TW201321422A - Adamantane-containing polymer - Google Patents
Adamantane-containing polymer Download PDFInfo
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
Abstract
Description
本發明係關於聚合物、含其之樹脂組成物及具有由該樹脂組成物所得到的硬化層之硬塗薄膜。 The present invention relates to a polymer, a resin composition containing the same, and a hard coat film having a hardened layer obtained from the resin composition.
在液晶顯示器、電漿顯示器、有機EL顯示器等使用種種機能性薄膜。其中近年以智慧型手機為代表的觸控式面板形式之裝置普及，而企求更硬、不易刮傷的薄膜。 Various functional films are used in liquid crystal displays, plasma displays, organic EL displays, and the like. Among them, in recent years, devices in the form of touch panels represented by smart phones have become popular, and films that are harder and less scratch-resistant have been sought.
賦予薄膜硬度的方法，硬塗紫外線硬化型樹脂之方法為一般的。但是，因紫外線硬化型樹脂之硬化收縮而有薄膜彎曲之問題，除在對顯示器表面之貼合步驟的生產性降低外，在貼合後之耐久性上亦有問題。 A method of imparting hardness to a film, and a method of hard-coating an ultraviolet curable resin is general. However, there is a problem that the film is bent due to curing shrinkage of the ultraviolet curable resin, and the productivity in the bonding step on the surface of the display is lowered, and the durability after bonding is also problematic.
為了解決上述問題，專利文獻1揭示於塑膠薄膜的至少一面上設置2層以上的硬塗層之方法。然而，該方法，有設置2層以上的硬塗層用的塗佈步驟變得繁複、生產花費變高的問題。 In order to solve the above problem, Patent Document 1 discloses a method of providing two or more hard coat layers on at least one surface of a plastic film. However, this method has a problem that the coating step for providing two or more layers of the hard coat layer becomes complicated and the production cost becomes high.
又，專利文獻2雖揭示使用含環氧基的(甲基)丙烯酸系共聚物與不飽和單羧酸進行加成反應的反應性聚合物於硬塗層，但硬塗層的硬度及彎曲抑制之平衡並不充分。 Further, Patent Document 2 discloses that a reactive polymer which is subjected to an addition reaction using an epoxy group-containing (meth)acrylic copolymer and an unsaturated monocarboxylic acid in a hard coat layer, but hardness and bending suppression of the hard coat layer The balance is not sufficient.
〔專利文獻1〕日本特開2005-53152號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-53152
〔專利文獻2〕日本特開2008-69303號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-69303
本發明目的，在於提供可製造高硬度且抑制彎曲的硬塗薄膜之聚合物。 It is an object of the present invention to provide a polymer which can produce a hard coat film having high hardness and suppressing bending.
根據本發明，提供以下的聚合物等。 According to the invention, the following polymers and the like are provided.
1.含有下述式(I)所表示之構造之聚合物。 A polymer comprising a structure represented by the following formula (I).
2.前述式(I)所表示之聚合物的R2為單鍵，m為0的第1項之聚合物。 2. The polymer of the first item wherein R 2 of the polymer represented by the above formula (I) is a single bond and m is 0.
3.使鍵結有金剛烷基的(甲基)丙烯酸酯與鍵結有環氧基的(甲基)丙烯酸酯共聚合而得的共聚物之環氧基與 (甲基)丙烯酸反應而得到的聚合物、或使鍵結有金剛烷基的(甲基)丙烯酸酯與(甲基)丙烯酸共聚合而得的共聚物之羧基與鍵結有環氧基的(甲基)丙烯酸酯反應而得的聚合物。 3. An epoxy group of a copolymer obtained by copolymerizing a (meth) acrylate having an adamantyl group and a (meth) acrylate bonded with an epoxy group; a polymer obtained by reacting (meth)acrylic acid, or a carboxyl group of a copolymer obtained by copolymerizing a (meth) acrylate bonded with an adamantyl group and (meth)acrylic acid, and an epoxy group bonded thereto A polymer obtained by reacting (meth) acrylate.
4.含有1~3中任一項記載之聚合物及光聚合起始劑的樹脂組成物。 4. A resin composition comprising the polymer according to any one of 1 to 3 and a photopolymerization initiator.
5.具有由4記載之樹脂組成物所得到的硬化層之硬塗薄膜。 5. A hard coat film having a hardened layer obtained from the resin composition described in 4.
根據本發明，可提供能製造高硬度且抑制彎曲的硬塗薄膜之聚合物。 According to the present invention, it is possible to provide a polymer capable of producing a hard coat film having high hardness and suppressing bending.
本發明的聚合物含有下述式(I)所表示之構造。 The polymer of the present invention contains a structure represented by the following formula (I).
R2及R5各自為含有由羥基、鹵素原子及雜原子所選出之1種以上的2價之脂肪族烴基、2價之脂肪族烴基或單鍵。 Each of R 2 and R 5 is a divalent aliphatic hydrocarbon group or a divalent aliphatic hydrocarbon group or a single bond selected from the group consisting of a hydroxyl group, a halogen atom and a hetero atom.
R3為烴基、鹵素取代烴基、環式烴基、鹵素取代環式烴基、鹵素原子、羥基、羧基、或側氧基(=O)。 R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or a pendant oxy group (=O).
m為0~15之整數。) m is an integer from 0 to 15. )
式(I)所表示之聚合物的各基如下。 The respective groups of the polymer represented by the formula (I) are as follows.
作為R2及R5的含有由羥基、鹵素原子及雜原子所選出之1種以上的2價之脂肪族烴基，可舉例如下述3個之構造。 As R 2 and R 5 contains at least one kind of divalent aliphatic hydrocarbon group having a hydroxyl group, a halogen atom and a hetero atom selected of, for example may be configured as the following three.
作為R2及R5的2價之脂肪族烴基，可舉例如亞甲基、伸乙基、伸丁基等。 Examples of the divalent aliphatic hydrocarbon group of R 2 and R 5 include a methylene group, an exoethyl group, and a butyl group.
R3之烴基，可舉例如甲基、乙基、丁基、t-丁基等。 The hydrocarbon group of R 3 may, for example, be a methyl group, an ethyl group, a butyl group or a t-butyl group.
R3之環式烴基，可舉例如環戊基、環己基等。 The cyclic hydrocarbon group of R 3 may, for example, be a cyclopentyl group or a cyclohexyl group.
R3之鹵素取代烴基為上述烴基的氫原子以鹵素原子取代的基。同樣地R3之鹵素取代環式烴基為上述環式烴基的氫原子以鹵素原子取代的基。 The halogen-substituted hydrocarbon group of R 3 is a group in which a hydrogen atom of the above hydrocarbon group is substituted with a halogen atom. Similarly, the halogen-substituted cyclic hydrocarbon group of R 3 is a group in which a hydrogen atom of the above cyclic hydrocarbon group is substituted with a halogen atom.
又，R3之側氧基為2個R3鍵結於金剛烷骨架之相同碳原子上，且該2個R3皆為羥基，且為此等羥基縮合之 情形。 And, R 3 of the side 2 R 3 group is bonded to the same carbon atom of the adamantane skeleton, and the two R 3 are both hydroxy, the hydroxyl condensation and for this and other situations.
式(I)所表示之聚合物較佳為R2為單鍵(直接鍵結)、m為0之聚合物。 The polymer represented by the formula (I) is preferably a polymer wherein R 2 is a single bond (direct bond) and m is 0.
含式(I)所表示之構造的聚合物，可藉由將鍵結有金剛烷基的(甲基)丙烯酸酯與鍵結有環氧基的(甲基)丙烯酸酯進行共聚合後，使得到的共聚物之環氧基與(甲基)丙烯酸進行反應；或將鍵結有金剛烷基的(甲基)丙烯酸酯與(甲基)丙烯酸進行共聚合後，使得到的共聚物之羧基與鍵結有環氧基的(甲基)丙烯酸酯進行反應而製造。 The polymer having the structure represented by the formula (I) can be copolymerized by copolymerizing a (meth) acrylate having an adamantyl group bonded thereto and an epoxy group-bonded (meth) acrylate. The epoxy group of the copolymer is reacted with (meth)acrylic acid; or the (meth) acrylate bonded with adamantyl group is copolymerized with (meth)acrylic acid to obtain a carboxyl group of the obtained copolymer It is produced by reacting with a (meth) acrylate having an epoxy group bonded thereto.
鍵結有金剛烷基的(甲基)丙烯酸酯，例如具有下述構造之化合物。 A (meth) acrylate having an adamantyl group bonded thereto, for example, a compound having the following structure.
鍵結有環氧基的(甲基)丙烯酸酯，例如具有下述構造之化合物。下述式中，R5，與開環的環氧基合併的基對應於R5。 A (meth) acrylate having an epoxy group bonded thereto, for example, a compound having the following structure. In the following formula, R 5 , a group bonded to the ring-opened epoxy group, corresponds to R 5 .
(甲基)丙烯酸，例如具有下述構造之化合物。 (Meth)acrylic acid, for example, a compound having the following structure.
上述共聚合，例如可以習知自由基聚合法實施，在溶劑中或者無溶劑，使用自由基聚合起始劑等進行聚合即可。 The above-mentioned copolymerization can be carried out, for example, by a conventional radical polymerization method, and polymerization can be carried out using a radical polymerization initiator or the like in a solvent or without a solvent.
自由基聚合起始劑，可舉例如2,2’-偶氮雙異正丁腈、2,2’-偶氮雙-甲基正丁腈等之偶氮系起始劑；過氧化苯甲醯基酯、甲基乙基酮過氧化物、甲基異丁基酮過氧化物等之過氧化物起始劑。 The radical polymerization initiator may, for example, be an azo initiator such as 2,2'-azobisisobutyronitrile or 2,2'-azobis-methyl-n-butyronitrile; A peroxide initiator such as mercaptoester, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide or the like.
又，因應必要可使用十二基硫醇、月桂基硫醇、巰基乙醇酸酯、巰基乙醇等之鏈轉移劑。 Further, a chain transfer agent such as dodecyl mercaptan, lauryl mercaptan, mercapto glycolate or mercaptoethanol may be used as necessary.
自由基聚合起始劑之使用量，相對於共聚合的鍵結有金剛烷基的(甲基)丙烯酸酯及鍵結有環氧基的(甲基)丙烯酸酯、或鍵結有金剛烷基的(甲基)丙烯酸酯及(甲基)丙烯酸之合計100質量份，通常為0.01~50質量份、較佳為0.01~30質量份。藉由使自由基聚合起始劑 之使用量在該範圍，可使反應時間及收率等為良好、且得到目標的重量平均分子量。 The amount of the radical polymerization initiator used is a (meth) acrylate in which an adamantyl group is bonded and an epoxy group-bonded (meth) acrylate, or an adamantyl group is bonded to the copolymerization. The total amount of the (meth) acrylate and the (meth)acrylic acid is usually from 0.01 to 50 parts by mass, preferably from 0.01 to 30 parts by mass, per 100 parts by mass. Free radical polymerization initiator When the amount used is in this range, the reaction time, the yield, and the like can be made good, and the desired weight average molecular weight can be obtained.
共聚合使用的溶劑，可舉例如甲醇、乙醇、n-丙醇、異丙醇等之烷基醇類；甲基溶纖劑、乙二醇二甲基醚、乙二醇二乙基醚、丙二醇單甲基醚、丙二醇單乙基醚等之二醇醚類；苯、甲苯、二甲苯、乙基苯等之芳香族烴類；環戊烷、環己烷、甲基環己烷等之脂環族烴類；四氫呋喃、二噁烷、二異丙基醚等之醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；乙酸甲酯、乙酸乙酯、乙酸-n-丙酯、丙酸乙酯、丙二醇單乙基醚乙酸酯等之酯類等。此等溶劑可1種單獨或2種以上組合使用。 The solvent used for the copolymerization may, for example, be an alkyl alcohol such as methanol, ethanol, n-propanol or isopropanol; methyl cellosolve, ethylene glycol dimethyl ether or ethylene glycol diethyl ether; a glycol ether such as propylene glycol monomethyl ether or propylene glycol monoethyl ether; an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene; cyclopentane, cyclohexane or methylcyclohexane; An alicyclic hydrocarbon; an ether such as tetrahydrofuran, dioxane or diisopropyl ether; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; methyl acetate or acetic acid; Esters such as ethyl ester, n-propyl acetate, ethyl propionate, propylene glycol monoethyl ether acetate, and the like. These solvents may be used alone or in combination of two or more.
共聚合使用的溶劑，使用共聚合成分(鍵結有金剛烷基的(甲基)丙烯酸酯及鍵結有環氧基的(甲基)丙烯酸酯、或鍵結有金剛烷基的(甲基)丙烯酸酯及(甲基)丙烯酸)的合計濃度，例如成為0.5質量%以上、較佳為5質量%以上之量即可。此時，共聚合成分雖可為懸濁狀態，但以溶解為佳。 The solvent used for the copolymerization, using a copolymerization component ((meth)acrylate bonded with adamantyl group and (meth)acrylate bonded with an epoxy group, or (methyl group bonded with an adamantyl group) The total concentration of the acrylate and the (meth)acrylic acid may be, for example, 0.5% by mass or more, preferably 5% by mass or more. In this case, the copolymerization component may be in a suspended state, but it is preferably dissolved.
共聚合反應的反應溫度，通常為0~200℃、較佳為20~150℃。溫度未達0℃之場合，有反應速度降低之虞。另一方面，溫度超過200℃之場合，有得到的聚合物的著色變得嚴重之虞。 The reaction temperature of the copolymerization reaction is usually 0 to 200 ° C, preferably 20 to 150 ° C. When the temperature is less than 0 ° C, there is a decrease in the reaction rate. On the other hand, when the temperature exceeds 200 ° C, the coloration of the obtained polymer becomes severe.
共聚合反應的反應壓力方面，通常絕對壓力為0.01~10MPa、較佳為常壓~1MPa。壓力超過10MPa之場合，除有安全上問題，且變得需要特別的裝置而不佳。 In terms of the reaction pressure of the copolymerization reaction, the absolute pressure is usually 0.01 to 10 MPa, preferably from atmospheric pressure to 1 MPa. In the case where the pressure exceeds 10 MPa, there is a safety problem and it becomes a need for a special device.
反應時間因聚合起始劑之種類或量、反應溫度等而左右，通常為1分鐘~24小時、較佳為1~10小時。 The reaction time varies depending on the type or amount of the polymerization initiator, the reaction temperature, and the like, and is usually from 1 minute to 24 hours, preferably from 1 to 10 hours.
共聚合反應時，在不損及本發明的效果範圍，可加入其他的(甲基)丙烯酸系單體作為共聚合成分。 In the copolymerization reaction, other (meth)acrylic monomers may be added as a copolymerization component without impairing the effect of the present invention.
其他的(甲基)丙烯酸系單體，可舉例如甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、二環戊烷基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、γ-丁內酯(甲基)丙烯酸酯等。 Examples of other (meth)acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, and cyclohexyl (meth) acrylate. Ester, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, γ-butyrolactone (Meth) acrylate, etc.
共聚合反應後之加成反應、亦即使鍵結有金剛烷基的(甲基)丙烯酸酯與鍵結有環氧基的(甲基)丙烯酸酯之共聚物與(甲基)丙烯酸進行加成之反應；或使鍵結有金剛烷基的(甲基)丙烯酸酯與(甲基)丙烯酸的共聚物與鍵結有環氧基的(甲基)丙烯酸酯進行加成之反應，使此等在溶劑中進行反應即可。 Addition reaction after copolymerization, even if a copolymer of (meth) acrylate bonded with adamantyl group and (meth) acrylate bonded with epoxy group is added with (meth)acrylic acid a reaction of adding a copolymer of a (meth) acrylate bonded to an adamantyl group to a (meth)acrylic acid with an epoxy group-bonded (meth) acrylate, such that The reaction can be carried out in a solvent.
加成反應可使用的溶劑，可舉例如環己烷、甲基環己烷、乙基環己烷、甲苯、二甲苯、MEK(甲基乙基酮)、MIBK(甲基異丁基酮)、DMF(二甲基甲醯胺)、NMP(N-甲基-2-吡咯烷酮)、DMAc(N,N-二甲基乙醯胺)、DMSO(二甲基亞碸)、及丙二醇單甲基醚乙酸酯等。 The solvent which can be used for the addition reaction may, for example, be cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone). , DMF (dimethylformamide), NMP (N-methyl-2-pyrrolidone), DMAc (N,N-dimethylacetamide), DMSO (dimethyl sulfoxide), and propylene glycol monomethyl Ethyl ether acetate and the like.
加成反應時可使用觸媒，該觸媒，可舉例如四甲基銨氯化物、四甲基銨溴化物、四乙基銨氯化物、四乙基銨溴化物、三苯基膦、吡啶等。 A catalyst may be used in the addition reaction, and examples of the catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, triphenylphosphine, and pyridine. Wait.
含式(I)所表示之構造的聚合物的金剛烷基單元與(甲基)丙烯基單元的構成單元比率(莫耳比)，反映共聚合時之搭配比，金剛烷基單元為1%~99%、較佳為10%~90%。金剛烷基單元未達10%則有得到的硬塗薄膜的彎曲變大之可能性、而即使超過90%得到的硬塗薄膜的物性不致有大差異。 The constituent unit ratio (mole ratio) of the adamantyl unit and the (meth)acryl-based unit of the polymer represented by the formula (I), reflecting the mixing ratio at the time of copolymerization, and the adamantyl unit is 1% ~99%, preferably 10%~90%. When the adamantyl unit is less than 10%, there is a possibility that the bending of the obtained hard coat film becomes large, and the physical properties of the hard coat film obtained by more than 90% are not greatly different.
又，式(I)所表示之聚合物的聚合形態不特別限制，例如無規共聚物。 Further, the polymerization form of the polymer represented by the formula (I) is not particularly limited, and examples thereof include a random copolymer.
含式(I)所表示之構造的聚合物為僅由式(I)的金剛烷基單元與(甲基)丙烯基單元所構成之聚合物(亦即、式(I)所表示之聚合物)、或由式(I)的金剛烷基單元與(甲基)丙烯基單元實質構成的聚合物。 The polymer having the structure represented by the formula (I) is a polymer composed only of an adamantyl unit of the formula (I) and a (meth)acryl-based unit (that is, a polymer represented by the formula (I) Or a polymer substantially composed of an adamantyl unit of the formula (I) and a (meth)acryl-based unit.
「實質構成的」係指聚合物中之式(I)的金剛烷基單元與(甲基)丙烯基單元的合計，例如90莫耳%以上、95莫耳%以上、98莫耳%以上、或99莫耳%以上，且在不 損及本發明的效果範圍，進而包含未反應環氧基末端、未反應(甲基)丙烯酸酯末端等之場合。 The term "substantially constituted" means a total of adamantyl unit and (meth)acryl-based unit of the formula (I) in the polymer, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more, Or 99% or more, and not The effect range of the present invention is impaired, and further includes an unreacted epoxy group terminal, an unreacted (meth) acrylate terminal or the like.
式(I)所表示之聚合物的重量平均分子量雖無特別限制，較佳為1,000~100,000。分子量未達1,000則有得到的硬塗薄膜的彎曲變大可能性。另一方面，分子量超過100,000則有樹脂溶液黏度變高、操作性變困難之場合。 The weight average molecular weight of the polymer represented by the formula (I) is not particularly limited, but is preferably from 1,000 to 100,000. When the molecular weight is less than 1,000, the curvature of the obtained hard coat film becomes large. On the other hand, when the molecular weight exceeds 100,000, the viscosity of the resin solution becomes high and the workability becomes difficult.
本發明的組成物含有上述本發明的聚合物及光聚合起始劑。 The composition of the present invention contains the above-described polymer of the present invention and a photopolymerization initiator.
光聚合起始劑，可使用習知光聚合起始劑，例如2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-{4-〔4-(2-羥基-2-甲基-丙醯基)-苄基〕苯基}-2-甲基-丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基-膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物等。 As the photopolymerization initiator, a conventional photopolymerization initiator such as 2,2-dimethoxy-1,2-diphenylethane-1-one or 1-hydroxy-cyclohexyl-phenyl-one can be used. 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane 1-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, and the like.
此等可單獨或2種以上混合使用。 These may be used alone or in combination of two or more.
上述光聚合起始劑中，可添加N,N-二甲基胺基安息香酸乙基酯、N,N-二甲基胺基安息香酸異戊基酯、戊基-4-二甲基胺基苯甲酸酯、三乙基胺、三乙醇胺等之第三級胺類等之光起始助劑。又，可見光領域具有吸收的CGI-784等(Ciba Specialty Chemicals Inc.製)的二茂鈦化合物等亦可以為了促進光反應而添加。 Among the above photopolymerization initiators, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylamine may be added. A photoinitiator such as a tertiary amine such as a benzoic acid ester, triethylamine or triethanolamine. Further, a titanocene compound or the like of CGI-784 or the like (manufactured by Ciba Specialty Chemicals Inc.) having absorption in the visible light region may be added in order to promote photoreaction.
又，光聚合起始劑為在紫外光或者可見光領域吸收光、使感光性的不飽和雙鍵進行自由基聚合之化合物即可，不限於光聚合起始劑、光起始助劑，皆可使用。 Further, the photopolymerization initiator is a compound which absorbs light in the ultraviolet light or visible light region and radically polymerizes a photosensitive unsaturated double bond, and is not limited to a photopolymerization initiator or a photoinitiator. use.
組成物中之光聚合起始劑之含量，例如為0.1~20質量%、較佳為1~10質量%。光聚合起始劑之含量未達0.1質量%之場合，有使光硬化性降低之虞、另一方面，超過20質量%之場合，有光聚合起始劑之結晶析出或造成塗膜底部光硬化不良之虞。 The content of the photopolymerization initiator in the composition is, for example, 0.1 to 20% by mass, preferably 1 to 10% by mass. When the content of the photopolymerization initiator is less than 0.1% by mass, the photocurability is lowered. On the other hand, when the content is more than 20% by mass, the crystal of the photopolymerization initiator is precipitated or the bottom of the coating film is caused. Poor hardening.
本發明的組成物含有式(I)所表示之聚合物及光聚合起始劑即可，此等成分可成為實質、或僅由此等成分構成。 The composition of the present invention may contain a polymer represented by the formula (I) and a photopolymerization initiator, and these components may be substantially or only composed of such components.
「成為實質」係指此等成分的組成物中之含量，例如90質量%以上、95質量%以上、97質量%以上、98質量%以上、或99質量%以上。 The term “substantially” means a content in the composition of the components, for example, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or 99% by mass or more.
本發明的組成物，因應必要可為溶解於溶劑之狀態。 The composition of the present invention may be dissolved in a solvent as necessary.
溶劑，可舉例如甲醇、乙醇、n-丙醇、異丙醇等之烷基醇類；甲基溶纖劑、乙二醇二甲基醚、乙二醇二乙基醚、丙二醇單甲基醚、丙二醇單乙基醚等之二醇醚類；苯、甲苯、二甲苯、乙基苯等之芳香族烴類；環戊烷、環己烷、甲基環己烷等之脂環族烴類；四氫呋喃、二噁烷、二異丙基醚等之醚類；丙酮、甲基乙基酮(MEK)、甲基異丁基酮(MIRK)、環己酮等之酮類；乙酸甲酯、乙酸 乙酯、乙酸-n-丙酯、丙酸乙酯、丙二醇單乙基醚乙酸酯等之酯類等。此等可單獨或2種以上混合使用。 The solvent may, for example, be an alkyl alcohol such as methanol, ethanol, n-propanol or isopropanol; methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol monomethyl a glycol ether such as ether or propylene glycol monoethyl ether; an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclohexane Ethers such as tetrahydrofuran, dioxane, diisopropyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIRK), cyclohexanone, etc.; Acetic acid Esters such as ethyl ester, n-propyl acetate, ethyl propionate, propylene glycol monoethyl ether acetate, and the like. These may be used alone or in combination of two or more.
溶劑之含量，例如為5質量%~90質量%、由乾燥觀點較佳為10質量%~50質量%。 The content of the solvent is, for example, 5 mass% to 90 mass%, and preferably 10 mass% to 50 mass% from the viewpoint of drying.
本發明的組成物在不損及本發明的效果，不損及性能平衡之範圍內，可進而含有其他的(甲基)丙烯酸系化合物、無機微粒子、塗平劑等。 The composition of the present invention may further contain other (meth)acrylic compounds, inorganic fine particles, a coating agent, and the like insofar as the effects of the present invention are not impaired and the balance of performance is not impaired.
其他的(甲基)丙烯酸化合物，可舉例如甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、t-丁基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、二環戊烷基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、γ-丁內酯(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、1,4-丁烷二醇二(甲基)丙烯酸酯、1,6-己烷二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、金剛烷二醇二(甲基)丙烯酸酯、金剛烷二甲醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、金剛烷三醇三(甲基)丙烯酸酯、金剛烷三甲醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、雙酚A環氧基(甲基)丙烯酸酯等。 Examples of the other (meth)acrylic compound include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, and cyclohexyl (meth) acrylate. Dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, γ-butyrolactone (A Acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tricyclic Decane dimethanol di(meth)acrylate, adamantanediol di(meth)acrylate, adamantane dimethanol di(meth)acrylate, pentaerythritol tri(meth)acrylate, adamantane triol (Meth) acrylate, adamantane trimethyl alcohol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy group (meth) acrylate or the like.
無機微粒子，因應用途可使用粒徑數nm~10μm者， 例如玻璃粉末、二氧化矽粉末、二氧化鈦、氧化鋅、氧化鋯及氧化鋁等之習知無機微粒子。 Inorganic microparticles, which can be used in the range of nm to 10 μm depending on the application. For example, conventional inorganic fine particles such as glass powder, cerium oxide powder, titanium oxide, zinc oxide, zirconium oxide, and aluminum oxide.
塗平劑，可舉例如矽酮系、氟系之塗平劑。 The coating agent may, for example, be an anthrone or a fluorine-based coating agent.
本發明的組成物，宜用作為形成硬塗層的硬塗樹脂組成物(硬塗劑)。因本發明的聚合物的金剛烷骨架，使硬塗層為高硬度、且抑制硬塗層的彎曲、因(甲基)丙烯酸酯成為交聯單元，而可使硬塗成為更高硬度。 The composition of the present invention is preferably used as a hard coat resin composition (hard coater) for forming a hard coat layer. According to the adamantane skeleton of the polymer of the present invention, the hard coat layer has a high hardness and the bending of the hard coat layer is suppressed, and since the (meth) acrylate becomes a crosslinking unit, the hard coat can be made to have a higher hardness.
使本發明的樹脂組成物硬化而成的硬塗層，因與聚酯薄膜的密著性優異，形成硬塗層時，即使不進行電暈處理等之表面處理，可於聚酯薄膜表面直接塗佈組成物、硬化而成為硬塗薄膜。 The hard coat layer obtained by curing the resin composition of the present invention is excellent in adhesion to a polyester film, and when a hard coat layer is formed, it can be directly applied to the surface of the polyester film without performing surface treatment such as corona treatment. The composition is applied and cured to form a hard coat film.
又，通常聚酯薄膜因加熱而寡聚物析出，薄膜白濁化、霧值變大，但藉由將本發明的組成物硬化而成的硬塗層層合於聚酯薄膜的兩面，可成為即使加熱亦不白濁化或可降低白濁化的硬塗薄膜。 Further, in general, the polyester film is precipitated by heating, and the film is clouded and the haze value is increased. However, the hard coat layer obtained by curing the composition of the present invention is laminated on both surfaces of the polyester film. A hard coat film which does not become cloudy or can reduce whitening even if heated.
硬塗劑主要為聚碳酸酯樹脂、丙烯酸樹脂、聚乙烯對苯二甲酸酯樹脂等之提升耐藥品性及防損傷用之材料。例如藉由以旋轉塗佈、噴塗、淋塗、浸漬等之塗佈方法，塗佈硬塗樹脂組成物及硬化，在基材上形成膜厚2~10μm的硬塗層，可賦予基材耐擦傷性。 The hard coating agent is mainly a material for improving chemical resistance and damage resistance such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin. For example, by coating a hard coating resin composition and curing by a coating method such as spin coating, spray coating, shower coating, or immersion, a hard coat layer having a thickness of 2 to 10 μm is formed on the substrate to impart resistance to the substrate. Scratch.
本發明的組成物的硬化方法，不特別限制，通常可使用加熱硬化法或紫外線照射之硬化法。 The curing method of the composition of the present invention is not particularly limited, and a curing method using a heat curing method or ultraviolet irradiation can be usually used.
加熱硬化法，硬化溫度通常為50~200℃左右、較佳為100~180℃。藉由在50℃以上則不產生硬化不良、在 200℃以下則不造成著色等。 The heat curing method has a curing temperature of usually about 50 to 200 ° C, preferably 100 to 180 ° C. No hardening failure occurs at 50 ° C or higher. Below 200 ° C does not cause coloring and the like.
硬化時間因組成物含有之成分而異，通常以0.5~6小時為佳。 The hardening time varies depending on the components contained in the composition, and is usually 0.5 to 6 hours.
以紫外線照射之硬化法，係使紫外線光量通常成為50~5000mJ/cm2左右、較佳為100~4000mJ/cm2之方式進行照射。紫外線照射後可進行後加熱、以在70~200℃進行0.5~12小時為佳。 In the curing method by ultraviolet irradiation, the amount of ultraviolet light is usually about 50 to 5000 mJ/cm 2 , preferably 100 to 4000 mJ/cm 2 . After the ultraviolet irradiation, post-heating may be performed, and it is preferably carried out at 70 to 200 ° C for 0.5 to 12 hours.
在具備迴流冷卻管、攪拌機、溫度計及氮導入管的1000mL圓底燒瓶中，加入1-金剛烷基甲基丙烯酸酯88.1g、環氧丙基甲基丙烯酸酯56.9g、及甲基異丁基酮300g，進行30分鐘氮打氣。之後，再加入偶氮雙異正丁腈8.2g，升溫至80℃後進行3小時反應。之後，使反應液冷卻至室溫，將氮導入管換成空氣導入管，加入丙烯酸29.4g、三苯基膦2.3g及MQ-F 35mg，邊進行空氣打氣，邊升溫至110℃，使酸價成為5mg-KOH/g以下為止進行12小時反應。 In a 1000 mL round bottom flask equipped with a reflux cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 88.1 g of 1-adamantyl methacrylate, 56.9 g of epoxy propyl methacrylate, and methyl isobutyl group were added. The ketone was 300 g and nitrogen was blown for 30 minutes. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C and then reacted for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and a nitrogen introduction tube was replaced with an air introduction tube, and 29.4 g of acrylic acid, 2.3 g of triphenylphosphine, and 35 mg of MQ-F were added, and the mixture was heated to 110 ° C while air-gasing to make an acid. The reaction was carried out for 12 hours until the valence became 5 mg-KOH/g or less.
使得到的聚合物溶液降至室溫，以固形分濃度成為35wt%之方式加入MIBK，得到反應性聚合物A溶液。 The obtained polymer solution was cooled to room temperature, and MIBK was added in such a manner that the solid content concentration became 35% by weight to obtain a reactive polymer A solution.
除為1-金剛烷基甲基丙烯酸酯112.2g、環氧丙基甲基丙烯酸酯33.5g、偶氮雙異正丁腈7.5g、丙烯酸17.3g、及三苯基膦1.4g外，與實施例1同樣地，得到反應性聚合物B溶液。 In addition to 112.2 g of 1-adamantyl methacrylate, 33.5 g of epoxy propyl methacrylate, 7.5 g of azobisiso-n-butyronitrile, 17.3 g of acrylic acid, and 1.4 g of triphenylphosphine, In the same manner as in Example 1, a reactive polymer B solution was obtained.
除為1-金剛烷基甲基丙烯酸酯52.9g、環氧丙基甲基丙烯酸酯79.6g、偶氮雙異正丁腈8.8g、丙烯酸41.2g、三苯基膦3.3g外，與實施例1同樣地，得到反應性聚合物C溶液。 In addition to 52.9 g of 1-adamantyl methacrylate, 79.6 g of epoxy propyl methacrylate, 8.8 g of azobisiso-n-butyronitrile, 41.2 g of acrylic acid, 3.3 g of triphenylphosphine, and examples In the same manner, a reactive polymer C solution was obtained.
在具備迴流冷卻管、攪拌機、溫度計及氮導入管的1000mL圓底燒瓶中，加入1-金剛烷基甲基丙烯酸酯88.1g、甲基丙烯酸34.4g、及甲基異丁基酮300g，進行30分鐘氮打氣。之後再加入偶氮雙異正丁腈8.2g，升溫至80℃後進行3小時反應。之後，使反應液冷卻至室溫，將氮導入管換成空氣導入管，加入環氧丙基甲基丙烯酸酯56.9g、三苯基膦2.7g、MQ-F 35mg。進行空氣打氣，並升溫至110℃，以酸價成為5mg-KOH/g以下為止進行12小時反應。 In a 1000 mL round bottom flask equipped with a reflux cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 88.1 g of 1-adamantyl methacrylate, 34.4 g of methacrylic acid, and 300 g of methyl isobutyl ketone were added, and 30 was carried out. A few minutes of nitrogen pumping. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C, and then reacted for 3 hours. Thereafter, the reaction liquid was cooled to room temperature, and a nitrogen introduction tube was replaced with an air introduction tube, and 56.9 g of epoxypropyl methacrylate, 2.7 g of triphenylphosphine, and 35 mg of MQ-F were added. Air blowing was performed, and the temperature was raised to 110 ° C, and the reaction was carried out for 12 hours at an acid value of 5 mg-KOH/g or less.
使得到的聚合物溶液降至室溫，以固形分濃度成為35wt%之方式加入MIBK，得到反應性聚合物D溶液。 The obtained polymer solution was cooled to room temperature, and MIBK was added in such a manner that the solid content concentration became 35 wt% to obtain a reactive polymer D solution.
除取代1-金剛烷基甲基丙烯酸酯，使用3-羥基-1-金剛烷基甲基丙烯酸酯94.5g外，與實施例1同樣地，得到反應性聚合物E溶液。 A reactive polymer E solution was obtained in the same manner as in Example 1 except that 1-adamantyl methacrylate was used instead of 94.5 g of 3-hydroxy-1-adamantyl methacrylate.
除取代1-金剛烷基甲基丙烯酸酯，為全氟-1-金剛烷基甲基丙烯酸酯117.6g、環氧丙基甲基丙烯酸酯79.6g、偶氮雙異正丁腈8.8g、甲基異丁基酮400g、丙烯酸41.2g、三苯基膦3.3g以外，與實施例1同樣地，得到反應性聚合物F溶液。 In addition to the substitution of 1-adamantyl methacrylate, it is 117.6 g of perfluoro-1-adamantyl methacrylate, 79.6 g of epoxy propyl methacrylate, 8.8 g of azobisiso-n-butyronitrile, A A reactive polymer F solution was obtained in the same manner as in Example 1 except that 400 g of isobutyl ketone, 41.2 g of acrylic acid, and 3.3 g of triphenylphosphine were used.
除取代1-金剛烷基甲基丙烯酸酯，使用甲基甲基丙烯酸酯55.1g，環氧丙基甲基丙烯酸酯78.2g、偶氮雙異正丁腈12.3g、丙烯酸40.4g及三苯基膦3.2g以外，與實施例1同樣地，得到反應性聚合物G溶液。 In addition to the substitution of 1-adamantyl methacrylate, 55.1 g of methyl methacrylate, 78.2 g of epoxy propyl methacrylate, 12.3 g of azobisiso-n-butyronitrile, 40.4 g of acrylic acid and triphenyl group were used. A reactive polymer G solution was obtained in the same manner as in Example 1 except that 3.2 g of phosphine was used.
於實施例1所調製的反應性聚合物A溶液200g中，加入作為聚合起始劑之1-羥基-環己基-苯基-酮(製品名：IRGACURE184)2.1g，調製硬塗樹脂溶液。 To 200 g of the reactive polymer A solution prepared in Example 1, 2.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone (product name: IRGACURE 184) as a polymerization initiator was added to prepare a hard coating resin solution.
在厚度100μm的PET薄膜(東麗(股)製 LumirrorT60)上，將調製的硬塗樹脂溶液使用棒塗佈器進行塗佈，在90℃進行2分鐘乾燥。之後使用高壓水銀燈以500mJ/min進行照射，使塗佈層硬化，形成厚度5μm的硬塗層。 PET film with a thickness of 100 μm (made by Toray Co., Ltd.) On Lumirror T60), the prepared hard coat resin solution was applied using a bar coater, and dried at 90 ° C for 2 minutes. Thereafter, the coating layer was irradiated with a high pressure mercury lamp at 500 mJ/min to form a hard coat layer having a thickness of 5 μm.
對得到的PET薄膜與硬塗層的層合體之硬塗薄膜，進行以下項目評估。結果如表2。 The hard coat film of the obtained PET film and the hard coat layer laminate was evaluated by the following items. The results are shown in Table 2.
遵循JIS K5600，使用750g荷重之鉛筆刮擦試驗機，測定硬塗薄膜的鉛筆硬度。 The pencil hardness of the hard coat film was measured in accordance with JIS K5600 using a 750 g load pencil scraping tester.
在鋼棉# 0000上施加200gf之荷重後，在硬塗薄膜的硬塗層上來回10次，表面擦傷狀況以目視觀察，用以下的基準評估。 After applying a load of 200 gf to the steel wool # 0000, the surface of the hard coating film was rubbed back and forth 10 times, and the surface scratching condition was visually observed and evaluated by the following criteria.
○：無擦傷 ○: no scratches
△：擦傷未達10條 △: The scratch is not up to 10
×：擦傷10條以上 ×: more than 10 scratches
切取硬塗薄膜10cm×10cm，測定薄膜4角的彎曲高度，將其平均值作為彎曲。 The hard coat film was cut out to 10 cm × 10 cm, and the bending height of the film 4 corner was measured, and the average value was used as a curve.
遵循JIS K5600，在硬塗層切棋盤格子(1mm×1mm、100個)，以玻璃紙膠帶實施剝離試驗，將剝離試驗後之硬塗層的殘存數評估為密著性。例如無剝離場合，殘存數成為100、全剝離場合，殘存數成為0。 The peeling test was carried out on a hard-coated cut-in checkerboard grid (1 mm × 1 mm, 100) in accordance with JIS K5600, and the residual number of the hard coat layer after the peeling test was evaluated as the adhesion. For example, in the case where there is no peeling, the number of remaining is 100, and the total number of peelings is 0.
使用HGM-2DP(司加試驗機公司製)，遵循JIS K7105，進行硬塗薄膜的全光線透過率測定(單位：%)。 The total light transmittance (unit: %) of the hard coat film was measured by using HGM-2DP (manufactured by Siegel Test Co., Ltd.) in accordance with JIS K7105.
依據表1配合量，與實施例8同樣地分別調製硬塗樹脂溶液，使用調製的硬塗樹脂溶液，與實施例8同樣地各自製造硬塗薄膜並進行評估。結果如表2。 The hard coat resin solution was prepared in the same manner as in Example 8 in the same manner as in Example 8, and a hard coat film was produced and evaluated in the same manner as in Example 8 except that the prepared hard coat resin solution was used. The results are shown in Table 2.
於厚度100μm的PET薄膜(東麗(股)製LumirrorT60)，將實施例12所調製的硬塗液使用棒塗佈器進行塗佈，在90℃進行2分鐘乾燥。之後使用高壓水銀燈以500mJ/min進行照射，使塗佈層硬化，形成厚度3μm的硬塗層。該操作在薄膜的相反面亦同樣進行，得到兩面形成有硬塗層的PET薄膜。 The hard coat liquid prepared in Example 12 was applied using a PET film (Lumirror T60, manufactured by Toray Industries, Inc.) having a thickness of 100 μm, and dried at 90 ° C for 2 minutes. Thereafter, the coating layer was irradiated with a high pressure mercury lamp at 500 mJ/min to form a hard coat layer having a thickness of 3 μm. This operation was also carried out on the opposite side of the film to obtain a PET film having a hard coat layer formed on both sides.
將得到的硬塗薄膜在150℃進行1小時加熱，測定加熱前後之全光線透過率與霧值。霧值係遵循JIS K7136以霧值儀測定。結果如表3。 The obtained hard coat film was heated at 150 ° C for 1 hour, and the total light transmittance and the haze value before and after the heating were measured. The haze value was measured by a haze meter in accordance with JIS K7136. The results are shown in Table 3.
除使用比較例2所調製的硬塗液外，與實施例15同樣地製造PET薄膜的兩面形成有硬塗層的硬塗薄膜，並評估。結果如表3。 A hard coat film in which a hard coat layer was formed on both surfaces of a PET film was produced and evaluated in the same manner as in Example 15 except that the hard coat liquid prepared in Comparative Example 2 was used. The results are shown in Table 3.
對PET薄膜(東麗(股)製LumirrorT60)，進行與實施例15同樣的評估。結果如表3。 The PET film (Lumirror T60, manufactured by Toray Industries, Inc.) was evaluated in the same manner as in Example 15. The results are shown in Table 3.
具有由含本發明聚合物之組成物所得到的硬塗層之硬塗薄膜，硬度高、可抑制彎曲，可用作為顯示器用薄膜、尤其觸控式面板用之薄膜。 A hard coat film having a hard coat layer obtained from the composition containing the polymer of the present invention has high hardness and can suppress bending, and can be used as a film for a display, particularly a film for a touch panel.
上述雖詳細說明了幾種本發明的實施形態及/或實施例，但該業者在實質上不違背本發明的新穎揭示及效果、可容易在此等例示的實施形態及/或實施例加以多種變更。因此，此等多種變更包含在本發明之範圍。 Although the embodiments and/or the embodiments of the present invention have been described in detail above, the present invention may be embodied in various embodiments and/or embodiments without departing from the spirit and scope of the invention. change. Accordingly, such various modifications are intended to be included within the scope of the present invention.
以此說明書記載之文獻及本發明巴黎優先權為基礎之日本申請案說明書內容全部在此引用。 The contents of the Japanese Patent Application Serial No.
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| CN106164145B (en) * | 2014-03-31 | 2020-05-22 | 可隆工业株式会社 | Polyester film and transparent electrode film using same |
| WO2020095774A1 (en) * | 2018-11-08 | 2020-05-14 | 昭和電工株式会社 | Copolymer, and resin composition containing copolymer |
| KR20220093101A (en) * | 2019-10-29 | 2022-07-05 | 세키스이가가쿠 고교가부시키가이샤 | Photocurable resin composition for electronic devices |
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| JP4090292B2 (en) * | 2002-06-27 | 2008-05-28 | 富士フイルム株式会社 | Dye-containing curable composition, color filter using the same, and method for producing the same |
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| KR20090104670A (en) * | 2008-03-31 | 2009-10-06 | 후지필름 가부시키가이샤 | Photosensitive resin composition, photospacer, method of producing the same, protection film, colored pattern, substrate for display device, and display device |
| WO2009133784A1 (en) * | 2008-04-28 | 2009-11-05 | 三菱化学株式会社 | Active energy ray-curable resin composition, cured film, laminate, optical recording medium, and method for producing cured film |
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