or a radiation graft method using an electron beam. In the production of component A, it is preferable to remove unreacted substances and reaction by-products after graft modification by these methods and then performing an appropriate post-treatment such as washing with a solvent.

  Specific examples of the olefin polymer used for Component A include high-density polyethylene, low-density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-vinyl acetate copolymer, and ethylene-butene-1 copolymer. Polymers, propylene-butene-1 copolymers, ethylene-acrylic acid ester copolymers, ethylene-maleic anhydride-acrylic acid ester copolymers, and zinc salts of ethylene-methacrylic acid copolymers, and And a mixture of two or more.

  In the present invention, the unmodified olefin polymer of component B may be a polyolefin resin that is not modified with an unsaturated carboxylic acid anhydride, having an ethylene unit or a propylene unit as a main component, an acid, or an epoxy group. It is a polyolefin-based thermoplastic resin that does not contain. Specific examples thereof include a polyethylene resin, a polypropylene resin, and an ethylene-α-olefin copolymer. These materials may be used alone or in combination of two or more resins.

  The polyethylene resin is not particularly limited. For example, polyethylene resin such as low density polyethylene, high density polyethylene, linear low density polyethylene, ultrahigh molecular weight polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate, etc. Copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-dimethylaminomethyl methacrylate copolymer, ethylene-vinyl alcohol copolymer, ethylene oxide of ethylene-vinyl alcohol copolymer A copolymer of ethylene and a polar monomer such as an adduct can be exemplified.

  The polypropylene resin is not particularly limited. For example, homoisotactic polypropylene, isotactic polypropylene random copolymer containing ethylene or 1-butene, isotactic polypropylene block copolymer containing ethylene propylene, Ziegler Natta-catalyzed isotactic polypropylene, metallocene-catalyzed isotactic polypropylene, metallocene-catalyzed syndiotactic polypropylene, polypropylene such as atactic polypropylene, polymer alloy of polypropylene and rubber, polypropylene / filler composite, chlorinated polypropylene, etc. The functionalized polypropylene is mentioned.

Although there is no limitation in particular as an ethylene-alpha-olefin copolymer, The ethylene propylene diene copolymer containing a diene component, the ethylene propylene copolymer of arbitrary composition ranges, etc. are mentioned. Moreover, ethylene-alpha-olefin copolymers other than an ethylene propylene copolymer, for example, an ethylene butene copolymer, an ethylene hexene copolymer, an ethylene octane copolymer, etc. are mentioned.

  Among these, polyethylene resins and ethylene-α-olefin copolymers are preferably used in the present invention, and more preferably obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms. It is an ethylene-α-olefin copolymer.

  Component B has a crystal melting point (Tm) of 100 ° C. or lower, preferably 97 ° C. or lower, and preferably 90 ° C. or lower, from the viewpoint of developing excellent moldability, total light transmittance and good color tone. More preferably, it is most preferable that it is 70 degrees C or less.

  Component B has sufficient compatibility with Component A, and from the viewpoint of sufficiently expressing mechanical properties such as a balance between rigidity and impact resistance and tensile properties, (1) Temperature rising elution fractionation of Component B ( The temperature of the peak having the maximum height in the elution curve of (TREF) is 90 ° C. or less, and (2) the peak height (H) with respect to the width (W) of 1/3 height in the maximum peak. ) Ratio (H / W) is preferably 2 or more, and it is preferable to satisfy the two conditions (1) and (2).

  Temperature rising elution fractionation (TREF) is a known analysis method in which an inert carrier which has been completely dissolved in a solvent at a high temperature and then cooled and present in the solution. When a thin polymer layer is formed on the surface and then the temperature of the formed polymer layer is increased continuously or stepwise, the low crystalline or amorphous components are eluted, and finally the high crystalline components are eluted. In this method, the polymer composition distribution is analyzed from the elution curve drawn by the elution amount and elution temperature at each temperature.

  Measurement of elution curve for temperature rising elution fractionation consists of a temperature rising elution fractionation (TREF) mechanism for fractionating the sample using the difference in dissolution temperature and a size exclusion chromatograph (Size) for further classifying the fractionated segments by molecular size. It can be measured using a cross fractionation apparatus (“CFC T150A” manufactured by Mitsubishi Chemical Corporation) connected online with Exception Chromatography (SEC).

  As the measurement conditions, for example, o-dichlorobenzene is used as a solvent, the sample concentration is 4 mg / mL, glass beads are used as an inert carrier, the cooling temperature range is 140 ° C. to 0 ° C., and the cooling rate is 1 ° C. / Min., And elution temperatures of 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, and 140 ° C., the waiting time at each elution temperature is 30 minutes, and the amount of sample solution injected into the SEC column at each elution temperature is The conditions are 2 mL, the injection rate is 1 mL / min, and the measurement interval of each elution segment in SEC is 39 minutes.

  In addition, the solution fractionated by molecular size with the SEC column was measured for absorbance proportional to the polymer concentration with the infrared spectrophotometer attached to the device (detected by the stretching vibration of methylene having a wavelength of 3.42 μm). A chromatogram of the temperature category is obtained. Furthermore, using the built-in data processing software, draw the baseline of the obtained chromatogram of each elution temperature section, calculate, integrate the area of each chromatogram, calculate the integrated elution curve, and also calculate this integrated elution curve The differential elution curve is calculated by differentiating the temperature with temperature, and the calculation result can be output to the printer.

Component B may have a Q value (weight average molecular weight / number average molecular weight) of 4 or less as a molecular weight distribution determined by size exclusion chromatography (SEC) from the viewpoint of not impairing the appearance of the surface of the molded article. Preferably, it is 3 or less, more preferably 2.5 or less.

Component B preferably has a density (according to JIS K7112) of 0.930 g / cm ³ or less from the viewpoint of obtaining good transparency. Component B contains a melt flow rate (19
0 ° C., 2.16 kg load) (according to JIS K6922-2) is preferably 1 to 30 g / 10 min from the viewpoint of preventing deterioration of moldability.

  Component B has a Q value (weight average molecular weight / number average molecular weight) as a molecular weight distribution determined by size exclusion chromatography (SEC) of 4 or less from the viewpoint of obtaining a good surface appearance when formed into a molded body. Preferably, it is 3 or less, more preferably 2.5 or less.

  The production method of component B is not particularly limited as long as the above properties are satisfied. Generally, in the presence of a catalyst, polymerization methods such as a gas phase method, a slurry method, a solution method, and a high-pressure ion polymerization method are preferable. It can obtain according to the method manufactured by the high voltage | pressure ion polymerization method, or these methods. As the component B having physical properties in the present invention, a commercially available product can be used, but it can also be produced using a known method such as the method described above or the method described in the following publication. Moreover, regarding the catalyst used for the said manufacture, a Ziegler catalyst, a metallocene catalyst, etc. can be used, Preferably a metallocene catalyst can be used.

  Examples of the metallocene catalyst include JP-A 58-19309, JP-A 60-35006, JP-A 60-35007, JP-A 60-35008, and JP-A 3-163088. Catalysts described in Patent Application Publication No. 420,436, US Pat. No. 5,055,438, and International Publication No. 91/04257, ie, metallocene compounds, metallocene compounds / alumoxane catalysts, etc. Alternatively, for example, a catalyst composed of a compound that reacts with a metallocene compound and a metallocene compound to form stable ions as disclosed in International Publication No. 92/07123 or the like can be mentioned.

  In the present invention, the weight content ratio of component A to component B (component A) / (component B) is the expression of thermoreversible crosslinkability, excellent moldability, excellent total light transmittance, and good color tone. From the viewpoint of achieving both, the ratio is 95/5 to 5/95. From the above viewpoint, the content ratio is preferably 70/30 to 5/95, and more preferably 65/35 to 10/90.

  In the present invention, component C is a polyhydric alcohol compound having at least two hydroxyl groups in the molecule. The number of carbon atoms of component C is not particularly limited, but the number average molecular weight of component C is preferably 200 to 10,000 from the viewpoint of preventing generation of smoke during molding and exhibiting good crosslinkability. 500 to 5,000 is more preferable. Component C may be one type or two or more types. Component C preferably has a melting point of 300 ° C. or less from the viewpoint of suppressing thermal degradation of Component A.

Examples of component C include glycols such as ethylene glycol, diethylene glycol, and triethylene glycol; 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and trimethylol. Alcohol compounds such as ethane, trimethylolpropane, pentaerythritol; saccharides such as arbitol, sorbitol, xylose, arabinose, glucose, galactose, sorbose, fructose, palatinose, maltotriose, maletoose; saponification of ethylene-vinyl acetate copolymer Polymers having a plurality of hydroxyl groups in the molecule, such as polymers, polyvinyl alcohol, olefin oligomers having a plurality of hydroxyl groups, and ethylene-hydroxyethyl (meth) acrylate copolymers; Loxypropane, 2,2-dimethyl-1,3-dihydroxypropane, trimethylolethane, 1,1,1-trimethylolpropane, 1,1,1-trimethylolhexane, 1,1,1-trimethyloldodecane, 2-cyclohexyl-2-methylol-1,3-dihydroxypropane, 2- (p-methylphenyl) -2-methylol-1,3-dihydroxypropane, pentaerythritol, glycerin, diglycerin, hexadiglycerin, octaglycerin, Polyoxyalkylene compounds obtained by addition reaction of ethylene oxide or propylene oxide with decaglycerol, etc .; glycerol monostearate, glycerol monooleate, glycerol monolaurate, glycerol monocaprylate, glycerol monohexanoate, Serine monophenethyl ester, glycerol monopropionate, diglycerol monostearate, diglycerol distearate, diglycerol monooleate, diglycerol monohexanoate, diglycerol dioctanoate, tetraglycerol monostearate, tetra Glycerol tristearate, tetraglycerol tetrastearate, tetraglycerol trihexanoate, tetraglycerol monophenethyl ester, hexaglycerol monostearate, hexaglycerol distearate, hexaglycerol pentastearate, hexaglycerol trioleate, hexaglycerol mono Laurate, hexaglycerin pentalaurate, decaglycerin monostearate, decaglycerin octastearate, decaglycerin Polyglycerol alkyl esters such as pentaoleate, decaglycerin dilaurate, pentadecaglycerin distearate, pentadecaglycerin decaoleate, octadecaglycerin tetrastearate; sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, Sorbitan monocaprylate, sorbitan monohexanoate, sorbitan monophenethyl ester, sorbitan monopropionate, sorbitan tristearate, sorbitan alkyl esters such as sorbitan tetrastearate;

  In the present specification, “(meth) acrylate” is a general term for methacrylate and acrylate, and means one or both of them.

  In the present invention, the content of component C relative to component A is an amount such that the molar ratio of the hydroxyl group in component C is 0.01 to 10 relative to the unit derived from the unsaturated carboxylic anhydride in component A. However, it is preferable from the viewpoint of effective introduction of a cross-linked structure in the molded body and expression of good moldability, and an amount of 0.05 to 5 is more preferable. When the unit derived from the unsaturated carboxylic acid anhydride in Component A is in the range of 0.1 to 1% by mass in Component A, the molar ratio of the hydroxyl group in Component C is the unsaturated carboxylic acid anhydride. More preferably, it is in the range of 0.1 to 5 with respect to the unit derived from.

  The resin composition of the present invention may contain other components other than the components A to C described above as long as the effects of the present invention are obtained. Examples of such other components include various additives commonly used in olefin-based resin compositions, such as antioxidants, light stabilizers, ultraviolet absorbers, nucleating agents, neutralizing agents, lubricants, and blocking agents. Examples include inhibitors, dispersants, fluidity improvers, mold release agents, flame retardants, colorants, and fillers.

  The resin composition of the present invention can be obtained by using a known method in which the components A to C described above are further added with optional components as necessary and the thermoplastic resin components are mixed. As such a method, for example, components A to C and an optional component are uniformly mixed by a mixer such as a Henschel mixer, a ribbon blender, a V-type blender, etc. A method of melt-kneading using a kneader such as Brabender can be mentioned.

The molded body of the present invention is formed by molding the above-described resin composition of the present invention. The molded body of the present invention is
It can be formed into a film, a sheet or other various shapes by a molding method usually used in ordinary thermoplastic resins. Examples of such molding methods include injection molding, extrusion molding, hollow molding, compression molding, and rotational molding.

  The molded body of the present invention can be used as a solar cell element sealing material. Such a solar electronic device sealing material is formed by, for example, molding the resin composition of the present invention into a film or sheet by the above-described molding method, and closely attaching the laminate including the solar cell device to the surface of the solar cell device. It can obtain by carrying out thermocompression bonding in the made state. Alternatively, the solar cell element sealing material can be obtained, for example, by melting the resin composition of the present invention and laminating it as a film or sheet on the surface of the solar cell element by the molding method described above.

  In this invention, a solar cell element sealing material is utilized as a sealing material layer formed in the surface or both surfaces of a solar cell element as mentioned above. The thickness of such a sealing material layer can be measured by a micrometer, and the thickness of the sealing material layer is not particularly limited, but when used for a sealing material layer of a solar electronic device. From the viewpoint of obtaining good strength and light transmittance, and improvement in workability related to installation of solar cell elements and cost reduction, it may be in the range of 100 to 1,000 μm, particularly in the range of 300 to 600 μm. preferable.

  In the molded body of the present invention, a crosslinked structure is formed in the molded body in the process of being cooled after heating at the time of molding, and then the crosslinked structure is dissociated when subjected to heating again. Thus, a crosslinked structure can be formed reversibly by heating during molding and subsequent cooling. Therefore, the molded article of the present invention exhibits excellent durability even when used under severe conditions such as outdoors.

  Further, in the molded article of the present invention, in forming the reversible crosslinked structure, the resin component itself is affected, and irreversible damage such as destruction or decomposition of the structure does not occur. For this reason, in the molded article of the present invention, decomposition components such as gas and impurities accompanying the irreversible damage phenomenon do not occur. Therefore, when used as a material directly applied to an electronic element, such as a solar cell element sealing material, there is no adverse effect on the electronic element due to decomposition components. In the electronic device using the molded body of the invention, the deterioration of the electronic element due to the molded body is prevented, and the durability of the electronic device is improved.

  The solar cell module of the present invention uses the above-described solar cell element sealing material of the present invention. Usually, the solar cell module of this invention has the sealing material layer mentioned above. The solar cell module of the present invention can be configured in the same manner as a normal solar cell module except that the sealing material layer is formed of the molded body of the present invention, and can be manufactured in the same manner. As such a solar cell module, for example, it has a solar cell element and a sealing material layer that seals the surface or both surfaces of the solar cell element, and may have other layers other than the sealing material layer. A good solar cell module is mentioned.

The solar cell element is a photovoltaic element, for example, a glass substrate, a plastic substrate, a metal substrate, or other substrate, a crystalline silicon such as a pn junction structure, an amorphous silicon such as a pin junction structure, A conventionally known element in which an electromotive force portion such as a compound semiconductor or a fullerene derivative is formed can be used. One or more solar cell elements may be used. As such a solar cell element, for example, a crystalline silicon solar electronic element such as a single crystal silicon type solar cell element, a polycrystalline silicon type solar cell element, an amorphous silicon solar cell element composed of a single junction type or a tandem structure type, etc. III-V compound semiconductor solar electronic devices such as gallium arsenide (GaAs) and indium phosphorus (InP), and II-VI compound semiconductor solar electronic devices such as cadmium tellurium (CdTe) and copper indium selenide (CuInSe ₂ ) , Organic thin film solar cell elements made of fullerene derivatives, etc., thin film polycrystalline silicon solar cell elements, thin film microcrystalline silicon solar cell elements, and hybrid elements of thin film crystalline silicon solar cell elements and amorphous silicon solar cell elements. .

  As described above, the sealing material layer can be formed by thermocompression bonding of the film or sheet to the solar cell element or direct molding of the film or sheet on the surface of the solar cell element.

  As other layers that the solar cell module of the present invention may have, various layers known for solar cell modules can be used, and they can be formed by a known method for forming these layers. . Examples of such other layers include a surface protective layer that is in close contact with the encapsulant layer on the electromotive surface side of the solar cell element, and a back surface of the solar cell element or an encapsulant layer on the back side of the solar cell element. And a back surface protective layer.

  The surface protective layer and back surface protective layer have various properties such as insulation, heat resistance, light resistance, water resistance, weather resistance, physical or chemical strength, toughness, scratch resistance, shock absorption, etc. It is preferable that it is excellent. The surface protective layer needs to further have transparency, and the back surface protective layer does not need to have transparency. These layers may be the same or different in properties other than the presence or absence of transparency.

  Examples of the material for such a protective layer include polyethylene resins, polypropylene resins, cyclic polyolefin resins, fluorine resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile-butadiene-styrene copolymers. Polymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, various polyamide resins such as nylon, Polyimide resins, polyamideimide resins, polyarylphthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfone resins, polyurethane resins, acetal resins, and Loin resins.

  Among these resins, in particular, from the viewpoint of excellent mechanical properties, chemical properties, physical properties, etc., specifically, weather resistance, heat resistance, water resistance, light resistance, moisture resistance, stain resistance, stain resistance, Excellent in robustness such as chemical properties and others, useful as a protective layer constituting solar cells, excellent in durability, protective functionality, etc. In addition, its flexibility, mechanical properties, chemical properties, etc. From the viewpoint of being lightweight, excellent in workability, etc., and having an advantage such as easy handling, a fluorine resin, a cyclic polyolefin resin, a polycarbonate resin, a poly (meth) acrylic resin, and a polyester resin A resin is more preferable.

  Specific examples of the fluororesin include polyvinyl fluoride resin (PVF) and a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE). Specific examples of the cyclic polyolefin resin include cyclopentadiene and derivatives thereof, dicyclopentadiene and derivatives thereof, and polymers or copolymers of cyclic dienes such as norbornadiene and derivatives thereof.

  About the said other layer, you may extend | stretch a uniaxial or biaxial direction to the film or sheet | seat of various resin as needed. Various plastic compounding agents and additives may be added to the other layers. For example, in order to improve weather resistance and puncture resistance, for example, one or more kinds of ultraviolet absorbers, antioxidants, or reinforcing fibers may be incorporated into the other layers.

As the ultraviolet absorber, one or more inorganic or organic ultraviolet absorbers can be used. Further, as the antioxidant, known antioxidants such as phenol, amine, sulfur and phosphoric acid can be used. Further, the ultraviolet absorber or antioxidant may be a polymer type ultraviolet absorber or antioxidant having a functional group exhibiting these functions in the main chain or side chain of the resin.

  Examples of the reinforcing fiber include glass fiber, carbon fiber, aramid fiber, polyamide fiber, polyester fiber, polypropylene fiber, polyacrylonitrile fiber, and natural fiber. The form of the reinforcing fiber is not particularly limited. Examples of the form of the reinforcing fiber include long fiber, short fiber, woven fabric, and nonwoven fabric.

  The other layers preferably have a thickness of 12 to 200 μm, and more preferably 25 to 150 μm.

  For the back surface protective layer, for example, two or more kinds of the above-described resin film or sheet are used, and a laminated material obtained by laminating them through an adhesive layer or the like, for example, an aluminum foil or the like on the above-described resin film or sheet In consideration of decorativeness, design, etc. on the back of laminated metal foils, metal plates, or solar cell modules, the above-mentioned resin films or sheets are used with coloring agents such as dyes and pigments. Then, a colored or decorated resin film or sheet can be used.

  From the viewpoint of further improving various properties related to mechanical strength such as strength, weather resistance, and scratch resistance of the solar cell module, the other layers are made of the above-described resin, unstretched, uniaxial to biaxial. It may comprise a further layer having a thickness on the order of a few μm to 300 μm, which may be stretched in the direction. The other layer may be any film of extrusion film formation, inflation film formation, or coating film.

  The solar cell module of the present invention is formed by, for example, sequentially stacking a surface protective layer sheet, a sealing material layer sheet, a solar cell element, a sealing material layer sheet, and a back protective layer sheet by a known method. These can be manufactured by integrating them by vacuum suction or the like and heat-pressing them.

  In such a production method, from the viewpoint of improving the adhesion between the respective layers, a heat-melt adhesive having a vehicle as a main component of a vehicle such as a (meth) acrylic resin, an olefin resin, a vinyl resin, or the like, You may further use adhesives, such as a solvent type adhesive agent and a photocurable adhesive agent. In the manufacturing method, a part of each sheet or element may be integrated in advance. Furthermore, in the manufacturing method described above, from the viewpoint of improving the tight adhesion of each layer, for example, using corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemicals, etc. A pretreatment such as an oxidation treatment may be optionally performed.

  Moreover, in the said manufacturing method, a primer coating agent layer, an undercoat agent layer, an adhesive bond layer, or an anchor coating agent layer can be arbitrarily formed in advance on the opposing surface of each layer, and surface pretreatment can also be performed. Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition comprising a main component of a vehicle, such as a polyolefin-based resin or a copolymer or modified resin thereof, and a cellulose-based resin, can be used. The coating agent layer is formed by using a coating method such as a solvent coating, an aqueous coating, or an emulsion coating using a roll coating method, a gravure roll coating method, a kiss coating method, or the like. Can do.

As apparent from the above description, the resin composition of the present invention focuses on the melting point of Component B and the composition ratio of Component A and Component B, and exhibits good moldability, color tone, and total light transmittance. Moreover, the strength is excellent and a useful resin composition applicable to various uses can be produced. In particular, when used as a sealing material layer of a solar cell module, the solar cell module can be used stably and at low cost without being affected by manufacturing conditions such as thermocompression bonding.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Example 1]
(1) Manufacture of olefin resin composition and molded product thereof MFR (190 ° C., 2.16 kg load) 3.6 g / 10 minutes, 100 parts by weight of low density polyethylene having a density of 0.89 g / cm ³ After mixing 0.6 part by weight of acid and 0.03 part by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane with a super mixer for about 1 minute, a twin-screw extruder (30 mm, L / D = 42) using a cylinder set temperature of 230 ° C., a screw rotation speed of 300 rpm, a discharge rate of 15 kg / hr, melt-kneaded, extruded into a strand shape, cut to a predetermined pellet size, and carboxylic anhydride group content 0 A modified olefin resin having a mass of 0.44% by mass, MFR (190 ° C., 2.16 kg load) 1.8 g / 10 min, and a density of 0.89 g / cm ³ was obtained. 25% of this modified olefin resin as component A
75 parts by mass of a PE copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name: “Kernel KF370”) using a metallocene catalyst as an unmodified olefin resin (component B) As component C), 1.3 parts by mass (hydroxy group / acid anhydride group = 1) of OH-terminated polybutadiene hydride (trade name, “Polytail H” manufactured by Mitsubishi Chemical Corporation), and phosphite system as an antioxidant Antioxidants (trade name, “ADEKA STAB PEP8” manufactured by ADEKA Co., Ltd., 2,000 ppm by mass, hindered amine light stabilizers (manufactured by BASF, product names, “CHIMASSORB 944”, “TINUVIN 770DF”) as light stabilizers, respectively. 1,000 ppm by weight, as UV absorber, benzotriazole UV absorber (BASF Manufactured under the trade name "TINUVIN 326FL") was mixed at 1,000 ppm by mass.

  For mixing, the three components are dry blended with a tumbler, melt-kneaded at 220 ° C using Toyo Seiki Brabender, the resulting kneaded product is pressed, and pellets of the olefin resin composition are produced using a pelletizer. did. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. In Table 1, the melting point (Tm) of component B is the melting point of component B measured according to JIS K7121.

(2) Measurement of pellet color tone The color tone of the pellets of the composition produced in the above (1) was measured using a color difference meter (manufactured by Nippon Denshoku Co., Ltd., device name, ZE2000) (Table 2).

(3) MFR measurement The MFR measurement of the said composition was performed as a judgment material which judges the sheet molding possibility of the composition manufactured in said (1), and fluidity | liquidity was evaluated. The measuring method was based on JIS K7210, and fluidity (g / 10 minutes) was measured at a test temperature of 230 ° C. and a load of 2.16 kg (Table 2).

(4) Determination of film forming possibility Next, film forming was performed using the above composition. Using a short-axis extruder PMS30-32 (resin temperature 220 ° C., resin pressure 1.5 MPa), a film having a thickness of 500 μm was manufactured, and whether or not film forming was possible was determined. The result was “◯” (Table 2). In Table 2, the film formation “◯” indicates that there is no unevenness and a film having a uniform thickness can be formed. In the case of “x”, it represents a film with a lot of irregularities, or the film cannot be formed.

(5) Measurement of total light transmittance In the above (4), the total light transmittance (%) was measured with a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-65W). ) Was measured. The results are shown in Table 2.

(6) Manufacture of Solar Cell Module In the above (4), a solar cell module was manufactured for the film whose film formation was “◯”.

A 100 μm-thick tetrafluoroethylene / ethylene copolymer (ETFE) film (trade name, “Aflex” manufactured by Asahi Glass Co., Ltd.), a 500 μm-thick film produced above, and a PEN (polyethylene naphthalate) substrate VHF-Technologies SA solar cell element made of amorphous silicon and having a thickness of 500 μm
The above-prepared film and the 100 μm-thick ETFE film (trade name, “Aflex”, manufactured by Asahi Glass Co., Ltd.) are stacked in this order, and the solar cell surface is faced up, and a vacuum laminator (stock) A solar cell module was manufactured by vacuum thermocompression bonding at 150 ° C. for 20 minutes using a device manufactured by NPC Corporation, device name, LM-50X50-S).

(7) Measurement of peel strength with ETFE film 100 μm thick ETFE film on the back surface of the solar cell module produced in the above (5), and a sealing material film which is a film of this example located inside the ETFE film T-type peel test (sample size: width 25 mm, bonded part) by strograph (Toyo Seiki, Strograph VES1D) with a chuck-to-chuck distance of 20 mm and a peel speed of 100 mm / min (continuous pullable distance: 560 mm). 110 mm, non-bonded part 50 mm, measurement n number: 5), and peel strength was measured (Table 2).

(8) Evaluation of solar cell module The performance of the solar cell module produced in (6) above was evaluated using a class A solar simulator meeting the requirements of IEC standard 60904-9 at an irradiance of 1,000 W / m ² . Measured (Table 2).

[Example 2]
In Example 1, the unmodified olefin resin (component B) was changed to a PE copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name “Kernel KS340T”) using a metallocene catalyst, and the modified olefin resin was used. The amount of (Component A) used was changed from 25 parts by weight to 10 parts by weight, the amount of unmodified olefin resin (Component B) was changed from 75 parts by weight to 90 parts by weight, and a polyhydric alcohol compound (Component C) ) Was changed from 1.3 parts by mass (hydroxyl group / acid anhydride group = 1) to 0.5 part by mass (hydroxyl group / acid anhydride group = 1). Manufactured. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, it carried out similarly to Example 1, and manufactured the film and the solar cell module, and performed various evaluation. The results are shown in Table 2.

[Example 3]
Example 1 except that the unmodified olefin resin (component B) in Example 1 was changed to a PE copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name, “Kernel KS340T”) using a metallocene catalyst. In the same manner, pellets were produced. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, it carried out similarly to Example 1, and manufactured the film and the solar cell module, and performed various evaluation. The results are shown in Table 2.

[Example 4]
In Example 1, the unmodified olefin resin (component B) was changed to a PE copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name “Kernel KS340T”) using a metallocene catalyst, and the modified olefin resin was used. The amount of (Component A) used was changed from 25 parts by weight to 50 parts by weight, the amount of unmodified olefin resin (Component B) was changed from 75 parts by weight to 50 parts by weight, and a polyhydric alcohol compound (Component C) ) Was changed from 1.3 parts by mass (hydroxyl group / acid anhydride group = 1) to 2.6 parts by mass (hydroxyl group / acid anhydride group = 1). Manufactured. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, it carried out similarly to Example 1, and manufactured the film and the solar cell module, and performed various evaluation. The results are shown in Table 2.

[Example 5]
In Example 1, the unmodified olefin resin (component B) was changed to a PE copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name “Kernel KS340T”) using a metallocene catalyst, and the modified olefin resin was used. The amount of (Component A) used was changed from 25 parts by weight to 65 parts by weight, the amount of unmodified olefin resin (Component B) used was changed from 75 parts by weight to 35 parts by weight, and a polyhydric alcohol compound (Component C) ) Was changed from 1.3 parts by mass (hydroxyl group / acid anhydride group = 1) to 3.4 parts by mass (hydroxyl group / acid anhydride group = 1). Manufactured. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, it carried out similarly to Example 1, and manufactured the film and the solar cell module, and performed various evaluation. The results are shown in Table 2.

[Comparative Example 1]
Example 1 except that the unmodified olefin resin (component B) was changed to a PE copolymer using a metallocene catalyst (manufactured by Nippon Polyethylene Co., Ltd., trade name, “Kernel KF282”) in Example 1. In the same manner, pellets were produced. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, although it tried to manufacture the film of an olefin type polymer composition similarly to Example 1, since the MFR value was very low and fluidity | liquidity was bad, a favorable molded object was not able to be obtained (Table 2). .

[Comparative Example 2]
In Example 1, the usage amount of the modified olefin resin (component A) was changed from 25 parts by mass to 100 parts by mass, and the usage amount of the unmodified olefin resin (component B) was changed from 75 parts by mass to 0 parts by mass. The amount of the polyhydric alcohol compound (component C) was changed from 1.3 parts by mass (hydroxyl group / acid anhydride group = 1) to 5.2 parts by mass (hydroxyl group / acid anhydride group = 1), Pellets were produced in the same manner as in Example 1. The weight content ratios of Component A and Component B are shown in Table 1. Moreover, although it tried to manufacture the film of an olefin type polymer composition similarly to Example 1, since the MFR value was very low and fluidity | liquidity was bad, a favorable molded object was not able to be obtained (Table 2). .

[Comparative Example 3]
In Example 1, the unmodified olefin resin (component B) was changed to a PE copolymer (manufactured by Nippon Polyethylene Co., Ltd., trade name “Kernel KS340T”) using a metallocene catalyst, and the modified olefin resin was used. The amount of (Component A) used is changed from 25 parts by weight to 75 parts by weight, the amount of unmodified olefin resin (Component B) is changed from 75 parts by weight to 25 parts by weight, and a polyhydric alcohol compound (Component C) is used. ) Was changed from 1.3 parts by mass (hydroxyl group / acid anhydride group = 1) to 3.9 parts by mass (hydroxyl group / acid anhydride group = 1). Manufactured. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, although it tried to manufacture the film of an olefin type polymer composition similarly to Example 1, since the MFR value was very low and fluidity | liquidity was bad, a favorable molded object was not able to be obtained (Table 2). .

[Comparative Example 4]
In Example 1, the usage amount of the modified olefin resin (component A) is changed from 25 parts by mass to 0 part by mass, and the usage amount of the unmodified olefin resin (component B) is changed from 75 parts by mass to 100 parts by mass. The amount of the polyhydric alcohol compound (component C) was changed from 1.3 parts by mass (hydroxyl group / acid anhydride group = 1) to 5.2 parts by mass (hydroxyl group / acid anhydride group = 1), Pellets were produced in the same manner as in Example 1. Table 1 shows the weight content ratio of Component A and Component B and the melting point of Component B. Moreover, it carried out similarly to Example 1, and manufactured the film and the solar cell module, and performed various evaluation. The results are shown in Table 2.

  As is clear from the measurement results shown in Table 2 above, the olefin-based resin compositions according to Examples 1 to 5 exhibit good fluidity in molding and can be formed into a uniform film. Is also excellent in total light transmittance and peel strength. Moreover, the solar cell module concerning the said Examples 1-5 has shown the high initial output value.

  Although the thermoreversible crosslinkable resin composition of the present invention can be used for various applications such as a solar cell module, it can be suitably used particularly for a solar cell module.

Claims (5)

Component A: a modified olefin polymer obtained by grafting at least one unsaturated carboxylic acid anhydride onto an olefin polymer at a component concentration of carboxylic acid anhydride group of 0.1 to 20% by mass,
Component B: an unmodified olefin polymer, and
Component C: a resin composition containing a polyhydric alcohol compound having at least two hydroxyl groups in the molecule,
The crystalline melting point (Tm) of component B is 100 ° C. or lower,
The resin composition, wherein the weight content ratio of component A to component B (component A) / (component B) is 95/5 to 5/95.   2. The resin composition according to claim 1, wherein the weight content ratio (component A) / (component B) of component A to component B is 70/30 to 5/95.   The molded object formed by shape | molding the resin composition of Claim 1 or 2.   The molded article according to claim 3, which is a solar cell element sealing material.   The solar cell module using the solar cell element sealing material of Claim 4.