TW201343352A - Method for preventing mutual adhesion of pellets for solar cell sealing materials - Google Patents
Method for preventing mutual adhesion of pellets for solar cell sealing materials Download PDFInfo
- Publication number
- TW201343352A TW201343352A TW102110743A TW102110743A TW201343352A TW 201343352 A TW201343352 A TW 201343352A TW 102110743 A TW102110743 A TW 102110743A TW 102110743 A TW102110743 A TW 102110743A TW 201343352 A TW201343352 A TW 201343352A
- Authority
- TW
- Taiwan
- Prior art keywords
- surfactant
- group
- solar cell
- ethylene
- formula
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/124—Treatment for improving the free-flowing characteristics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Abstract
Description
本發明係關於一種太陽能電池密封材用小粒之防止結塊方法等。 The present invention relates to a method for preventing agglomeration of small particles for a solar cell sealing material, and the like.
已知有利用無機化合物粉末或低分子量聚乙烯蠟塗佈小粒之表面而防止小粒彼此結塊之方法(日本專利特開平1-288408號公報、日本專利特開2001-342259號公報及日本專利特公平2-014934號公報)。 A method of coating a surface of a small particle with an inorganic compound powder or a low molecular weight polyethylene wax to prevent agglomeration of small particles from each other is known (Japanese Patent Laid-Open No. Hei 1-188408, Japanese Patent Laid-Open No. 2001-342259, and Japanese Patent No. Fair No. 2-014934).
本發明包括以下發明。 The invention includes the following invention.
[1]一種太陽能電池密封材用小粒之防止結塊方法，其係將包含乙烯-不飽和酯共聚物與不具有金屬之界面活性劑的水性乳液賦予至太陽能電池密封材用小粒。 [1] A method for preventing agglomeration of small particles for a solar cell encapsulant, which comprises imparting an aqueous emulsion comprising an ethylene-unsaturated ester copolymer and a surfactant having no metal to a pellet for a solar cell encapsulant.
[2]如[1]之方法，其中不具有金屬之界面活性劑包含式(I)所表示之界面活性劑、以及選自由與式(I)所表示之界面活性劑結構不同、具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種基、於10℃~50℃下為液體之界面活性劑所組成之群中之至少1種界面活性劑，
[3]如[3]之方法，其中不具有金屬之界面活性劑包含式(I)所表示之界面活性劑。 [3] The method according to [3], wherein the surfactant having no metal comprises the surfactant represented by the formula (I).
[4]如[2]或[3]之方法，其中不具有金屬之界面活性劑包含式(I)所表示之界面活性劑、及與式(I)所表示之界面活性劑結構不同、具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種基、於10℃~50℃下為液體的界面活性劑。 [4] The method according to [2] or [3] wherein the surfactant having no metal comprises a surfactant represented by the formula (I) and a structure different from the surfactant represented by the formula (I), A surfactant which is a liquid at 10 ° C to 50 ° C is selected from at least one of the group consisting of an ethyloxy group and an oxypropyl group.
[5]一種抗結塊劑，其係太陽能電池密封材用小粒之抗結塊劑，且其包含乙烯-不飽和酯共聚物與不具有金屬之界面活性劑。 [5] An anti-caking agent which is a small-particle anti-caking agent for a solar cell encapsulant, and which comprises an ethylene-unsaturated ester copolymer and a surfactant having no metal.
[6]如[5]之抗結塊劑，其中不具有金屬之界面活性劑為式(I)所表示之界面活性劑、以及選自由與式(I)所表示之界面活性劑結構不同、具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種基、於10℃~50℃下為液體之界面活性劑所組成之群中之至少1種界面活性劑，
[7]如[6]之抗結塊劑，其中不具有金屬之界面活性劑包含式(I)所表示之界面活性劑。 [7] The anti-caking agent according to [6], wherein the surfactant having no metal comprises the surfactant represented by the formula (I).
[8]如[6]或[7]之抗結塊劑，其中不具有金屬之界面活性劑包含式(I)所表示之界面活性劑、及與式(I)所表示之界面活性劑結構不同、 具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種基、於10℃~50℃下為液體的界面活性劑。 [8] The anti-caking agent according to [6] or [7], wherein the surfactant having no metal comprises the surfactant represented by the formula (I), and the surfactant structure represented by the formula (I) different, A surfactant having at least one group selected from the group consisting of an oxyethyl group and an oxypropyl group, and a liquid at 10 ° C to 50 ° C.
[9]如[5]至[8]中任一項之抗結塊劑，其中平均粒徑為0.01μm以上且30μm以下。 [9] The anti-caking agent according to any one of [5] to [8] wherein the average particle diameter is 0.01 μm or more and 30 μm or less.
[10]一種太陽能電池密封材用小粒，其表面附著有如[5]至[9]中任一項之抗結塊劑。 [10] A small particle for a solar cell sealing material, the surface of which is an anti-caking agent according to any one of [5] to [9].
[11]一種太陽能電池密封材用小粒之製造方法，其係於太陽能電池密封材用小粒之表面附著有抗結塊劑之太陽能電池密封材用小粒之製造方法，其將包含乙烯-不飽和酯共聚物與不具有金屬之界面活性劑的水性乳液賦予至太陽能電池密封材用小粒之表面。 [11] A method for producing a pellet for a solar cell encapsulant, which is a method for producing a pellet for a solar cell encapsulant having an anti-caking agent attached to a surface of a pellet for a solar cell encapsulant, which comprises an ethylene-unsaturated ester The aqueous emulsion of the copolymer and the surfactant having no metal is imparted to the surface of the pellet for the solar cell sealing material.
[12]一種太陽能電池密封材，其係使用如[10]之太陽能電池密封材用小粒而獲得。 [12] A solar cell encapsulant obtained by using a pellet for a solar cell encapsulant such as [10].
水性乳液包含乙烯-不飽和酯共聚物與不具有金屬之界面活性劑。 The aqueous emulsion comprises an ethylene-unsaturated ester copolymer and a surfactant having no metal.
水性乳液包含乙烯-不飽和酯共聚物。 The aqueous emulsion comprises an ethylene-unsaturated ester copolymer.
就提高加工性、透明性之觀點而言，乙烯-不飽和酯共聚物之源自不飽和酯之結構單元的含有率較佳為10質量%以上且35質量%以下，更佳為15質量%以上且30質量%以下，進而較佳為18質量%以上且30質量%以下。再者，於乙烯-不飽和酯共聚物含有兩種以上源自不飽和酯之結構單元的情形時，將該乙烯-不飽和酯共聚物所含有之所有源自不飽和酯之結構單元之含量的合計作為源自不飽和酯之結構 單元之含有率。 The content of the structural unit derived from the unsaturated ester of the ethylene-unsaturated ester copolymer is preferably 10% by mass or more and 35% by mass or less, more preferably 15% by mass, from the viewpoint of improving workability and transparency. The above is 30% by mass or less, and more preferably 18% by mass or more and 30% by mass or less. Further, in the case where the ethylene-unsaturated ester copolymer contains two or more structural units derived from an unsaturated ester, the content of all structural units derived from the unsaturated ester contained in the ethylene-unsaturated ester copolymer Total as a structure derived from unsaturated esters The content of the unit.
作為不飽和酯，可列舉：羧酸乙烯酯、不飽和羧酸烷基酯等。 作為羧酸乙烯酯，可列舉：乙酸乙烯酯、丙酸乙烯酯等。作為不飽和羧酸烷基酯，可列舉：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸縮水甘油酯等。 Examples of the unsaturated esters include vinyl carboxylates and unsaturated carboxylic acid alkyl esters. Examples of the vinyl carboxylate include vinyl acetate and vinyl propionate. Examples of the unsaturated carboxylic acid alkyl ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and glycidyl methacrylate.
作為乙烯-不飽和酯共聚物，可列舉：乙烯-乙酸乙烯酯共聚物、乙烯-丙酸乙烯酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸乙酯共聚物、乙烯-甲基丙烯酸縮水甘油酯共聚物及乙烯-乙酸乙烯酯-甲基丙烯酸甲酯共聚物等。 Examples of the ethylene-unsaturated ester copolymer include ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate. Copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer, and ethylene-vinyl acetate-methyl methacrylate copolymer.
就提高加工性之觀點而言，乙烯-不飽和酯共聚物之熔融流動速率(MFR)較佳為4g/10min以上且100g/10min以下。MFR之上限更佳為40g/10min以下。MFR之下限更佳為5g/10min以上。MFR係指利用JIS K7210-1995所規定之方法於溫度190℃、荷重21.18N之條件下測得者。 The melt flow rate (MFR) of the ethylene-unsaturated ester copolymer is preferably 4 g/10 min or more and 100 g/10 min or less from the viewpoint of improving workability. The upper limit of the MFR is preferably 40 g/10 min or less. The lower limit of the MFR is more preferably 5 g/10 min or more. MFR means a method measured by a method specified in JIS K7210-1995 at a temperature of 190 ° C and a load of 21.18 N.
作為乙烯-乙酸乙烯酯共聚物，可列舉Sumitate KA-40(住友化學公司製造)，作為乙烯-甲基丙烯酸甲酯共聚物，例如可列舉：Acryft WH303、Acryft WH302(均為住友化學公司製造)，作為乙烯-甲基丙烯酸縮水甘油酯共聚物，例如可列舉：Bondfast E、Bondfast CG5001(均為住友化學公司製造)等。 Examples of the ethylene-vinyl acetate copolymer include Sumitate KA-40 (manufactured by Sumitomo Chemical Co., Ltd.), and examples of the ethylene-methyl methacrylate copolymer include Acryft WH303 and Acryft WH302 (both manufactured by Sumitomo Chemical Co., Ltd.). Examples of the ethylene-glycidyl methacrylate copolymer include Bondfast E and Bondfast CG5001 (both manufactured by Sumitomo Chemical Co., Ltd.).
乙烯-不飽和酯共聚物之含量相對於水性乳液之總量，通常為80質量%以下，較佳為70質量%以下，更佳為60質量%以下，且例如為10質量%以上，較佳為15質量%以上，更佳為20質量%以上，進而較佳為30質量%以上。 The content of the ethylene-unsaturated ester copolymer is usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and preferably 10% by mass or more, based on the total amount of the aqueous emulsion. It is 15% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more.
乙烯-不飽和酯共聚物可藉由使用自由基聚合起始劑使作為單體成分之乙烯與不飽和酯進行自由基聚合反應而製造。作為進行自由基 聚合反應之聚合槽(聚合反應器)，可列舉皿型反應器或管型反應器。 The ethylene-unsaturated ester copolymer can be produced by radically polymerizing ethylene as a monomer component with an unsaturated ester by using a radical polymerization initiator. As a free radical The polymerization tank (polymerization reactor) for the polymerization reaction may be a dish reactor or a tubular reactor.
水性乳液亦可含有乙烯-不飽和酯共聚物以外之其他樹脂。 The aqueous emulsion may also contain other resins than the ethylenically unsaturated ester copolymer.
作為其他樹脂，可列舉：聚烯烴系樹脂、丙烯酸系樹脂(PMMA)、聚氯乙烯(PVC)、聚偏二氯乙烯、聚苯乙烯(PS)、聚乙酸乙烯酯(PVAc)、聚四氟乙烯(PTFE)、丙烯腈-丁二烯-苯乙烯樹脂(ABS樹脂)、AS(Acrylonitrile-styrene，丙烯腈-苯乙烯)樹脂等聚合物及共聚物以及改性聚合物及改性物等各種者。該等可單獨使用或將2種以上混合使用。 Examples of other resins include polyolefin resin, acrylic resin (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), and polytetrafluoroethylene. Various polymers and copolymers such as ethylene (PTFE), acrylonitrile-butadiene-styrene resin (ABS resin), AS (Acrylonitrile-styrene) resin, modified polymers and modified materials By. These may be used alone or in combination of two or more.
所謂界面活性劑，係作為乳化劑而發揮作用之兩親媒性分子，本發明中所謂不具有金屬之界面活性劑，係不具有成對之金屬陽離子之上述兩親媒性分子。不具有金屬之界面活性劑可單獨使用，亦可將2種以上組合使用，較佳為將2種以上組合使用。 The surfactant is a two-parent molecule that functions as an emulsifier. In the present invention, a surfactant having no metal is the above-described amphiphilic molecule having no pair of metal cations. The surfactant having no metal may be used singly or in combination of two or more kinds, and it is preferred to use two or more types in combination.
作為不具有金屬之界面活性劑，可列舉：高分子型界面活性劑、低分子型界面活性劑、及各自之陽離子性之界面活性劑、陰離子性之界面活性劑、非離子性之界面活性劑及兩性之界面活性劑。較佳為陰離子性之界面活性劑及非離子性界面活性劑，更佳為陰離子性之界面活性劑。 Examples of the surfactant having no metal include a polymer type surfactant, a low molecular type surfactant, and a cationic surfactant, an anionic surfactant, and a nonionic surfactant. And amphoteric surfactants. An anionic surfactant and a nonionic surfactant are preferred, and an anionic surfactant is more preferred.
較佳為可列舉式(I)所表示之界面活性劑。 Preferably, the surfactant represented by the formula (I) is exemplified.
(式(I)中，X表示氫原子或-SO3M，M表示氫原子或NH4。n表示1 ~3之整數。m表示1~100之整數)。 (In the formula (I), X represents a hydrogen atom or -SO 3 M, and M represents a hydrogen atom or NH 4 . n represents an integer of 1 to 3. m represents an integer of 1 to 100).
作為陰離子性之界面活性劑，可列舉：高級醇之硫酸酯鹽、高級烷磺酸鹽、高級羧酸鹽、烷基苯磺酸鹽、聚氧乙烯烷基硫酸酯鹽、聚氧乙烯烷基苯基醚硫酸酯鹽、磺基丁二酸乙烯酯及式(A)所表示之化合物等。較佳為式(A)所表示之化合物。 Examples of the anionic surfactant include a sulfate ester of a higher alcohol, a higher alkanesulfonate, a higher carboxylate, an alkylbenzenesulfonate, a polyoxyethylene alkyl sulfate, and a polyoxyethylene alkyl group. A phenyl ether sulfate salt, a sulfosuccinate, a compound represented by the formula (A), and the like. Preferred is a compound represented by the formula (A).
作為高分子型之陰離子性界面活性劑，可列舉：丙烯酸、甲基丙烯酸、及其酯之共聚物、順丁烯二酸酐-苯乙烯共聚物等。 Examples of the polymer type anionic surfactant include a copolymer of acrylic acid, methacrylic acid, and an ester thereof, and a maleic anhydride-styrene copolymer.
作為陽離子性之界面活性劑，可列舉：十二烷基三甲基銨鹽及十六烷基三甲基銨鹽等烷基銨鹽、十六烷基吡啶鎓鹽及癸基吡啶鎓鹽等烷基吡啶鎓鹽、氧基伸烷基三烷基銨鹽、二氧基伸烷基二烷基銨鹽、烯丙基三烷基銨鹽、二烯丙基二烷基銨鹽等。 Examples of the cationic surfactant include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, cetylpyridinium salt and decylpyridinium salt. An alkyl pyridinium salt, an alkyloxyalkyltrialkylammonium salt, a dioxyalkylene dialkylammonium salt, an allyltrialkylammonium salt, a diallyldialkylammonium salt or the like.
作為非離子性之界面活性劑，可列舉：聚氧乙烯伸丙醚等聚氧乙烯烷基醚、聚氧乙烯烷基苯醚、聚乙二醇脂肪酸酯、環氧乙烷環氧丙烷嵌段共聚物、聚氧乙烯脂肪酸醯胺、環氧乙烷-環氧丙烷共聚物及式(B)所表示之化合物等具有聚氧乙烯結構之化合物或聚氧乙烯山梨糖醇酐脂肪酸酯等山梨糖醇酐衍生物等。 Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, and ethylene oxide propylene oxide. a compound having a polyoxyethylene structure or a polyoxyethylene sorbitan fatty acid ester, etc., such as a segment copolymer, a polyoxyethylene fatty acid decylamine, an ethylene oxide-propylene oxide copolymer, and a compound represented by the formula (B) A sorbitan derivative or the like.
作為高分子型之非離子性界面活性劑，可列舉聚乙二醇-聚丙二醇共聚物等。 Examples of the polymer type nonionic surfactant include a polyethylene glycol-polypropylene glycol copolymer.
作為兩性之界面活性劑，可列舉月桂基甜菜鹼、月桂基二甲基 氧化胺等。 As the amphoteric surfactant, lauryl betaine and lauryl dimethyl Amine oxide and the like.
作為不具有金屬之界面活性劑，具體而言，可列舉日本專利特開昭58-127752號公報所記載之界面活性劑：Latemul AD-25(花王股份有限公司製造)、Latemul E-1000A(花王股份有限公司製造)、Noigen EA-177(第一工業製藥股份有限公司製造)等。其中，較佳為Latemul E-1000A(花王股份有限公司製造)。 Specific examples of the surfactant which does not have a metal include the surfactants described in JP-A-58-127752: Latemul AD-25 (manufactured by Kao Co., Ltd.), and Latemul E-1000A (King) Manufacturing Co., Ltd.), Noigen EA-177 (manufactured by Daiichi Kogyo Co., Ltd.), etc. Among them, it is preferably Latemul E-1000A (manufactured by Kao Corporation).
此種界面活性劑可自市場容易地獲得。 Such surfactants are readily available from the market.
又，作為較佳之不具有金屬之界面活性劑，可列舉：具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種結構、於10℃~50℃下為液體之界面活性劑。該界面活性劑於可防止濕潤時小粒之結塊方面係較佳。 Moreover, as a surfactant which does not have a metal preferably, the interface which has at least 1 structure selected from the group consisting of an oxy-ethyl group and an oxy-propyl-propyl group, and is liquid at 10 degreeC - 50 degreeC. Active agent. The surfactant is preferred in terms of preventing agglomeration of small particles during wetting.
上述界面活性劑可為陰離子性，可為陽離子性，可為非離子性，亦可為兩性，又，可為具有芳香族基者，亦可為僅由脂肪族結構構成者，但較佳為非離子性且僅由脂肪族結構構成者。其中，更佳為具有氧基伸丙基者。 The surfactant may be anionic, cationic, nonionic or amphoteric, or may have an aromatic group or may be composed of only an aliphatic structure, but is preferably Non-ionic and composed only of aliphatic structures. Among them, those having an oxypropyl group are more preferred.
作為上述界面活性劑，可列舉：聚氧乙烯伸丙醚等聚氧乙烯烷基醚、聚氧乙烯烷基苯醚、聚乙二醇脂肪酸酯、環氧乙烷環氧丙烷共聚物、聚氧乙烯脂肪酸醯胺、聚氧乙烯山梨糖醇酐脂肪酸酯等。較佳為環氧乙烷環氧丙烷共聚物。其中，更佳為聚環氧乙烷-聚環氧丙烷嵌段共聚物。 Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide copolymers, and polycondensation resins. Oxyethylene fatty acid decylamine, polyoxyethylene sorbitan fatty acid ester, and the like. Preferred is an ethylene oxide propylene oxide copolymer. Among them, a polyethylene oxide-polypropylene oxide block copolymer is more preferred.
此種界面活性劑可自市場容易地獲得。作為市售品，可列舉：Pluronic L-62、Pluronic L-64、Pluronic L-81、Pluronic L-92(ADEKA公司製造)等。 Such surfactants are readily available from the market. Commercially available products include Pluronic L-62, Pluronic L-64, Pluronic L-81, and Pluronic L-92 (manufactured by Adeka Co., Ltd.).
作為不具有金屬之界面活性劑，特佳為式(I)所表示之界面活性劑、與具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種結構且於10℃~50℃下為液體之界面活性劑的組合。 The surfactant having no metal is particularly preferably a surfactant represented by the formula (I) and at least one structure selected from the group consisting of an ethyloxy group and an oxypropyl group, and is 10 ° C. A combination of liquid surfactants at ~50 °C.
不具有金屬之界面活性劑之含量通常相對於乙烯-不飽和酯共聚物100質量份，為0.1~50質量份，較佳為0.1~20質量份，更佳為0.1~10質量份。 The content of the surfactant having no metal is usually 0.1 to 50 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the ethylene-unsaturated ester copolymer.
於水性乳液包含具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種結構且於10℃~50℃下為液體之界面活性劑、與此外之不具有金屬之界面活性劑的情形時，相對於不具有金屬之界面活性劑之總量，具有選自由氧基伸乙基及氧基伸丙基所組成之群中之至少1種結構且於10℃~50℃下為液體之界面活性劑之含量通常為0.1質量%以上，較佳為1質量%以上，更佳為2質量%以上，又，通常為30%以下，較佳為20%以下，更佳為10%以下。 The aqueous emulsion comprises at least one structure selected from the group consisting of an ethyloxy group and an oxypropyl group, and is a liquid surfactant at 10 ° C to 50 ° C, and has no metal interfacial activity. In the case of the agent, it has at least one structure selected from the group consisting of an oxyethyl group and an oxypropyl group, and is a liquid at 10 ° C to 50 ° C with respect to the total amount of the surfactant having no metal. The content of the surfactant is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and usually 30% or less, preferably 20% or less, more preferably 10% or less. .
水性乳液亦可進而含有鹼性化合物。 The aqueous emulsion may further contain a basic compound.
作為鹼性化合物，較佳為可中和羧基者，例如，較佳為氨或有機胺化合物等。特別是沸點為200℃以下之有機胺化合物可藉由通常之乾燥而容易地蒸發，於使用水性乳液提高防止小粒結塊性能時較佳。 As the basic compound, those which can neutralize the carboxyl group are preferable, and for example, ammonia or an organic amine compound or the like is preferable. In particular, the organic amine compound having a boiling point of 200 ° C or less can be easily evaporated by usual drying, and it is preferable to use an aqueous emulsion to improve the prevention of small particle agglomeration.
作為有機胺化合物，例如可列舉：三乙胺、N,N-二甲基乙醇胺、胺基乙醇胺、N-甲基-N,N-二乙醇胺、異丙基胺、亞胺基雙丙基胺、乙基胺、二乙胺、3-乙氧基丙基胺、3-二乙基胺基丙基胺、第二丁基胺、丙基胺、甲基胺基丙基胺、3-甲氧基丙基胺、單乙醇胺、啉、N-甲基啉、N-乙基啉等。其中，較佳為N,N-二甲基乙醇胺等。 Examples of the organic amine compound include triethylamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine, and iminodipropylamine. , ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, second butylamine, propylamine, methylaminopropylamine, 3-methyl Oxypropyl propylamine, monoethanolamine, Porphyrin, N-methyl Porphyrin, N-ethyl Porphyrin and the like. Among them, N,N-dimethylethanolamine or the like is preferred.
於水性乳液含有鹼性化合物之情形時，其含量較佳為相對於乙烯-不飽和酯共聚物為1~30質量%，更佳為2~20質量%，進而較佳為2~10質量%。 When the aqueous emulsion contains a basic compound, the content thereof is preferably from 1 to 30% by mass, more preferably from 2 to 20% by mass, even more preferably from 2 to 10% by mass, based on the ethylene-unsaturated ester copolymer. .
水性乳液所含有之水通常可使用自來水或去離子水等。 The water contained in the aqueous emulsion can usually be used in tap water or deionized water.
水性乳液較佳為不含有溶劑，但亦可含有溶劑。作為溶劑，可列舉：甲苯、二甲苯等芳香族烴，己烷等脂肪族烴，乙酸乙酯、乙酸丁酯等酯，甲基乙基酮、甲基異丁基酮等酮，甲醇、乙醇、正丙醇、異丙醇、正丁醇等醇，乙二醇、二乙二醇、三乙二醇、丙二醇等二醇系溶劑，甲基賽路蘇、賽路蘇、丁基賽路蘇、二烷、MTBE(甲基第三丁基醚)、丁基卡必醇等賽路蘇系溶劑，二乙二醇單甲醚、三乙二醇單甲醚、丙二醇單甲醚、3-甲氧基-3-甲基-1-丁醇等二醇系溶劑，乙二醇單甲醚乙酸酯、PMA(丙二醇單甲醚乙酸酯)、二乙二醇單丁醚乙酸酯、二乙二醇單***乙酸酯等二醇酯系溶劑；等有機溶劑。該等可單獨使用，亦可組合使用。 The aqueous emulsion preferably contains no solvent, but may also contain a solvent. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and methanol and ethanol. , n-propanol, isopropanol, n-butanol and other alcohols, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, methyl sarsusu, 赛路苏, butyl race road Su, two Acetone, MTBE (methyl tert-butyl ether), butyl carbitol, etc., sulphate solvent, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy a glycol solvent such as benzyl-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, and a glycol ester solvent such as ethylene glycol monoethyl ether acetate; or an organic solvent. These may be used alone or in combination.
於水性乳液含有溶劑之情形時，將乙烯-不飽和酯共聚物設為100質量份，溶劑含量通常為0.001~30質量份，較佳為0.001~10質量份，更佳為0.001~5質量份。 When the aqueous emulsion contains a solvent, the ethylene-unsaturated ester copolymer is 100 parts by mass, and the solvent content is usually 0.001 to 30 parts by mass, preferably 0.001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass. .
水性乳液中，根據需要亦可含有酚系穩定劑、亞磷酸酯系穩定劑、胺系穩定劑、醯胺系穩定劑、抗老化劑、耐候穩定劑、抗沈澱劑、抗氧化劑、熱穩定劑、光穩定劑等穩定劑；觸變劑、增黏劑、分散劑、消泡劑、黏度調整劑、防腐劑、耐候劑、顏料、顏料分散劑、抗靜電劑、潤滑劑、成核劑、阻燃劑、油劑、染料、硬化劑(交聯劑)等添加劑；氧化鈦(金紅石型)、氧化鋅等過渡金屬化合物、碳黑等顏料；玻璃纖維、碳纖維、鈦酸鉀纖維、矽灰石、碳酸鈣、硫酸鈣、滑石、玻璃薄片、硫酸鋇、黏土、高嶺土、二氧化矽細粉末、雲母、矽酸鈣、氫氧化鋁、氫氧化鎂、氧化鋁、氧化鎂、氧化鋁、矽藻土等無機、有機填充劑等。 The aqueous emulsion may further contain a phenolic stabilizer, a phosphite stabilizer, an amine stabilizer, a guanamine stabilizer, an ageing agent, a weathering stabilizer, an antiprecipitant, an antioxidant, and a heat stabilizer. Stabilizers such as light stabilizers; thixotropic agents, tackifiers, dispersants, defoamers, viscosity modifiers, preservatives, weathering agents, pigments, pigment dispersants, antistatic agents, lubricants, nucleating agents, Additives such as flame retardants, oil agents, dyes, hardeners (crosslinkers); transition metal compounds such as titanium oxide (rutile) and zinc oxide, pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, and strontium Gray stone, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, cerium oxide fine powder, mica, calcium citrate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, aluminum oxide, Inorganic and organic fillers such as diatomaceous earth.
水性乳液之製造方法係可利用該領域中公知之方法進行製造，例如，使共聚物聚合後使該共聚物分散於水性介質中後利用乳化法(例如，機械乳化法、強制乳化法、自乳化法、轉相乳化法等)之任一種進行製造。 The method for producing an aqueous emulsion can be produced by a method known in the art. For example, after the copolymer is polymerized, the copolymer is dispersed in an aqueous medium and then subjected to an emulsification method (for example, mechanical emulsification method, forced emulsification method, self-emulsification method). Any one of the phase inversion emulsification method, etc., is manufactured.
具體而言，可列舉：(1)於反應器中投入乙烯-不飽和酯共聚物及溶劑並進行攪拌、加熱溶解，於其中投入不具有金屬之界面活性劑、水及/或溶劑並進行加熱及攪拌，於此前後進而任意地投入水及/或溶劑並進行攪拌的方法；(2)於混練機中投入乙烯-不飽和酯共聚物，且任意地投入溶劑，進行攪拌、加熱熔融，於其中投入不具有金屬之界面活性劑、水及/或溶劑並進行加熱及攪拌，於此前後進而任意地投入水及/或溶劑並進行攪拌的方法等。 Specifically, (1) an ethylene-unsaturated ester copolymer and a solvent are charged into a reactor, stirred, heated and dissolved, and a surfactant, water, and/or a solvent having no metal is introduced and heated. And a method of stirring and adding water and/or a solvent to the mixture before and after, and (2) introducing an ethylene-unsaturated ester copolymer into a kneading machine, optionally introducing a solvent, stirring, heating and melting. Among them, a method in which a metal surfactant, water, and/or a solvent is not added, and heating and stirring are carried out, and water and/or a solvent are arbitrarily added thereto before and after stirring.
於上述(1)之製造方法中，作為反應器，可使用具備可加熱之加熱裝置、及可對內容物賦予剪切力等之攪拌機的容器(較佳為密閉及/或耐壓容器)。 In the production method of the above (1), as the reactor, a container (preferably a sealed and/or pressure-resistant container) having a heating device capable of heating and a stirrer capable of imparting shearing force to the contents can be used.
攪拌機可使用通常者。作為此種耐壓容器，可列舉附帶攪拌機之耐壓高壓釜等。攪拌例如可於常壓或減壓之任一種下進行。又，攪拌機之轉速係例如可以50~1000rpm左右之轉速進行。較佳為，根據需要隨著水性乳液之分散/攪拌之進行而提高轉速。 The mixer can be used in the usual way. As such a pressure-resistant container, a pressure-resistant autoclave equipped with a stirrer or the like can be given. Stirring can be carried out, for example, at any of normal pressure or reduced pressure. Further, the rotation speed of the agitator can be performed, for example, at a number of revolutions of about 50 to 1000 rpm. Preferably, the number of revolutions is increased as the dispersion/stirring of the aqueous emulsion proceeds as needed.
加熱係於通常50~200℃、較佳為60~150℃、進而較佳為70~100℃下進行。 The heating is carried out usually at 50 to 200 ° C, preferably 60 to 150 ° C, and more preferably 70 to 100 ° C.
較佳為，攪拌後自獲得之分散體蒸餾去除(較佳為減壓/加壓蒸餾去除)溶劑。此處之蒸餾去除之方法可利用該領域中公知之方法。減壓/加壓之程度可列舉±0.001~1MPa左右，較佳為±0.001~0.5MPa左右。 Preferably, the solvent is removed by distillation (preferably reduced pressure/pressure distillation) from the obtained dispersion after stirring. The method of distillation removal herein can utilize methods well known in the art. The degree of pressure reduction/pressurization may be about ±0.001 to 1 MPa, preferably about ±0.001 to 0.5 MPa.
於上述(2)之製造方法中，作為混練器，可列舉：輥磨機、捏合 機、擠出機、墨輥、班伯里混合機等。特別是可使用於套管內具有1根或2根以上螺桿之擠出機或多軸擠出機。 In the production method of the above (2), examples of the kneader include a roll mill and kneading. Machine, extruder, ink roller, Banbury mixer, etc. In particular, it can be used in an extruder or a multi-screw extruder having one or more screws in the sleeve.
作為使用擠出機進行攪拌之方法，係將熔融之乙烯-不飽和酯共聚物及不具有金屬之界面活性劑混合，將其自擠出機之料斗或供給口連續地供給，對其進行加熱熔融混練，進而自設置於擠出機之壓縮區域、計量區域及脫氣區域等之至少1個供給口供給水，利用螺桿進行混練後，自模嘴連續地擠出。 As a method of stirring using an extruder, a molten ethylene-unsaturated ester copolymer and a surfactant having no metal are mixed, and the hopper or the supply port of the extruder is continuously supplied and heated. In the melt kneading, water is supplied from at least one supply port provided in the compression zone, the metering zone, and the degassing zone of the extruder, and is kneaded by a screw, and then continuously extruded from the die.
於過量地使用不具有金屬之界面活性劑之情形時，可自獲得之水性乳液分離去除過量之不具有金屬之界面活性劑。不具有金屬之界面活性劑之分離去除例如可列舉使用離心分離機、具有平均孔徑小於水性乳液所含有之分散質之平均粒徑之細孔的過濾片(較佳為具有0.05~0.5μm之平均孔徑之微濾膜)或超濾膜等之方法。 In the case where the surfactant having no metal is used in excess, the excess surfactant-free surfactant can be removed from the obtained aqueous emulsion. The separation and removal of the surfactant having no metal may, for example, be a filter using a centrifugal separator and pores having an average pore diameter smaller than the average particle diameter of the dispersion contained in the aqueous emulsion (preferably having an average of 0.05 to 0.5 μm). A method of a microfiltration membrane of a pore size or an ultrafiltration membrane.
獲得之水性乳液較佳為進行冷卻。藉此，獲得含有細微分散質之水性乳液。作為冷卻方法，可列舉於常溫下進行放置之方法等。根據於常溫下進行放置之方法，於冷卻過程中乙烯-不飽和酯共聚物等未凝聚而可獲得細微且均質之水性乳液。 The aqueous emulsion obtained is preferably cooled. Thereby, an aqueous emulsion containing a finely dispersed substance is obtained. As a cooling method, the method of carrying out at normal temperature, etc. are mentioned. According to the method of placing at room temperature, an ethylene-unsaturated ester copolymer or the like is not aggregated during cooling to obtain a fine and homogeneous aqueous emulsion.
又，獲得之水性乳液亦可根據需要例如使用具有各種孔徑之過濾片等進行過濾。 Further, the obtained aqueous emulsion may be filtered, for example, using a filter sheet having various pore diameters or the like as needed.
水性乳液所含有之分散質之平均粒徑可作為體積基準中值粒徑進行測定。分散質之平均粒徑通常為30μm以下，較佳為0.01~20μm，更佳為0.01~10μm，只要為該範圍內，則靜置穩定性良好。所謂體積基準中值粒徑，為以體積基準計累計粒徑分佈之值相當於50%時之粒徑。 The average particle size of the dispersoid contained in the aqueous emulsion can be measured as a volume-based median diameter. The average particle diameter of the dispersoid is usually 30 μm or less, preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, and if it is within this range, the standing stability is good. The volume-based median diameter is a particle diameter when the value of the cumulative particle size distribution is equivalent to 50% on a volume basis.
分散質包含乙烯-不飽和酯共聚物、及不具有金屬之界面活性劑。 The dispersoid contains an ethylene-unsaturated ester copolymer and a surfactant having no metal.
本發明中之抗結塊劑係均勻地含於自水性乳液所含有之分散質 去除水而成者中。 The anti-caking agent in the present invention is uniformly contained in the dispersoid contained in the aqueous emulsion Remove water from the body.
水性乳液所含有之分散質之粒徑基本不因水之有無而變化，因此水性乳液所含有之分散質之平均粒徑與抗結塊劑之平均粒徑大致相同。 The particle size of the dispersoid contained in the aqueous emulsion does not substantially change depending on the presence or absence of water. Therefore, the average particle diameter of the dispersoid contained in the aqueous emulsion is substantially the same as the average particle diameter of the anti-caking agent.
太陽能電池密封材用小粒(以下，有時稱為本小粒)包含乙烯-不飽和酯共聚物。 The pellet for solar cell sealing material (hereinafter, sometimes referred to as the pellet) contains an ethylene-unsaturated ester copolymer.
就提高加工性、透明性之觀點而言，上述乙烯-不飽和酯共聚物之源自不飽和酯之結構單元的含有率較佳為23質量%以上且33質量%以下，更佳為25質量%以上且32質量%以下。再者，於本發明之乙烯-不飽和酯共聚物含有兩種以上源自不飽和酯之結構單元之情形時，將該乙烯-不飽和酯共聚物所含有之所有源自不飽和酯之結構單元之含量的合計作為源自不飽和酯之結構單元之含有率。 The content of the structural unit derived from the unsaturated ester of the ethylene-unsaturated ester copolymer is preferably 23% by mass or more and 33% by mass or less, more preferably 25%, from the viewpoint of improving workability and transparency. % or more and 32% by mass or less. Further, in the case where the ethylene-unsaturated ester copolymer of the present invention contains two or more structural units derived from an unsaturated ester, all of the unsaturated ester-derived structures contained in the ethylene-unsaturated ester copolymer are contained. The total content of the units is the content ratio of the structural unit derived from the unsaturated ester.
作為不飽和酯，可列舉與上述相同者。 The unsaturated ester is the same as the above.
作為本小粒之乙烯-不飽和酯共聚物，例如可列舉與上述水性乳液所含有之乙烯-不飽和酯共聚物相同者。 The ethylene-unsaturated ester copolymer of the present pellets may, for example, be the same as the ethylene-unsaturated ester copolymer contained in the aqueous emulsion.
就提高加工性之觀點而言，本小粒之乙烯-不飽和酯共聚物之熔融流動速率(MFR)較佳為4g/10min以上且50g/10min以下。MFR之上限更佳為40g/10min以下。MFR之下限更佳為5g/10min以上。MFR係指利用JIS K7210-1995所規定之方法，於溫度190℃、荷重21.18N之條件下測定者。 The melt flow rate (MFR) of the ethylene-unsaturated ester copolymer of the present pellet is preferably 4 g/10 min or more and 50 g/10 min or less from the viewpoint of improving workability. The upper limit of the MFR is preferably 40 g/10 min or less. The lower limit of the MFR is more preferably 5 g/10 min or more. MFR is a method which is measured under the conditions of a temperature of 190 ° C and a load of 21.18 N by the method specified in JIS K7210-1995.
就提高加工性之觀點而言，本小粒之乙烯-不飽和酯共聚物之分子量分佈(Mw/Mn)較佳為2以上且8以下，更佳為2.5以上且4以下。再者，Mw係指上述共聚物之重量平均分子量，Mn係指上述共聚物之數量平均分子量。 The molecular weight distribution (Mw/Mn) of the ethylene-unsaturated ester copolymer of the present pellets is preferably 2 or more and 8 or less, and more preferably 2.5 or more and 4 or less, from the viewpoint of improving workability. Further, Mw means the weight average molecular weight of the above copolymer, and Mn means the number average molecular weight of the above copolymer.
本小粒之乙烯-不飽和酯共聚物之聚乙烯換算之重量平均分子量 較佳為40000~80000，更佳為50000~70000。聚乙烯換算之重量平均分子量係利用凝膠滲透層析測定而求出聚苯乙烯換算之重量平均分子量，再求上述聚苯乙烯換算之重量平均分子量、與聚乙烯與聚苯乙烯之Q因子之比(17.7/41.3)的積，求出聚乙烯換算之重量平均分子量。 The weight average molecular weight of the ethylene-unsaturated ester copolymer of the pellets in terms of polyethylene It is preferably from 40,000 to 80,000, more preferably from 50,000 to 70,000. The weight average molecular weight in terms of polyethylene is determined by gel permeation chromatography to obtain a weight average molecular weight in terms of polystyrene, and the weight average molecular weight in terms of polystyrene and the Q factor of polyethylene and polystyrene are determined. The weight average molecular weight in terms of polyethylene was determined from the product of (17.7/41.3).
作為本小粒之乙烯-不飽和酯共聚物之製造方法，可列舉與上述水性乳液所含有之乙烯-不飽和酯共聚物相同者。 The method for producing the ethylene-unsaturated ester copolymer of the present pellets is the same as the ethylene-unsaturated ester copolymer contained in the aqueous emulsion.
本小粒之形狀例如可列舉：球狀、橢圓球狀、圓柱狀、橢圓柱狀、角狀、棒狀等。又，本小粒之大小較佳為直徑或長度為3mm以上且5mm以下。 Examples of the shape of the granules include a spherical shape, an elliptical shape, a cylindrical shape, an elliptical column shape, an angular shape, and a rod shape. Further, the size of the granules is preferably 3 mm or more and 5 mm or less in diameter or length.
將水性乳液賦予至本小粒之表面並去除水，藉此獲得表面上附著有抗結塊劑之本小粒。附著有抗結塊劑之本小粒防止結塊性能優異。 An aqueous emulsion is applied to the surface of the granules and water is removed, whereby the granules having an anti-caking agent attached to the surface are obtained. The granules to which the anti-caking agent is attached prevent excellent agglomeration performance.
作為將水性乳液賦予至本小粒之表面並去除水之方法，例如可列舉：於料斗內或空氣輸送管線內噴霧水性乳液而以水性乳液被覆本小粒後，藉由進行乾燥而去除水之方法；或將本小粒與水性乳液放入容器中攪拌後進行乾燥之方法等。 As a method of imparting an aqueous emulsion to the surface of the granules and removing water, for example, a method of spraying an aqueous emulsion in a hopper or an air transfer line and coating the granules with an aqueous emulsion, and then removing the water by drying; Alternatively, the granules and the aqueous emulsion are placed in a container and stirred, followed by drying.
又，以工業規模進行時，必需以連續且簡單之操作進行包裝(例如，裝入袋、筒罐、塑膠容器等)等作業(包裝步驟之一例)，因此例如利用如下所述之方法將抗結塊劑賦予至本小粒。 Further, when it is carried out on an industrial scale, it is necessary to perform packaging (for example, loading a bag, a can, a plastic container, or the like) in a continuous and simple operation (an example of a packaging step), and thus, for example, the method described below is used. An agglomerating agent is imparted to the granules.
作為將水性乳液賦予至本小粒之表面並去除水之方法，可列舉具有如下步驟之方法：步驟1a)自擠出機擠出乙烯-不飽和酯共聚物，於水中切割成小粒狀而製造本小粒之步驟，步驟1b)一面使本小粒通過空氣輸送管線移送至下一步驟，一面於該空氣輸送管線內將水性乳液賦予至本小粒表面的步驟， 步驟1c)對表面賦予有水性乳液之本小粒進行乾燥，而去除於步驟1a)中附著之水，獲得表面附著有抗結塊劑之本小粒的步驟，及步驟1d)對表面附著有抗結塊劑之本小粒進行包裝之步驟；或具有如下步驟之方法：步驟2a)自擠出機擠出乙烯-不飽和酯共聚物，於水中切割成小粒狀而製造本小粒的步驟，步驟2b)使本小粒通過空氣輸送管線而向料斗移送的步驟，步驟2c)於料斗內將水性乳液賦予至本小粒表面的步驟，步驟2d)對表面賦予有水性乳液之本小粒進行乾燥，而去除於步驟2a)中附著之水，獲得表面附著有抗結塊劑之本小粒的步驟，及步驟2e)對表面附著有抗結塊劑之本小粒進行包裝之步驟。 As a method of imparting an aqueous emulsion to the surface of the granule and removing water, a method having the following steps: Step 1a) extruding an ethylene-unsaturated ester copolymer from an extruder and cutting it into small granules in water to produce the present invention a step of granules, step 1b) of transferring the granules through the air transfer line to the next step, and applying an aqueous emulsion to the surface of the granules in the air transfer line, Step 1c) drying the granules to which the aqueous emulsion is applied, removing the water adhered in the step 1a), obtaining the granules having the anti-caking agent attached to the surface, and the step 1d) attaching the anti-knot to the surface a step of packaging the granules of the granules; or a method having the following steps: Step 2a) a step of extruding an ethylene-unsaturated ester copolymer from an extruder and cutting into small granules in water to produce the granules, step 2b) a step of transferring the granules to the hopper through the air transfer line, a step 2c) of imparting an aqueous emulsion to the surface of the granules in the hopper, and a step 2d) of drying the granules having the aqueous emulsion on the surface, and removing the granules from the surface. 2a) the step of attaching the water to obtain the granules to which the anti-caking agent is attached, and the step of ejecting the granules to which the anti-caking agent is attached.
步驟2d)亦可於步驟2c)之料斗內進行。 Step 2d) can also be carried out in the hopper of step 2c).
亦可於步驟1a)與步驟1b)之間，或步驟2a)與步驟2b)之間，設置步驟b')進行本小粒之水分去除之步驟。 Steps b') may also be performed between step 1a) and step 1b), or between steps 2a) and 2b), to perform the step of removing moisture from the granules.
附著於本小粒表面之抗結塊劑之量可藉由如下方式算出：於水中對表面附著有抗結塊劑之本小粒進行超音波清洗，使溶出至水中之抗結塊劑乾燥並進行稱量。 The amount of the anti-caking agent attached to the surface of the granules can be calculated by ultrasonically washing the granules having an anti-caking agent attached to the surface in water, and drying the anti-caking agent dissolved in the water and weighing the amount.
相對於本小粒100質量份，使抗結塊劑所含有之乙烯-不飽和酯共聚物0.001~5質量份附著，此情況於抑制本小粒彼此結塊方面較佳。 The 0.001 to 5 parts by mass of the ethylene-unsaturated ester copolymer contained in the anti-caking agent is attached to 100 parts by mass of the granules, and this is preferable in suppressing the agglomeration of the granules.
根據需要，可於小粒中揉合選自由耐光穩定劑、紫外線吸收劑、抗氧化劑、潤滑劑所組成之群中之一種以上化合物，又，亦可使之與抗結塊劑一起附著於本小粒之表面。 If necessary, one or more compounds selected from the group consisting of light stabilizers, ultraviolet absorbers, antioxidants, and lubricants may be blended in the granules, or may be attached to the granules together with the anti-caking agent. The surface.
作為耐光穩定劑，例如可列舉受阻胺系化合物等。作為紫外線吸收劑，例如可列舉二苯基酮系化合物等。作為抗氧化劑，例如可列舉酚系化合物、磷系化合物等。作為潤滑劑，可列舉油酸醯胺、芥酸醯胺、硬脂酸醯胺、二十二烷酸醯胺、乙烯雙油酸醯胺、乙烯雙硬脂 酸醯胺等脂肪酸醯胺化合物等。 Examples of the light stabilizer include a hindered amine compound and the like. Examples of the ultraviolet absorber include a diphenylketone compound and the like. Examples of the antioxidant include a phenol compound and a phosphorus compound. Examples of the lubricant include decyl oleate, decyl erucamide, decylamine stearate, decyl octadecanoate, decyl ethylene oleate, and ethylene double stearin. A fatty acid guanamine compound such as decylamine.
使用本發明之表面附著有抗結塊劑之本小粒而獲得之樹脂製品體積電阻率提高。因此，使用本發明之表面附著有抗結塊劑之本小粒製作之片材等可較佳地用於太陽能電池元件(結晶、多晶、非晶等)之密封及保護所使用之太陽能電池密封材。 The resin article obtained by using the present pellet having the anti-caking agent adhered to the surface of the present invention has an increased volume resistivity. Therefore, the sheet made of the granules to which the anti-caking agent is adhered on the surface of the present invention can be preferably used for sealing and protecting solar cell elements (crystalline, polycrystalline, amorphous, etc.) for solar cell sealing. material.
片狀之太陽能電池密封材之製造方法可列舉如下方法：使用T型模嘴擠出機、壓延成形機等對表面賦予有乙烯-不飽和酯共聚物之本小粒進行加工。於加工成片材之階段，亦可添加耐光穩定劑、紫外線吸收劑、抗氧化劑、潤滑劑、交聯劑、交聯助劑、防霧劑、塑化劑、界面活性劑、著色劑、抗靜電劑、阻燃劑、結晶成核劑等。 The method for producing a sheet-like solar cell sealing material may be a method in which a small particle having an ethylene-unsaturated ester copolymer is applied to a surface by using a T-die extruder or a calender molding machine. At the stage of processing into a sheet, a light stabilizer, a UV absorber, an antioxidant, a lubricant, a crosslinking agent, a crosslinking assistant, an antifogging agent, a plasticizer, a surfactant, a colorant, and an anti-wear agent may be added. An electrostatic agent, a flame retardant, a crystallization nucleating agent, and the like.
以下，例示實施例進一步詳細地說明本發明。只要未特別事先說明，則例中之份及%表示質量基準。 Hereinafter, the present invention will be described in further detail by way of examples. Unless otherwise stated in advance, the parts and % in the examples represent the quality basis.
物性之測定及評價等係利用以下方法進行。 The measurement and evaluation of physical properties were carried out by the following methods.
水性乳液之不揮發成分濃度係利用依據JIS K-6828-1之方法進行測定。 The concentration of the nonvolatile component of the aqueous emulsion was measured by the method according to JIS K-6828-1.
水性乳液所含有之分散質之平均粒徑係使用雷射繞射式粒度分佈測定裝置LA-950V2(堀場製作所股份有限公司製造)，作為粒子折射率1.50時獲得之體積基準中值粒徑進行測定。 The average particle size of the dispersoid contained in the aqueous emulsion was measured by using a laser diffraction type particle size distribution measuring apparatus LA-950V2 (manufactured by Horiba, Ltd.) as a volume-based median diameter obtained when the refractive index of the particle was 1.50. .
源自乙烯-乙酸乙烯酯共聚物所含有之乙酸乙烯酯之結構單元的含有率係將源自乙烯之結構單元之含有率與源自乙酸乙烯酯之結構單元之含有率的總和設為100質量%時的值，依據JIS K7192進行測定。 The content of the structural unit derived from the vinyl acetate contained in the ethylene-vinyl acetate copolymer is such that the sum of the content of the structural unit derived from ethylene and the content of the structural unit derived from vinyl acetate is 100 mass. The value at % is measured in accordance with JIS K7192.
共聚物之熔融流動速率係藉由JIS K7210-1995所規定之方法，於溫度190℃、荷重21.18N之條件下進行測定。 The melt flow rate of the copolymer was measured by a method specified in JIS K7210-1995 at a temperature of 190 ° C and a load of 21.18 N.
於具備攪拌機、溫度計、回流冷卻管之容器1L之分離式燒瓶反應容器中，加入甲苯200份、及乙烯-不飽和酯共聚物(A-1)[乙烯-甲基丙烯酸甲酯共聚物，Acryft WH303住友化學公司製造]100份，於95℃下進行攪拌。繼而，耗費10分鐘向反應容器中滴加作為界面活性劑之Latemul E-1000A(30%水溶液，花王股份有限公司製造)33.3份。進而攪拌5分鐘後，投入28%氨水溶液16.7份，進而攪拌5分鐘。繼而，於反應容器中，一面耗費30分鐘滴加離子交換水300份一面繼續攪拌，獲得乳白色之分散液。 200 parts of toluene and ethylene-unsaturated ester copolymer (A-1) [ethylene-methyl methacrylate copolymer, Acryft) were placed in a separate flask reaction vessel equipped with a stirrer, a thermometer, and a reflux cooling tube. 100 parts manufactured by Sumitomo Chemical Co., Ltd., and stirred at 95 ° C. Then, 33.3 parts of Latemul E-1000A (30% aqueous solution, manufactured by Kao Co., Ltd.) as a surfactant was added dropwise to the reaction container over 10 minutes. After further stirring for 5 minutes, 16.7 parts of a 28% aqueous ammonia solution was added, and the mixture was further stirred for 5 minutes. Then, while stirring 300 parts of ion-exchanged water for 30 minutes in the reaction container, stirring was continued to obtain a milky white dispersion.
將獲得之分散液投入至2L圓底燒瓶中，利用蒸發器進行減壓蒸餾去除，利用200目尼龍網進行過濾，獲得包含乙烯-不飽和酯共聚物(A-1)及界面活性劑之水性乳液(E-1)。獲得之水性乳液(E-1)所含有之分散質之平均粒徑(體積基準)為1.35μm，不揮發成分濃度為43%。 The obtained dispersion liquid was placed in a 2 L round bottom flask, and distilled under reduced pressure by an evaporator, and filtered through a 200-mesh nylon mesh to obtain an aqueous solution containing the ethylene-unsaturated ester copolymer (A-1) and a surfactant. Emulsion (E-1). The average particle diameter (volume basis) of the dispersoid contained in the obtained aqueous emulsion (E-1) was 1.35 μm, and the concentration of the nonvolatile matter was 43%.
利用高壓釜式反應器，於反應溫度188~195℃、反應壓力180~185MPa、進氣組成(乙烯：63~68wt%、乙酸乙烯酯：37~32wt%)之條件下，使用過氧化2-乙基己酸第三丁酯作為起始劑而合成乙烯-乙酸乙烯酯共聚物，製作包含乙烯-乙酸乙烯酯共聚物之太陽能電池密封材用小粒(P1)(乙酸乙烯酯含量32質量%，MFR 37，小粒質量32g)。 Using an autoclave reactor, using a peroxidation at a reaction temperature of 188 to 195 ° C, a reaction pressure of 180 to 185 MPa, and an intake composition (ethylene: 63 to 68 wt%, vinyl acetate: 37 to 32 wt%) Synthesis of ethylene-vinyl acetate copolymer using tributyl butyl hexanoate as a starter to prepare a pellet (P1) for a solar cell sealing material comprising an ethylene-vinyl acetate copolymer (vinyl acetate content of 32% by mass, MFR 37, small particle mass 32g).
將太陽能電池密封材用小粒(P1)100份、與水性乳液(E-1)(不揮發 成分濃度43%)0.698份(以固形物成分計為0.3份)裝入聚乙烯製之容器中攪拌5分鐘後，吹送乾燥氮氣並且進而乾燥2小時，獲得表面附著有抗結塊劑之太陽能電池密封材用小粒(Q1)。 100 parts of small particles (P1) for solar cell sealing materials, and aqueous emulsion (E-1) (non-volatile 0.698 parts (0.3 parts by weight of the solid content) was placed in a polyethylene container and stirred for 5 minutes, and then dried with nitrogen gas and further dried for 2 hours to obtain a solar cell having an anti-caking agent attached to the surface thereof. Small particles (Q1) for sealing materials.
不實施乾燥，除此以外，以與<Q1之製造例1>相同之方式，獲得濕潤狀態之表面附著有抗結塊劑之太陽能電池密封材用小粒(Q2)。 In the same manner as in Production Example 1 of <Q1, a small particle (Q2) for a solar cell sealing material having an anti-caking agent adhered to the surface of the wet state was obtained.
於60mm×85mm之附有夾具之聚乙烯袋中裝入小粒(Q1)32g，閉合夾具。繼而，於40℃下，對上述袋施加100g/cm2之荷重並保持24小時，此後於5℃下保持24小時。其後，卸掉荷重於23℃下保持24小時。其後，將袋破壞，取出小粒(Q1)進行觀察，以○、×進行評價。 A small particle (Q1) 32 g was placed in a 60 mm × 85 mm polyethylene bag with a jig, and the jig was closed. Then, a load of 100 g/cm 2 was applied to the above bag at 40 ° C for 24 hours, and thereafter kept at 5 ° C for 24 hours. Thereafter, the load was removed and maintained at 23 ° C for 24 hours. Thereafter, the bag was broken, and the small particles (Q1) were taken out for observation, and evaluated by ○ and ×.
○：無小粒之結塊 ○: no agglomeration of small particles
△：5~50粒小粒黏結 △: 5~50 small grain bonds
×：51粒以上之小粒黏結 ×: small particle bonding of more than 51 grains
於底經封口膜密封之聚乙烯製漏斗中裝入小粒(Q2)100g，繼而於40℃下進行24小時靜置保管。 100 g of small particles (Q2) was placed in a polyethylene funnel sealed with a sealing film at the bottom, and then stored at 40 ° C for 24 hours.
保管後，恢復至室溫後取下密封之封口膜，測定小粒自漏斗全部流完之時間(流下時間)，以○、×進行評價。 After storage, after returning to room temperature, the sealed sealing film was taken out, and the time (flow time) at which the small particles flowed out from the funnel was measured, and evaluated by ○ and ×.
○：未達30秒全部流完。 ○: It has not flowed for 30 seconds.
△：30秒~未達3分鐘全部流完。 △: 30 seconds~ not completed for 3 minutes.
×：經過3分鐘以上亦未流完。 ×: It has not flowed out after more than 3 minutes.
利用密閉型混練機將小粒(Q1)100質量份、過氧化2-乙基己基碳酸第三丁酯(PERBUTYL E，日本油脂股份有限公司製造，1小時半生期溫度121℃：作為交聯劑之有機過氧化物)0.4份、 異氰尿酸三烯丙酯(TAIC，東京化成工業股份有限公司製造：交聯助劑)0.9份、γ-甲基丙烯醯氧基丙基三甲氧基矽烷(Silquest A-174，Momentive Performance Materials Japan有限公司製造：矽烷偶合劑)0.12份、2-羥基-4-正辛氧基二苯基酮(Sumisorb 130，Sumika Chemtex股份有限公司製造，平均粒徑178μm)0.3份、及雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(Tinuvin770 DF，BASF公司製造)0.08份 100 parts by mass of small particles (Q1) and tert-butyl peroxyethyl 2-ethylhexyl carbonate (PERBUTYL E, manufactured by Nippon Oil & Fat Co., Ltd., 1 hour and half-life temperature: 121 ° C: as a crosslinking agent) by a closed type kneader Organic peroxide) 0.4 parts, Triallyl isocyanurate (TAIC, manufactured by Tokyo Chemical Industry Co., Ltd.: cross-linking auxiliary) 0.9 parts, γ-methacryloxypropyltrimethoxydecane (Silquest A-174, Momentive Performance Materials Japan) Co., Ltd. manufactured: decane coupling agent) 0.12 parts, 2-hydroxy-4-n-octyloxydiphenyl ketone (Sumisorb 130, manufactured by Sumika Chemtex Co., Ltd., average particle diameter 178 μm) 0.3 parts, and double (2, 2 ,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770 DF, manufactured by BASF Corporation) 0.08 parts
進行5分鐘混練後，利用150℃之熱壓機以2MPa之壓力進行5分鐘壓製，利用30℃之冷卻壓製機進行5分鐘冷卻，製作厚度約500μm之片材(S1)。 After kneading for 5 minutes, the film was pressed at a pressure of 2 MPa for 5 minutes by a hot press at 150 ° C, and cooled by a cooling press at 30 ° C for 5 minutes to prepare a sheet (S1) having a thickness of about 500 μm.
將片材(S1)設置於平板試樣用大徑電極(東亞DKK股份有限公司製造SME-8310)上，施加500V之電壓，利用數位絕緣計(東亞DKK股份有限公司製造，DSM-8103)測定1分鐘後之電阻值，以該值為基礎算出體積電阻率值。 The sheet (S1) was placed on a large-diameter electrode (SME-8310 manufactured by Tosoh DKK Co., Ltd.) for a flat plate sample, and a voltage of 500 V was applied thereto, and it was measured by a digital insulation meter (manufactured by Toago DKK Co., Ltd., DSM-8103). The resistance value after 1 minute, and the volume resistivity value was calculated based on the value.
利用分光光度計(島津製作所股份有限公司製造UV-3150)測定片材(S1)之厚度方向之光線透過光譜，算出波長範圍400~1200nm時之透光率之平均值。 The light transmission spectrum in the thickness direction of the sheet (S1) was measured by a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation), and the average value of the light transmittance in the wavelength range of 400 to 1200 nm was calculated.
將乙烯-不飽和酯共聚物(A-1)變更為乙烯-不飽和酯共聚物(A-2)[乙烯-甲基丙烯酸甲酯共聚物，Acryft WH302住友化學公司製造]，除此以外，以與實施例1相同之方式製造水性乳液(E-2)，並進行評價。 The ethylene-unsaturated ester copolymer (A-1) was changed to an ethylene-unsaturated ester copolymer (A-2) [ethylene-methyl methacrylate copolymer, manufactured by Acryft WH302 Sumitomo Chemical Co., Ltd.], in addition to An aqueous emulsion (E-2) was produced in the same manner as in Example 1 and evaluated.
將乙烯-不飽和酯共聚物(A-1)變更為乙烯-不飽和酯共聚物(A-3)[乙烯-乙酸乙烯酯共聚物，MFR 9，乙酸乙烯酯濃度18wt%，住友化學公司製造]，除此以外，以與實施例1相同之方式製造水性乳液(E-3)，並進行評價。 The ethylene-unsaturated ester copolymer (A-1) was changed to an ethylene-unsaturated ester copolymer (A-3) [ethylene-vinyl acetate copolymer, MFR 9, vinyl acetate concentration: 18% by weight, manufactured by Sumitomo Chemical Co., Ltd. The aqueous emulsion (E-3) was produced and evaluated in the same manner as in Example 1 except for the above.
於水性乳液(E-3)中添加Pluronic L-64(ADEKA公司製造)4份，充分進行攪拌而製造水性乳液(E-3-1)，並進行評價。 Four parts of Pluronic L-64 (manufactured by Adeka Co., Ltd.) was added to the aqueous emulsion (E-3), and the mixture was sufficiently stirred to prepare an aqueous emulsion (E-3-1), which was evaluated.
於水性乳液(E-3)中添加Pluronic L-64(ADEKA公司製造)6份，充分進行攪拌而製造水性乳液(E-3-2)，並進行評價。 To the aqueous emulsion (E-3), 6 parts of Pluronic L-64 (manufactured by Adeka Co., Ltd.) was added, and the aqueous emulsion (E-3-2) was sufficiently stirred and evaluated.
將乙烯-不飽和酯共聚物(A-1)變更為乙烯-不飽和酯共聚物(A-4)[乙烯-甲基丙烯酸甲酯共聚物，Acryft CM5021住友化學公司製造]，除此以外，以與實施例1相同之方式製造水性乳液(E-4)，並進行評價。 The ethylene-unsaturated ester copolymer (A-1) was changed to an ethylene-unsaturated ester copolymer (A-4) [ethylene-methyl methacrylate copolymer, manufactured by Acryf CM5021 Sumitomo Chemical Co., Ltd.], in addition to An aqueous emulsion (E-4) was produced in the same manner as in Example 1 and evaluated.
將丙烯酸30.0份、丙烯酸乙酯60份、甲基丙烯酸月桂酯10.0份、及異丙醇150份加入至安裝有攪拌機、回流冷卻管、溫度計、滴加漏斗之4口燒瓶內，進行氮氣置換後，以2,2'-偶氮異丁腈0.6份作為起始劑，於80℃下聚合3小時。繼而，利用28%氨水溶液37.9份進行中和後，一面蒸餾去除異丙醇，一面添加水進行置換，最終獲得不揮發成分30%之黏稠之丙烯酸系聚合物之中和物的水溶液(X-1)。 30.0 parts of acrylic acid, 60 parts of ethyl acrylate, 10.0 parts of lauryl methacrylate, and 150 parts of isopropyl alcohol were placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a dropping funnel, and after nitrogen substitution. With 0.6 parts of 2,2'-azoisobutyronitrile as a starter, polymerization was carried out at 80 ° C for 3 hours. Then, after neutralizing with 37.9 parts of a 28% aqueous ammonia solution, the isopropanol was distilled off, and water was added for replacement, and finally, an aqueous solution of a viscous acrylic polymer neutralized product having a nonvolatile content of 30% was obtained (X- 1).
將乙烯-不飽和酯共聚物(A-1)以100份/小時之比率自同方向旋轉嚙合型雙螺旋擠出機(池貝鐵工公司商品名PCM45，三線螺紋淺溝型，L/D30)之料斗連續地進行供給。 The ethylene-unsaturated ester copolymer (A-1) was rotated from the same direction at a ratio of 100 parts per hour to the intermeshing twin-screw extruder (Chibei Iron & Steel Co., Ltd. trade name PCM45, three-threaded shallow groove type, L/D30) The hopper is continuously supplied.
又，自設置於上述擠出機之通氣孔部之供給口，將水溶液(X-1)26.8份(作為不揮發成分為8份)中進而加入有水113.2份者以140份/小時之比率利用齒輪泵進行加壓並連續地供給，於加熱溫度130℃下連續地擠出，獲得乳白色之水性乳液(E-5)。若以與實施例1相同之方式進行評價，則獲得與實施例1相同之結果。 Further, from the supply port of the vent hole of the extruder, 26.8 parts of the aqueous solution (X-1) (as a nonvolatile component: 8 parts) was further added with 113.2 parts of water at a ratio of 140 parts per hour. The mixture was pressurized by a gear pump and continuously supplied, and continuously extruded at a heating temperature of 130 ° C to obtain a milky white aqueous emulsion (E-5). When the evaluation was carried out in the same manner as in Example 1, the same results as in Example 1 were obtained.
使用丙烯酸21.6份、丙烯酸乙酯30份、甲基丙烯酸丁酯56.8份、28%氨水溶液18.2份，除此以外，以與<高分子型之陰離子性界面活性劑水溶液之製造例1>相同之方式，獲得不揮發成分30%之黏稠之丙烯酸系聚合物之中和物的水溶液(X-2)，進而利用與<實施例5>相同之方法獲得水性乳液(E-6)。若以與實施例1相同之方式進行評價，則獲得與實施例1相同之結果。 In the same manner as in the production example 1 of the polymer type anionic surfactant aqueous solution, except that 21.6 parts of acrylic acid, 30 parts of ethyl acrylate, 56.8 parts of butyl methacrylate, and 28.8 parts of a 28% aqueous ammonia solution were used. In the manner, an aqueous solution (X-2) of a viscous acrylic polymer neutralized product having a nonvolatile content of 30% was obtained, and an aqueous emulsion (E-6) was obtained by the same method as in <Example 5>. When the evaluation was carried out in the same manner as in Example 1, the same results as in Example 1 were obtained.
將二氧化矽(Sylysia 430，Fuji Silysia化學公司製造，平均粒徑2.9μm)0.30質量份未磨碎而使用來代替水性乳液(E-1)，除此以外，以與實施例1相同之方式進行評價。 In the same manner as in Example 1, except that 0.30 parts by mass of cerium oxide (Sylysia 430, manufactured by Fuji Silysia Chemical Co., Ltd., average particle diameter: 2.9 μm) was not ground and used instead of the aqueous emulsion (E-1). Conduct an evaluation.
將硬脂酸鈣(共同藥品股份有限公司製造，平均粒徑9.3μm)0.10質量份未磨碎而使用來代替水性乳液(E-1)，除此以外，以與實施例1相同之方式進行評價。 In the same manner as in Example 1, except that 0.10 parts by mass of calcium stearate (manufactured by Co-Pharmaceutical Co., Ltd., average particle diameter: 9.3 μm) was used without being ground, instead of the aqueous emulsion (E-1). Evaluation.
不使用水性乳液，除此以外，以與實施例1相同之方式進行評價。 Evaluation was carried out in the same manner as in Example 1 except that the aqueous emulsion was not used.
實施例1~4中，結塊得到防止，體積電阻率及透光率與參考例相同。另一方面，比較例1與參考例相比透光率下降，比較例2與參考例相比體積電阻率下降。 In Examples 1 to 4, agglomeration was prevented, and volume resistivity and light transmittance were the same as in the reference example. On the other hand, in Comparative Example 1, the light transmittance was lowered as compared with the reference example, and in Comparative Example 2, the volume resistivity was decreased as compared with the reference example.
本發明之方法係用作太陽能電池密封材用小粒之防止結塊方法。 The method of the present invention is used as a method of preventing agglomeration of small particles for a solar cell sealing material.
Claims (12)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012073087 | 2012-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201343352A true TW201343352A (en) | 2013-11-01 |
Family
ID=49260546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102110743A TW201343352A (en) | 2012-03-28 | 2013-03-26 | Method for preventing mutual adhesion of pellets for solar cell sealing materials |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5989763B2 (en) |
| KR (1) | KR20140148413A (en) |
| SG (1) | SG11201405699VA (en) |
| TW (1) | TW201343352A (en) |
| WO (1) | WO2013147313A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200347215A1 (en) * | 2018-02-14 | 2020-11-05 | Dow-Mitsui Polychemicals Co., Ltd. | Resin composition for laminated glass interlayer film or solar cell encapsulant, laminated glass interlayer film, laminated glass, solar cell encapsulant, and solar cell module |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216373B (en) * | 2008-11-19 | 2013-10-30 | 埃克森美孚化学专利公司 | Adhesive compositions and methods of making same |
| TW201109351A (en) * | 2009-08-07 | 2011-03-16 | Toyo Ink Mfg Co | Manufacturing method of resin compositions used in solar battery sealant, resin compositions used in solar battery sealant, solar battery sealant, and solar battery module |
| US9460829B2 (en) * | 2011-09-01 | 2016-10-04 | Sumitomo Chemical Company, Limited | Resin composition, resin pellet, method for producing resin pellet, and solar cell encapsulant |
| JP2014189617A (en) * | 2013-03-27 | 2014-10-06 | Sumitomo Chemical Co Ltd | Aqueous emulsion |
-
2013
- 2013-03-26 TW TW102110743A patent/TW201343352A/en unknown
- 2013-03-27 SG SG11201405699VA patent/SG11201405699VA/en unknown
- 2013-03-27 JP JP2014508262A patent/JP5989763B2/en not_active Expired - Fee Related
- 2013-03-27 WO PCT/JP2013/060140 patent/WO2013147313A1/en active Application Filing
- 2013-03-27 KR KR1020147028452A patent/KR20140148413A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP5989763B2 (en) | 2016-09-07 |
| KR20140148413A (en) | 2014-12-31 |
| SG11201405699VA (en) | 2014-11-27 |
| JPWO2013147313A1 (en) | 2015-12-14 |
| WO2013147313A1 (en) | 2013-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102549025B (en) | Process for producing ethylene/vinyl alcohol copolymer | |
| JP5852234B2 (en) | Method for producing solar cell encapsulant sheet | |
| JP2009091426A (en) | Aqueous dispersion, its manufacturing method and layered product | |
| EP2989134B1 (en) | Polyolefin/ (meth)acrylic impact modifier and method of preparing same | |
| JP5484642B2 (en) | Chlorinated polyolefin resin composition | |
| JP5200475B2 (en) | Method for producing aqueous resin dispersion composition | |
| JP6597025B2 (en) | Water-based resin dispersion, paint, adhesive and laminate | |
| WO2010146300A1 (en) | Master mixture composition including a peroxide | |
| JP6011612B2 (en) | Process for producing modified polyolefin aqueous dispersion composition | |
| TWI711658B (en) | Specific block copolymer hydrogenated pellets, method for preventing agglomeration of pellets, and manufacturing method of molded body | |
| JP5037012B2 (en) | Method for producing aqueous polyolefin resin dispersion | |
| US9460829B2 (en) | Resin composition, resin pellet, method for producing resin pellet, and solar cell encapsulant | |
| TW201343352A (en) | Method for preventing mutual adhesion of pellets for solar cell sealing materials | |
| KR20160091817A (en) | Aqueous dispersion composition containing modified polyolefin | |
| JP2014189617A (en) | Aqueous emulsion | |
| TW201731924A (en) | Process for preparing waterborne heat seal coating compositions | |
| JP2008056877A (en) | Method for manufacturing polyolefin resin aqueous dispersion | |
| TW201546144A (en) | Highly adhesive resin composition and molded article produced from same, and laminate | |
| JP5586509B2 (en) | Method for producing acid-modified olefin-based aqueous dispersion | |
| JP6897427B2 (en) | Masterbatch for solar cell encapsulation sheet and manufacturing method of solar cell encapsulation sheet | |
| JP2013127069A (en) | Water-base resin-dispersed composition | |
| JP2010065196A (en) | Aqueous adhesive, heat-sealing material and laminate | |
| JPWO2019225424A1 (en) | Adhesive resin manufacturing method | |
| TW201410750A (en) | Resin pellet, method for producing resin pellet, and solar cell sealing material | |
| JP2016216665A (en) | Manufacturing method of resin composition for crosslinking |