JP5576375B2 - Master Badge - Google Patents

Description

Related applications

  This application claims the priority of Japanese Patent Application No. 2009-177350 filed on July 30, 2009, and the specification of this Japanese application is incorporated herein by reference. Is done.

The present invention relates to a masterbatch . More specifically , a photovoltaic module including a polymer (hereinafter sometimes referred to as a “polymer binding functional agent”) bonded with a functional agent selected from an ultraviolet absorber, a light stabilizer, and an antioxidant . The present invention relates to a masterbatch that is used in a sealing material.

  The modern society is increasingly dependent on electricity as an energy source. Looking at dependence on electricity, for example, the use of electrical appliances and information equipment in traditional homes and civic life, as well as power sources and information transmission in public facilities, commercial facilities and all industrial fields in cities It is used in electronic equipment, and in transportation, not only mass transportation such as trains and trains, but also the power source of automobiles for personal use has been attempted from plug-in hybrid systems to fully electric vehicles.

  With regard to these power supply sources, there is concern about environmental problems and safety, especially global warming due to carbon dioxide emissions, due to the dependence of conventional fossil fuels such as coal, oil and natural gas on thermal power generation and nuclear power generation. The demand for clean energy is increasing from the feeling. In addition to conventional hydroelectric power generation, there are wind power generation, geothermal power generation, etc., but as a clean energy, solar power generation modules can be used from small devices to large facilities, installation location is not limited, ordinary houses and offices There is a lot of interest in terms of ease of installation, such as on the roof, and safety. The national and local governments are also promoting their introduction and are rapidly spreading. In addition, the development of secondary batteries has enabled direct use of electricity from solar power generation modules, and sales of electricity in addition to electricity sales, leading to expanded use.

  In solar power generation, solar energy is directly converted into electric energy by an energy conversion element such as a silicon cell semiconductor. When this energy conversion element is directly exposed to the external environment, the function of the energy conversion element is lowered and the deterioration further proceeds. Therefore, the energy conversion element is sandwiched between adhesive resin layers called sealing materials and covered with a protective film. As this sealing material sheet, ethylene / vinyl acetate copolymer, ethylene / acrylate copolymer, its carboxylic acid copolymer, ionomer, etc. from adhesiveness, transparency, strength, impact resistance, chemical resistance, etc. Butyral resin is used. Resin materials with excellent durability have been selected as the resin materials used for these encapsulants, but since the usage period is very long, coloring and discoloration may occur as they are, or the resin physical properties may deteriorate. Cracks may occur. Therefore, improvement in weather resistance has been demanded.

  As one method for improving the physical properties of resin materials, an improved method has been proposed in which an ultraviolet absorber, a light stabilizer, a thermal antioxidant, and an organic peroxide are blended in the encapsulant resin layer (patent) Literature 1: JP-A-9-116182). It has also been proposed that benzotriazole- and triazine-based UV absorbers, hindered amine light stabilizers, and hindered phenolic antioxidants be blended into ethylene / (meth) acrylic acid copolymers or their ionomers. (Patent Document 2: JP 2001-261904 A). It has also been proposed to add white inorganic pigments, crosslinking agents, and triallyl cyanurate to ethylene / polar monomer copolymers, and to add additives selected from ultraviolet absorbers, light stabilizers, and antioxidants. (Patent Document 3: JP-A-2006-36874). It has also been proposed to use cerium oxide as an ultraviolet absorber and to use a benzophenone ultraviolet absorber as the ultraviolet absorber (Patent Document 4: JP-A 2006-186233).

  Also known is a polymer-binding functional agent in which a functional agent such as an ultraviolet absorber, a light stabilizer, or an antioxidant is bound to a polymer chain (Patent Document 5: JP-A-2001-19711, Patent Document). 6: Japanese Patent Laid-Open No. 2003-253248, Japanese Patent Laid-Open No. 2005-054183). However, these documents do not disclose that these polymer-binding functional agents are used in combination with a resin member used in a photovoltaic power generation module.

JP-A-9-116182 JP 2001-261904 A JP 2006-36874 A JP 2006-186233 A JP 2001-19711 A JP 2003-253248 A JP-A-2005-054183

  However, many additives such as ultraviolet absorbers, light stabilizers, and antioxidants are not sufficient in solubility and compatibility with resin materials, particularly polyolefin resin materials. In addition, if the amount added was large, the surface gradually bleeded out during the period of use, or a decrease in transparency appeared. Moreover, since these are low molecular weight compounds, they may be volatilized when added to the resin material and subjected to heat kneading, and the effect is reduced when the actual content is reduced. At the same time, this volatilization resulted in material loss, and there were concerns that it would cause contamination of the molding machine and the work environment. In addition, there were concerns about the elution of these compounds into warm water, acidic or alkaline water, and elution into solvents and oils. In particular, amine-based light stabilizers have a risk of performance deterioration or elution due to acid rain. Thus, it is difficult for the above additives to obtain sufficient stability required for long-term use, and further improvement and development of the above functional agents have been demanded.

The present inventors have recently applied a polymer material obtained by combining the above-described various functional agents to a polymer and applying the polymer material to a sealing material used in a photovoltaic power generation module. The present inventors have found that the problem can be solved and have completed the present invention.

Accordingly, an object of the present invention is to provide a master batch for improving the outdoor exposure physical properties of the sealing material used in the photovoltaic power generation module .

The masterbatch used in the sealing material of the photovoltaic module according to the present invention is an ethylene / vinyl acetate copolymer resin, ethylene / ethyl acrylate copolymer or polyvinyl butyral used in the photovoltaic module. A masterbatch that is used in combination with the sealing material to improve the outdoor exposure physical properties of the sealing material made of a resin material, and includes an ultraviolet absorber, a hindered amine light stabilizer, and a hindered phenolic antioxidant. three functional agent of agent, the same resin as the resin material or the one or more polymers of a synthetic resin having a resin material compatible, each of the polymer bound functional agent ing by each bond the blended synthetic resin having the same resin or the resin material compatibility, and the resin material, as well as kneading, one Sea Composite polymer binding function comprising the above three functional agents combined in the same resin as the resin material or in the synthetic resin having compatibility with the resin material by molding into a shaped or pellet shaped molded body As one type of molded product of the agent, it is used by blending with the sealing material, and the polymer binding functional agent is such that the bond between the polymer and the functional agent is a residue of the functional agent. It is formed by the reaction between the introduced reactive group and the polymer, and the polymer-binding functional agent contains 5-95% by mass of the functional agent residue therein. And the said polymer binding functional agent is contained in the said masterbatch so that the content rate in the said masterbatch of the said functional agent part may be 2-30 mass%.

According to the present invention, it is possible to impart good durability to sealing material used in the photovoltaic module. Ultraviolet absorbers, hindered de amine light stabilizer, and since the function component of the hindered de phenolic antioxidant is chemically bonded to the polymer, or loss due to sublimation even when heated process, the environmental pollution There is an effect that the effect can be effectively maintained over a long period of time without being caused, and without being eluted with rain water, environmental water, oil or solvent. Furthermore, by selecting a polymer that is compatible with the resin material used for the sealing material of the photovoltaic power generation module and that has good compatibility, a large amount of the functional agent component can be stably resinated. It can be added to the material. The master batch of the present invention, it is easy to use by adding plural kinds of functional ingredients simultaneously in a resin material, it is advantageous in the point that can improve various properties of the resin at the same time.

<Resin members used in photovoltaic modules>
Examples of the resin member used in the solar power generation module to which the master batch of the present invention can be applied include a sealing material resin, a surface coating resin, and an adhesive resin member.

  The basic configuration of the photovoltaic panel is to sandwich the top and bottom of the photovoltaic cell material (solar cell) with the resin layer of the sealing material, and attach the glass plate to the sealing resin layer on the front side that receives sunlight, A film of a surface coating resin (back sheet) is attached to the sealing resin layer on the back and side surfaces.

  The sealing resin has excellent long-term adhesion to glass, solar cells, and backsheets, is flexible and has excellent solar cell sealing properties, and has high solar ray transmittance and excellent transparency. It is required to have. Furthermore, durability such as heat resistance, high temperature resistance, water / moisture resistance, weather resistance, and reactivity such as easy crosslinkability are required.

  Examples of the sealing resin having these properties include polyolefin polymers, polyether polymers, polyester polymers, polyamide polymers, polyvinyl polymers, polysilicone polymers, polyurethane polymers, and the like. Is mentioned. Among them, polyolefin polymers are preferable, and ethylene copolymer resins have the above-described performance, and are preferable as sealing material resins. For example, ethylene / vinyl acetate copolymer, ethylene / unsaturated carboxylic acid alkyl (carbon number 1 to 8) ester copolymer, ethylene / unsaturated carboxylic acid copolymer, ethylene / unsaturated carboxylic acid alkyl (carbon number 1 -8) Esters / unsaturated carboxylic acid copolymers and their ionomers, particularly ethylene / vinyl acetate copolymers; ethylene / (meth) methyl acrylate copolymers, ethylene / (meta ) Ethyl acrylate copolymer, etc .; Ethylene, unsaturated such as ethylene, methyl (meth) acrylate, (meth) acrylic acid copolymer, ethylene, ethyl (meth) acrylate, (meth) acrylic acid copolymer Carboxylic acid copolymers and their ionomers, and also polyvinyl butyral resins, urethane resins, silicone resins Such as fluorine resin is also preferred.

  The surface coating resin, that is, the back sheet is a resin film that covers the back surface or the side surface, and is directly exposed to the external environment at the installation site. Therefore, in addition to mechanical strength, electrical insulation, chemical resistance, etc., environmental resistance such as heat resistance, water resistance, moisture resistance, salt damage resistance is a very important property. As the resin, known fluororesins, polyolefin resins, polyvinyl resins, poly (meth) acrylic resins, polyether resins, polyester resins, polyamide resins, polycarbonate resins, polysilicon resins, etc. with excellent weather resistance Is mentioned. In particular, polyester resins, fluorine resins, and cyclic polyolefin resins are preferable.

  Examples of the polyester resin include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyester film such as polytrimethylene naphthalate and polybutylene naphthalate, and aluminum foil laminated polyester film and metal. Vapor-deposited or silica-deposited polyester films are also used.

  The physical property improving agent according to the present invention can be added to an adhesive used for a photovoltaic power generation module.

  As the adhesive, an adhesive used in a known laminating method or melting method is preferably used. Examples of the laminating adhesive include a dry laminating adhesive, a wet laminating adhesive, a non-solvent laminating adhesive, and a hot melt adhesive depending on the form of the adhesive. Examples of the resin component of these adhesives include ethylene copolymer resins such as ethylene / vinyl acetate resin, ethylene / acrylic ester resin, ethylene / methacrylic ester resin, acrylic resins such as acrylic ester resin and methacrylate ester resin. , Rubber resins such as nitrile rubber, chloroprene rubber, styrene-butadiene rubber, styrene-isoprene rubber, hydrogenated resins of these rubber resins, polyester resins, polyurethane resins, polyamide resins, polyamide-imide resins, polyimide resins, silicones Examples thereof include an adhesive such as a resin. Further, a reactive adhesive or self-crosslinking in which a reactive group such as an epoxy group, an isocyanate group, a masked isocyanate group, an alkoxymethyl group, a carbodiimide group, a hydroxyl group, or a carboxyl group is introduced into the polymer chain of the resin component of the adhesive. Mold adhesives. Furthermore, crosslinkable adhesives in which known crosslinkers such as epoxy crosslinkers, isocyanate crosslinkers, and alkoxymethylmelamine crosslinkers are used in combination with the above reactive adhesives or self-crosslinkable adhesives. Furthermore, polymerizable adhesives including a polymerizable oligomer such as a heat polymerizable adhesive, an ultraviolet curable adhesive, and an electron beam curable adhesive, and a polyfunctional polymerizable monomer can be used.

  Examples of the resin component of the melt-extruded adhesive include, for example, polyethylene resin, ethylene and acrylic acid, methacrylic acid, their metal salts, vinyl acetate, acrylic acid ester, methacrylic acid ester and other comonomers. Examples thereof include known thermoplastic resins such as resins, polypropylene resins, and acid-modified polypropylene resins.

<Polymer binding functional agent>
In the present invention, one obtained by binding one or more functional agents selected from an ultraviolet absorber, a light stabilizer, and an antioxidant to a polymer is referred to as a polymer binding functional agent.

  In the present invention, the functional agent constituting the polymer binding functional agent is selected from an ultraviolet absorber, a light stabilizer, and an antioxidant. Examples of the ultraviolet absorber include benzotriazole, hydroxyphenyltriazine, benzophenone, benzoate, salicylate, and cyanoacrylate ultraviolet absorbers. Examples of the light stabilizer include hindered amine light stabilizers. Antioxidants include hindered phenol and phosphite antioxidants.

  These functional agents may be used alone or in combination, and it is also preferable to use those having different functions in combination. This is because the multifaceted physical properties such as the sealing material resin can be improved. Such use in combination may be performed by using a combination of a plurality of functional agents bonded in the same polymer molecule, or a combination of polymers combined with the respective functional agents. It is also possible to combine both methods.

  In the present invention, the polymer constituting the polymer binding functional agent is preferably selected in consideration of the type of resin member used in the photovoltaic power generation module to be improved, and particularly used in the photovoltaic power generation module. It is preferable to select a polymer that is compatible with the resin member to be formed. Preferred polymers include polyolefin polymers, poly (meth) acrylic ester polymers, polyvinyl polymers, polyether polymers, polyester polymers, polyamide polymers, polysilicone polymers, or polyurethane polymers. Examples include polymer chains such as polymers.

  Regarding ethylene-based copolymers most used as encapsulant resins for photovoltaic modules, polymer chains include ethylene / vinyl alcohol copolymers having hydroxyl groups as reactive groups, ethylene / vinyl alcohol / vinyl acetate. Copolymer, vinyl alcohol / vinyl butyral copolymer, etc .; ethylene / (meth) acrylic acid copolymer having a carboxylic acid derivative group such as carboxyl group, acid anhydride group, acid halogenide group, lower alkyl ester group, Ethylene / (meth) acrylic acid (carbon number: 1 to 8) ester / (meth) acrylic acid copolymer, acid halide derivatives thereof, ethylene / maleic anhydride copolymer, ethylene / (meth) acrylic acid lower alkyl (Carbon number: 1 to 4) ester copolymer; Ethyl having glycidyl group or chlorohydrin group And (meth) acrylic acid glycidyl ester copolymer, ethylene (meth) acrylic acid alkyl (carbon number: 1 to 8) ester and (meth) acrylic acid glycidyl ester copolymer, and the like. Polymers obtained by reacting one or more polymers are preferably used.

  Even in the case of a backsheet resin, it is preferable in terms of compatibility and physical properties to use the same polymer chain as that resin. Specific examples thereof include a fluorine polymer and a polyolefin polymer. , Polyvinyl polymer, poly (meth) acrylic polymer, polyether polymer, polyester polymer, polyamide polymer, polycarbonate polymer, and polysilicone polymer.

  In particular, when the back sheet resin is a polyester resin film, ethylene glycol, trimethylene glycol or butylene glycol is used as the diol, and dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid and their methyl esters and diglycol esters are used as the dicarboxylic acid. A polyester chain using a derivative such as benzene or halogenide is preferred.

  The bonding method between the polymer and the functional agent is preferably formed by a reaction between a reactive group introduced into the functional agent residue and the polymer.

  The polymer-binding functional agent used in the present invention may be produced by a known method. For example, the method described in JP-A No. 2001-19711, JP-A No. 2003-253248, JP-A No. 2005-054183 and the like can be used. It can be manufactured similarly.

  The functional agent residue, which is a chemical structure exhibiting various functionalities, has various reactive groups that can be bonded to the polymer, or has been introduced, and binds to the polymer via the reactive groups. .

As a functional agent residue of a specific compound of a benzotriazole-based ultraviolet absorber, for example, [3 -alkyl (0 to 4 carbon atoms) -4-hydroxy-5- (2H-benzotriazol-2-yl) -phenyl ] Residue, [3 -alkyl (0 to 4 carbon atoms) -4-hydroxy-5- (2H-benzotriazol-2-yl) -phenyl] residue, [2 -alkyl (0 to 4 carbon atoms)- 3-hydroxy-4- (2H-benzotriazol-2-yl) -phenyl-oxy] residue, [2 -alkyl (0 to 4 carbon atoms) -3-hydroxy-4- (5-chloro-2H-benzo] And benzotriazole-based ultraviolet absorber residues such as triazol-2-yl) -phenyl-oxy] residue.

The reactive group introduced into the ultraviolet absorber residue, A alkylene (1-6 carbon atoms) carboxylic acids, lower alkyl (1-6 carbon atoms) esters, acid halogenide, hydroxyalkyl (1 carbon atoms 10) ester, (2-hydroxy-3-alkyl (C1-20) oxy ) propyl ester, (2-hydroxy-3-phenyl-oxy ) propyl ester , alkylene (C1-6) alcohol , ( 2 - hydroxy-3- alkyl Le (20 1 to 20 carbon atoms) oxy) propane, (2-hydroxy-3-phenyl - oxy) propane, (2-hydroxy-3- alkyl (having 1 to 20 carbon atoms) carbonyloxy) Propane, and tricarboxylic acid anhydride, tetracarboxylic acid anhydride, tricarboxylic acid anhydride / monohalogenide Glycidol, such as bifunctional derivative groups obtained by reacting a polyfunctional compound such as diepoxy compounds. In consideration of the reactive group possessed by the polymer, one or more reactive groups are selected from the above, and one or two or more reactive groups are introduced into the functional agent residue for bonding with the polymer. used.

As the functional agent residues triazine-based UV absorber, [4- [4,6-bis (alkyl (0-4 carbon atoms) phenyl) -1,3,5-triazin-2-yl] -3 - hydroxy Schiff Eniru - oxy] residues, [4- (4,6 - di-phenyl-1,3,5-triazin-2-yl) -3 - hydroxy Schiff Eniru - oxy] residues, and the like, the reaction similar to the above as gender group, an alkylene (1-6 carbon atoms) carboxylic acids, lower alkyl (1-6 carbon atoms) esters, acid halogenide, hydroxyalkyl (C1-10) ester, (2- hydroxy-3- alkyl (having 1 to 20 carbon atoms) oxy) propyl ester, (2-hydroxy-3-phenyl -) propyl ester, an alkylene (1-6 carbon atoms) alcohol, (2-hydroxy 3-alkyl (C1-20) oxy) propane, (2-hydroxy-3-phenyl - oxy) propane, (2-hydroxy-3- alkyl (having 1 to 20 carbon atoms) include carbonyloxy) propane Furthermore, a bifunctional derivative group obtained by reacting these with a tricarboxylic acid anhydride / monocarboxylic acid, a tetracarboxylic acid anhydride, a tricarboxylic acid anhydride / monohalogenide, glycidol, or a diepoxy compound may be used. In the same manner as described above, one or two or more types of reactive groups are selected in consideration of the reactive group of the polymer, and one or two or more reactive groups are introduced into the functional agent residue. Used for binding.

  Examples of the hindered amine light stabilizer having a reactive group include 4-hydroxy-2,2,6,6-tetramethyl-4-piperidine, 4-hydroxy-1,2,2, and the like. 6,6-pentamethyl-4-piperidine, 1-octyloxy-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine, 2,4-bis [N-butyl-N- (1-cyclohexyl) And oxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine. One or more reactive hindered amine light stabilizers can be combined with the polymer.

  Examples of the hindered phenol antioxidant having a reactive group include 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid ethyl ester, 3- ( 3-t-butyl-5-methyl-4-hydroxyphenyl) propionic acid ethyl ester, 3,5-di-t-butyl-4-hydroxybenzoic acid ethyl ester and the like. One or more reactive hindered phenolic antioxidants can be combined with the polymer.

  When the polymer is a polyester resin film, a bifunctional derivative is used as a functional agent to be bonded to the polymer chain to introduce it into the main chain of the polymer chain, and 1 for bonding to the side chain or terminal of the polymer. It is preferable to use one having a functional reactive group introduced therein.

  As a preferable method for introducing the functional agent into the polymer, there is a method in which a bifunctional compound in which two functional agents are made reactive is added, and this functional agent is added during the polymerization of the polyester, and a co-condensation reaction is performed together. It is done. As the functional agent, in addition to the functional agent in which two hydroxyl groups or carboxyl groups are introduced into the molecule as described above, a functional agent having one hydroxyl group is selected from butanetetracarboxylic anhydride, trimellitic anhydride, pyromellitic. Reaction with acid anhydride, trimellitic acid anhydride / monochloride, etc. to react bifunctional functional agent with two carboxyl groups introduced, and further functional agent with one carboxyl group with glycidol or diepoxy compound Thus, a bifunctional functional agent having two hydroxyl groups can be preferably used.

<Masterbatch / Liquid composition>
The resin physical property improving agent according to the present invention may be used in the form of a polymer to which a functional agent is bound. However, for ease of use, the physical property of the polymer to which the functional agent is bound should be improved. It is preferable to use it in the form of a master batch which is mixed with a resin member to be prepared or a synthetic resin and / or resin wax having compatibility therewith, kneaded, and molded into, for example, a sheet or pellet form.

  According to a preferred embodiment of the present invention, the content of the polymer-binding functional agent in the master batch is appropriately determined in consideration of the required performance, the type and combination of functional agents used, the type of resin member to be applied, and the like. A polymer binding functional agent containing 5 to 95% by mass, preferably 10 to 60% by mass of a functional agent residue may be used alone or in combination, and a synthetic resin or wax as a dispersion medium, and a master batch. It is preferable that the content of the functional agent portion is in the range of 2 to 30% by mass.

  The amount of the master batch added to the resin member used in the photovoltaic module may be appropriately determined in consideration of the required performance, the type and combination of functional agents used, the type of resin member applied, and the like. However, generally, a masterbatch is added so that the sum total of the functional agent component contained in 100 mass parts of resin members may become a ratio of 2-30 mass parts.

  Further, according to another aspect of the present invention, the resin property improving agent according to the present invention is a liquid composition in which a polymer binding functional agent is dispersed or dissolved in an appropriate liquid medium, and this is used as a paint or a coating agent. It is also preferable to do. The addition amount of the polymer binding functional agent in the liquid composition may be appropriately determined in consideration of the required performance, the type and combination of functional agents used, the type of resin member to be applied, etc. The polymer binding functional agent containing 5 to 95% by mass of the functional agent residue is set to a concentration at which the functional agent part contains 2 to 30% by mass. A film-forming material may be added to the liquid composition according to this embodiment as necessary.

  Specific examples of the liquid medium of the liquid composition according to the present invention include ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohesanone, and hydrocarbon solvents such as cyclohexane, methylcyclohexane and xylene. Known solvents such as solvents, glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate, and alcohol solvents such as isopropanol and butanol can be used.

  Specific examples of the film-forming material added to the liquid composition according to the present invention as needed include, for example, ethylene and vinyl acetate, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid and the like. Copolymer resins with monomers, acrylic resins such as acrylic ester resins and methacrylic ester resins, polyester resins, polyurethane resins, etc., and epoxy resins, isocyanate groups, masked isocyanate groups, alkoxymethyl groups, carbodiimides, etc. Examples thereof include a reactive resin or a self-crosslinking resin into which a reactive group such as a group, a hydroxyl group or a carboxyl group is introduced. Furthermore, known coating film forming materials such as crosslinkable resins using the above reactive resins or self-crosslinking resins in combination with known crosslinking agents such as epoxy crosslinking agents, isocyanate crosslinking agents, and alkoxymethylmelamine crosslinking agents. It is done.

  In the present invention, the polymer-binding functional agent is used as it is, or as a master batch or liquid composition containing the same, to improve the physical properties of the resin material used for the photovoltaic power generation module. The amount of may be determined as appropriate. According to one preferable aspect of the present invention, the amount of the functional agent component is 0.5 to 15 parts by mass of the ultraviolet absorber content or application amount relative to the resin material, and the light stabilizer is 0.5 to 20 parts. It is preferable that a mass part and antioxidant are 0.1-20 mass parts. According to a preferred embodiment of the present invention, the functional agents are preferably used in combination. As described above, a plurality of functional agents bonded in the same polymer molecule may be used, or a polymer in which each functional agent is bonded may be used in combination. You may combine. It is also preferable to use the same kind of functional agent components in combination. For example, it is also preferable to use a benzotriazole-based UV absorber polymer-binding functional agent in combination with a triazine-based UV absorber polymer-binding functional agent.

  It does not specifically limit as a photovoltaic power generation cell to which this invention is applied, A well-known cell is used. As a silicon system, a single crystal, polycrystal, microcrystal, or amorphous silicon film is used in a thin film type, a hybrid type, a tandem type, a spherical type, or the like. Known compound systems, dye-sensitized titanium oxide types, organic thin film types, quantum dot types, and the like are used.

  Sealing material sheet (high weather resistance / high resin physical property sealing material sheet) and back coat film (high weather resistance / high physical property back) in which the polymer binding functional agent of the present invention is internally added to improve weather resistance and resin physical properties A method for preparing a photovoltaic power generation module using a coated film is performed according to a conventional method. For example, the photovoltaic cell module is sandwiched from the front and back surfaces with a high weather resistance and high resin property sealing material sheet containing a polymer binding functional agent, and the whole is sealed. It is coated with a high weather resistance / high resin property sealing material sheet. Place a glass plate on the top, use an electric heating laminator to reduce the whole pressure to 3 minutes, heat the hot plate to 120 ° C to 140 ° C to soften the resin layer, and press to integrate the whole. Then, the hot plate is heated to 150 ° C. to 160 ° C. and held for 10 minutes to 40 minutes to form a cross-linking bond, and the whole is sealed to prepare a photovoltaic power generation module.

  Next, the present invention will be described in more detail with reference to specific production examples and examples. In the text, g and% are based on mass unless otherwise specified.

<Synthesis Example 1> (Synthesis of Polymer Bonded UV Absorber-1)
In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen blower, and a reflux condenser connected to a decompressor, an ethylene / methyl methacrylate copolymer (methyl methacrylate content 28%) as a polymer having a reactive group , Melt flow (MFR) 450 g / 10 min) 357.0 g (0.997 equivalents) and 2- [4- (2-hydroxy-3- (2′-ethylhexyl) oxy] as a UV absorber having a reactive group ) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (molecular weight: 584) 160.9 g (0.276 mol) was charged while nitrogen was blown in. Heated to melt. Catalysts 0.89 g of tin octylate and 1.79 g of 2,6-di-tert-butyl-4-methylphenol (BHT) were added, and the temperature was raised to 200 ° C. The reaction was carried out for 6 hours while adding 50 g of xylene, and further 0.89 g of tin octylate was added and reacted for 7 hours. Methanol generated during the reaction was removed from the system with a cooler. The progress of the reaction was confirmed by infrared absorption spectrum. After completion of the reaction, xylene was distilled off under reduced pressure, and then cooled and poured into isopropyl alcohol to precipitate a reaction product and filtered. The polymer was washed with isopropyl alcohol and dried to obtain "Polymer-bound UV absorber-1". The product was confirmed by infrared absorption spectrum and NMR. The content of the ultraviolet absorber residue was 30.2%.

<Synthesis Example 2> (Synthesis of polymer-bound ultraviolet absorber-2)
In the same reactor as in Synthesis Example 1, an ethylene / vinyl alcohol / vinyl acetate copolymer (mass ratio; 82.1: 14.7: 3.1, hydroxyl group equivalent: 299.4) 375.4 g (1.254) Equivalent), xylene 200 g, 3- [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-tert-butyl-phenyl] propionic acid ethyl ester (molecular weight: 367.4) 182.6 g ( 0.497 mol) was charged and dissolved by heating. As a catalyst, 0.38 g of monobutyltin oxide and 0.76 g of BHT were added and subjected to a heat reaction in the same manner as in Synthesis Example 1 to obtain “Polymer-bound UV absorber-2”. The product was confirmed by infrared absorption spectrum and NMR. The content of the ultraviolet absorber residue was 30.1%.

<Synthesis Example 3> (Synthesis of Polymer Bonded UV Absorber-3)
378.5 g (0.9735 equivalent) of ethylene / methyl methacrylate copolymer and 2- [3-hydroxy-4- (2H-benzotriazol-2-yl) -phenyl-oxy] -ethyl alcohol (molecular weight: 270.3) 165.2 g (0.611 mol), 0.87 g of tin octylate and 1.74 g of BHT were used as a catalyst in the same manner as in Synthesis Example 1 to prepare “Polymer-bound UV absorber-3”. Obtained. The product was confirmed by infrared absorption spectrum and NMR. The content of the ultraviolet absorber residue was 30.3%.

<Synthesis Example 4> (Synthesis of polymer-bound light stabilizer-1)
374.4 g (1.046 equivalent) of ethylene / methyl methacrylate copolymer and 132.0 g (0. 1) of 4-hydroxy-1,2,2,6,6-pentamethyl-piperidine (molecular weight: 171.3) 771 mol), and a polymer-bonded light stabilizer-1 was obtained in the same manner as in Synthesis Example 1 except that 0.75 g of tetrabutyl titanate and 1.87 g of BHT were used as catalysts. The product was confirmed by infrared absorption spectrum and NMR.

<Synthesis Example 5> (Synthesis of polymer-bound antioxidant-1)
308.0 g (1.029 equivalent) of ethylene / vinyl alcohol / vinyl acetate copolymer and 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid ethyl ester (average molecular weight: 306 .4) “Polymer bound antioxidant-1” was prepared in the same manner as in Synthesis Example 2 except that 234.8 g (0.766 mol) and 0.59 g of monobutyltin oxide and 1.17 g of BHT were used as the catalyst. Obtained. The product was confirmed by infrared absorption spectrum and NMR.

<Synthesis Example 6> (Synthesis of Polymer Bonded UV Absorber-4)
In the same manner as in Synthesis Example 2 except that polyvinyl butyral resin (vinyl alcohol content: 20% by mass) was used in place of the ethylene / vinyl alcohol / vinyl acetate copolymer, a polyvinyl butyral resin-based “polymer-bonded ultraviolet absorber” was used. -4 "was synthesized.

<Synthesis Example 7> (Synthesis of polymer-bound ultraviolet absorber-5)
2- [4- [ (2-Hydroxy-3- (2′-ethylhexyl) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- 2- [4- [ (2- (carboxyethylcarbonyloxy) -3- (2′-ethylhexyl) propyl) oxy ] -2-hydroxyphenyl] -4,6-, obtained by reacting triazine with succinic anhydride A polyvinyl butyral resin-based “polymer-bonded ultraviolet absorber-5” was synthesized in the same manner as in Synthesis Example 6 except that bis (2,4-dimethylphenyl) -1,3,5-triazine was used.

<Synthesis Example 8> (Synthesis of polymer-bound light stabilizer-2)
1,2,2,6,6-pentamethyl-piperidine-4-oxycarbonylethylcarboxylic acid obtained by reacting 4-hydroxy-1,2,2,6,6-pentamethyl-piperidine with succinic anhydride is used Except that, polyvinyl butyral resin-based “polymer-bound light stabilizer-2” was synthesized in the same manner as in Synthesis Example 6.

<Synthesis Example 9> (Synthesis of polymer-bound antioxidant-2)
A polyvinyl butyral resin-based “polymer-bound antioxidant” was used in the same manner as in Synthesis Example 6 except that 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid ethyl ester was used. -2 "was synthesized.

<Production Example 1> (Production Example of Masterbatch Containing Polymer Bonded UV Absorber)
The heavy weight obtained in Synthesis Example 1 was added to 33.77 parts of an ethylene / vinyl acetate copolymer resin (vinyl acetate content: 28%, MFR: 15 g / 10 min) that can be used as a sealing material resin for a photovoltaic module. 66.23 parts of united-bonded UV absorber-1 is kneaded with a mixing roll (roll surface temperature: 120 ° C.), drawn out as a sheet using a sheeting machine, and cut to a polymer-bonded UV of about 20 cm × 20 cm × 5 mm. A masterbatch containing the absorbent was obtained. This master batch contains 20% by mass in terms of triazine-based ultraviolet absorber. Hereinafter, it is referred to as polymer-bound ultraviolet absorber masterbatch-1.

<Production Example 2> (Production Example of Masterbatch Containing Polymer Binding Functional Agent)
In the same manner as in Production Example 1, each master batch containing 20% by mass of the functional agent component of the polymer binding functional agent obtained in Synthesis Examples 2 to 5 was prepared. Polymer bound UV absorber-2 is 66.45 parts, Polymer bound UV absorber-3 is 66.01 parts, Polymer bound light stabilizer-1 is 79.68 parts, Polymer bound antioxidant-1 Each sampled 52.08 parts, blended with ethylene-vinyl acetate copolymer resin so that the total mass would be 100 parts, kneaded with a mixing roll, cut using a sheeting machine, each master batch It was. They are referred to as Polymer Bonded UV Absorber Masterbatch-2, Polymer Bonded UV Absorber Masterbatch-3, Polymer Bonded Light Stabilizer Masterbatch-1 and Polymer Bonded Antioxidant Masterbatch-1, respectively.

<Production Example 3> (Example of production of a masterbatch containing a composite of a polymer binding functional agent)
As a functional agent component, a master batch of a polymer binding functional agent containing a composite of an ultraviolet absorber, a light stabilizer, and an antioxidant was prepared. Ethylene / ethyl acrylate copolymer resin (ethyl acrylate content: 20% by mass) 32.51 parts used as encapsulant resin, 16.56 parts of polymer-bonded UV absorber-1 and polymer bond 16.61 parts of UV absorber-2, 23.90 parts of polymer-bound light stabilizer-1 and 10.42 parts of polymer-bound antioxidant-1 are blended, kneaded, cut, and masterbatch Got. The total content of the functional agent component is 20% by mass, and as the functional agent component, hydroxyphenyltriazine-based UV absorber: benzotriazole-based UV absorber: hindered amine-based light stabilizer: hindered phenol-based antioxidant In a composite at 25: 25: 30: 20. Hereinafter, this is referred to as polymer binding functional agent composite masterbatch-1.

<Production Example 4> (Production Example of Polyvinyl Butyral Resin Master Batch)
Using the polyvinyl butyral resin used as the sealing material resin instead of the ethylene-vinyl acetate copolymer resin used in Production Example 1, the polymer-bonded ultraviolet absorber-4 obtained in Synthesis Example 6 and Synthesis Example 7 The polymer-bonded UV absorber-5 obtained in 1 above, the polymer-bound light stabilizer-2 obtained in Synthesis Example 8 and the polymer-bonded antioxidant-2 obtained in Synthesis Example 9 were blended, kneaded and sheeted. As a result, a polyvinyl butyral resin master batch of each polymer binding functional agent was obtained. This is preferably used for a polyvinyl butyral resin-based sealing material.

<Production Example 5> (Production Example of Additive Masterbatch)
40 parts of the ethylene / vinyl acetate copolymer resin used in Production Example 1, 50 parts of titanium oxide white pigment and 10 parts of triallyl cyanurate were blended and kneaded in a twin-screw extruder to obtain a master batch. It was. Hereinafter, this is referred to as “additive masterbatch”.

Next, using the masterbatch obtained above, the properties of the polymer binding functional agent in the sealing material resin by actual blending were examined.
7.5 parts of polymer-bound UV absorber masterbatch-1 and 5.0 parts of polymer-bound UV absorber masterbatch-3, 75.0 parts of ethylene / vinyl acetate copolymer resin, polymer-bound light stabilizer 7.5 parts of masterbatch-1 and 5.0 parts of polymer-bound antioxidant masterbatch-1 were blended, kneaded with a mixing roll, and molded with a hot press to prepare a sheet having a thickness of about 1 mm. . Naturally, the polymer binding functional agent did not sublime during the heating and kneading, and there was no contamination of the processing machine.

The test piece produced from the obtained sheet showed sufficiently good results in the physical property test. Further, the obtained sheet was heated in a gear oven at 60 ° C., and the blooming phenomenon of the added polymer binding functional agent on the sheet surface was examined from the state of cloudiness on the surface. Naturally, the polymer-binding functional agent sheet did not show any blooming phenomenon to the surface.
Similarly, the masterbatch using the polymer-bound ultraviolet absorbers-2 and -4, the polymer-bound light stabilizer-2 and the polymer-bound antioxidant-2 showed the same excellent performance.
The functional agents such as known low molecular weight UV absorbers used for comparison caused significant blooming of the functional agent on the surface.

The thermal stability was compared with known low molecular weight UV absorbers, light stabilizers and antioxidants. The polymer binding functional agent shows a slight decrease in weight that is thought to be attributable to the polymer component, but almost no weight loss is observed, whereas known UV absorbers, light stabilizers, and antioxidants At about 190 ° C to 200 ° C, there was a significant weight loss due to sublimation, confirming that the conditions of use were limited.
Moreover, the masterbatch which used the polymer coupling | bonding functional agent produced by the above other synthesis examples and manufacture examples also showed the same outstanding performance.

<Example 1>
An ethylene / vinyl acetate copolymer resin-based encapsulant with an internally added polymer-bound composite functional agent used in a photovoltaic power generation module was prepared as follows.
The ethylene / vinyl acetate copolymer resin (vinyl acetate content: 28%, MFR: 15 g / 10 min) used as a sealing material resin for the photovoltaic module is 49.5 parts, and the weight obtained in Production Example 1 is used. 7.5 parts of combined-bonded UV absorber masterbatch-1, 5.0 parts of polymer-bonded UV absorbent masterbatch-3 obtained in Production Example 2, and 7 parts of polymer-bonded light stabilizer masterbatch-1 5 parts, 5.0 parts of polymer-bound antioxidant masterbatch-1 and 20.0 parts of an additive masterbatch containing the white pigment and polyfunctional monomer obtained in Preparation Example 5, peroxide As a mixture, 2.0 parts of t-butylperoxyisopropyl carbonate and 0.5 parts of vinyltrimethoxysilane as a silane coupling agent were mixed, mixed thoroughly, and then kneaded at 100 ° C. with an extruder. It was extruded into 1mm sheet.

  According to a conventional method, the silicon cell module was sandwiched from the front and back with the ethylene / vinyl acetate copolymer resin-based sealing material sheet obtained above, and the whole was sealed. It was covered with a back sheet made of a polyethylene terephthalate film (high weather resistance and high physical property PET film) having improved weather resistance and resin physical properties by internally adding a polyester-based polymer binding functional agent. A glass plate was placed on the upper surface, and the whole was reduced in pressure using an electrothermal laminator and evacuated for 3 minutes. The hot plate was heated to 135 ° C. to soften the resin layer, and pressed to integrate the whole. Next, the hot plate was heated to 150 ° C. and held for 15 minutes to form a cross-linked bond, and the whole was sealed to prepare a photovoltaic power generation module.

<Example 2>
An ethylene-ethyl acrylate copolymer resin-based sealing material into which a polymer-bonded composite functional agent used for a photovoltaic power generation module was internally added was prepared as follows. 30% of the polymer-binding functional agent composite masterbatch-1 obtained in Production Example 3 was added to 47.5 parts of an ethylene / ethyl acrylate copolymer resin (ethyl acrylate content: 20% by mass) as a sealing material resin. 0.0 part, and 20.0 parts of an additive masterbatch containing the white pigment and polyfunctional monomer obtained in Production Example 5, 2.0 parts of t-butylperoxyisopropyl carbonate as a peroxide, and a silane cup 0.5 parts of vinyltrimethoxysilane was blended as a ring agent, mixed well, kneaded with a twin screw extruder, and extruded into a sheet.

  In the same manner as in Example 1, the silicon cell module was sealed with the above-obtained ethylene-acrylic ester copolymer resin-based sealing material sheet, covered with a highly weather-resistant, high-physical PET film, and a glass plate on the upper surface. Was placed in a vacuum with an electric heating laminator, heated and pressed to form a cross-linked bond, and the whole was sealed to prepare a photovoltaic module.

<Example 3>
A polyvinyl butyral resin-based encapsulant with an internally added polymer-bonded composite functional agent used for a solar power generation module was prepared in the same manner as in Example 1. Polymer-bonded UV absorber-4, polymer-bonded UV absorber-5, polymer-bonded light stabilizer-2 and polymer-bonded polymer obtained in Production Example 4 were added to the polyvinyl butyral resin used as the sealing material resin. Each masterbatch containing antioxidant-2 and the additive masterbatch containing white pigment and multifunctional monomer obtained in Production Example 6, t-butylperoxyisopropyl carbonate and vinyltrimethoxysilane were blended, and After mixing, the mixture was kneaded with an extruder and extruded into a sheet.

  In the same manner as in Example 1, the silicon cell module was sealed with the polyvinyl butyral resin-based sealing material sheet obtained above, covered with a highly weather-resistant and high physical property PET film, a glass plate was placed on the upper surface, and electrothermal heating was performed. A solar power generation module was prepared by evacuating with a type laminator, heating and pressing to form a cross-linked bond, and sealing the whole.

  The photovoltaic power generation module according to the present invention has improved compatibility with the resin member of the polymer-bonded composite functional agent, and can add a necessary amount sufficiently. The effect could be sustained effectively over a long period of time without causing contamination and without leaching with rain water, environmental water, oil or solvent.

Claims (6)

Blended with the above-mentioned encapsulant to improve the outdoor exposure properties of encapsulants made of ethylene / vinyl acetate copolymer resin, ethylene / ethyl acrylate copolymer or polyvinyl butyral resin used in photovoltaic modules A masterbatch used as
One or more kinds of functional agents including an ultraviolet absorber, a hindered amine light stabilizer, and a hindered phenol antioxidant are the same resin as the resin material, or a synthetic resin compatible with the resin material . the polymer, each polymer binding functional agent ing by respectively coupled, blended synthetic resin having the same resin or the resin material compatibility, and the resin material, as well as kneading, one sheet or A composite polymer-binding functional agent containing the three functional agents in combination in the same resin as the resin material or in the synthetic resin having compatibility with the resin material by molding into a pellet-shaped molded body As one type of molded body, it is used by blending with the sealing material,
The polymer-binding functional agent is formed by a reaction between the polymer and the functional agent, a reactive group introduced into a residue of the functional agent and the polymer,
The polymer binding functional agent contains 5 to 95% by mass of the functional agent residue therein, and the polymer binding functional agent is contained in the master batch of the functional agent part. It is contained in the said masterbatch so that a rate may be 2-30 mass%, The masterbatch characterized by the above-mentioned.   The functional agent is one or more ultraviolet absorbers selected from the group consisting of benzotriazole, hydroxyphenyltriazine, benzophenone, benzoate, salicylate, and cyanoacrylate ultraviolet absorbers. The described master batch. The functional agent residues are [3-alkyl (0 to 4 carbon atoms) -4-hydroxy-5- (2H-benzotriazol-2-yl) -phenyl] residue, [3-alkyl (0 carbon atoms). -4) -4-hydroxy-5- (2H-benzotriazol-2-yl) -phenyl] residue, [2-alkyl (0 to 4 carbon atoms) -3-hydroxy-4- (2H-benzotriazole- 2-yl) -phenyl-oxy] residue, [2-alkyl (0-4 carbons) -3-hydroxy-4- (5-chloro-2H-benzotriazol-2-yl) -phenyl-oxy] residue One or more benzotriazole ultraviolet absorber residues selected from the group consisting of groups,
The reactive group is alkylene (carbon number 1-6) carboxylic acid, its lower alkyl (carbon number 1-6) ester, acid halide, hydroxyalkyl (carbon number 1-10) ester, (2-hydroxy-3- Alkyl (C1-C20) oxy) propyl ester, (2-hydroxy-3-phenyl-oxy) propyl ester, alkylene (C1-C6) alcohol, (2-hydroxy-3-alkyl (C1-C1) 20) Oxy) propane, (2-hydroxy-3-phenyl-oxy) propane, or (2-hydroxy-3-alkyl (C1-20) carbonyloxy) propane, and these and tricarboxylic acid anhydride・ Monocarboxylic acid, tetracarboxylic acid anhydride, tricarboxylic acid anhydride ・ Monohalogenide, glycidol, di It is one or two or more reactive groups selected from the group consisting of reactive groups of the bifunctional derivatives obtained by reacting a epoxy compound, masterbatch according to claim 1. The residue of the functional agent is [4- [4,6-bis (alkyl (0 to 4 carbon atoms) phenyl] -1,3,5-triazin-2-yl] -3-hydroxyphenyl-oxy] residue. Group, [4- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-hydroxyphenyl-oxy] residue selected from the group consisting of one or more triazine-based ultraviolet rays An absorbent residue,
The reactive group is alkylene (carbon number 1-6) carboxylic acid, its lower alkyl (carbon number 1-6) ester, acid halide, hydroxyalkyl (carbon number 1-10) ester, (2-hydroxy-3- Alkyl (C1-C20) oxy) propyl ester, (2-hydroxy-3-phenyl-oxy) propyl ester, alkylene (C1-C6) alcohol, (2-hydroxy-3-alkyl (C1-C1) 20) Oxy) propane, (2-hydroxy-3-phenyl-oxy) propane, or (2-hydroxy-3-alkyl (C1-20) carbonyloxy) propane, and these and tricarboxylic acid anhydride・ Monocarboxylic acid, tetracarboxylic acid anhydride, tricarboxylic acid anhydride ・ Monohalogenide, glycidol, di It is one or two or more reactive groups selected from the group consisting of reactive groups of the bifunctional derivatives obtained by reacting a epoxy compound, masterbatch according to claim 1.   The functional agent is 4-hydroxy-2,2,6,6-tetramethyl-4-piperidine, 4-hydroxy-1,2,2,6,6-pentamethyl-4-piperidine, 1-octyloxy-4 -Hydroxy-2,2,6,6-tetramethyl-4-piperidine and 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4 -Il) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine is one or more reactive hindered amine light stabilizers selected from the group consisting of. Master Badge.   The functional agent is 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid ethyl ester, 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propion 1 or more reactive hindered phenolic antioxidants selected from the group consisting of acid ethyl ester and 3,5-di-t-butyl-4-hydroxybenzoic acid ethyl ester The described master batch.