TWI464189B - Hardened resin composition - Google Patents
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- TWI464189B TWI464189B TW098137268A TW98137268A TWI464189B TW I464189 B TWI464189 B TW I464189B TW 098137268 A TW098137268 A TW 098137268A TW 98137268 A TW98137268 A TW 98137268A TW I464189 B TWI464189 B TW I464189B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Description
本發明係關於硬化性樹脂組成物、塗膜、圖型及顯示裝置。The present invention relates to a curable resin composition, a coating film, a pattern, and a display device.
目前有提出於液晶顯示裝置或觸控面板等,在構成顯示裝置之濾色器與陣列基板之間,以使用了感光性樹脂之光微影術而形成間隔器(光刻型間隔器)一事。藉由此方法,可在任意之場所形成間隔器。作為光微影術所用之組成物,已知含有黏合劑樹脂、光聚合性化合物、光聚合開始劑及溶劑之感光性樹脂組成物(專利文獻1)。At present, a liquid crystal display device, a touch panel, or the like is formed between a color filter constituting a display device and an array substrate, and a spacer (lithographic spacer) is formed by photolithography using a photosensitive resin. . By this method, a spacer can be formed at any place. A photosensitive resin composition containing a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent is known as a composition for photolithography (Patent Document 1).
然而,此般之光微影術由於係經由製膜、曝光、顯像等之步驟而形成間隔器之圖型,其步驟為長且複雜,又,大規模之製造設備則為必要。However, such photolithography is a pattern of spacers formed by steps of film formation, exposure, development, etc., the steps are long and complicated, and large-scale manufacturing equipment is necessary.
光微影術以外之方法已知有藉由噴墨印刷法、橡皮凸板印刷法(flexographic printing)等之印刷法,將含有硬化性樹脂組成物而成之液狀油墨塗佈於被印刷基材上之特定位置,而形成圖型之方法(專利文獻2)。A method other than photolithography is known in which a liquid ink containing a curable resin composition is applied to a printed substrate by a printing method such as an inkjet printing method or a flexographic printing method. A method of forming a pattern by a specific position on a material (Patent Document 2).
[專利文獻1]特開2006-171160號公報[Patent Document 1] JP-A-2006-171160
[專利文獻2]特開2008-158284號公報[Patent Document 2] JP-A-2008-158284
然而,專利文獻1記載之感光性樹脂組成物所含之溶劑之量相對於全組成物為60質量%以上,專利文獻2記載之硬化性樹脂組成物所含之溶劑之量相對於全組成物為80質量%以上,於印刷後去除溶劑用之乾燥則需要長時間,於印刷後或乾燥中因有形狀變化,其並非係容易使用於印刷法。However, the amount of the solvent contained in the photosensitive resin composition described in Patent Document 1 is 60% by mass or more based on the total composition, and the amount of the solvent contained in the curable resin composition described in Patent Document 2 is relative to the total composition. When it is 80% by mass or more, it takes a long time to remove the solvent after printing, and it is not easy to use in the printing method because of shape change after printing or drying.
本發明之課題,在於提供藉由印刷法,可形成高透過率之塗膜或圖型的硬化性樹脂組成物。An object of the present invention is to provide a curable resin composition which can form a coating film or a pattern having a high transmittance by a printing method.
本發明者,為了找出可解決前述課題之硬化性樹脂組成物經過探討之結果,發現藉由將所含之溶劑的量使其相對於全組成物為20質量%以上未滿60質量%,以印刷法可得到可形成高透過率之塗膜或圖型的硬化性樹脂組成物,而完成本發明。The inventors of the present invention have found that the amount of the solvent to be contained is 20% by mass or more and less than 60% by mass based on the total composition, in order to find a result of the curable resin composition which can solve the above-mentioned problems. The present invention has been completed by a printing method to obtain a curable resin composition which can form a coating film or a pattern having a high transmittance.
即,本發明係提供以下之[1]~[16]者。That is, the present invention provides the following [1] to [16].
[1]一種硬化性樹脂組成物,其含有黏合劑樹脂(A)、聚合性化合物(B)及溶劑(D),相對於黏合劑樹脂(A)、聚合性化合物(B)及溶劑(D)之合計量,溶劑(D)之量為20質量%以上未滿60質量%。[1] A curable resin composition comprising a binder resin (A), a polymerizable compound (B), and a solvent (D), with respect to a binder resin (A), a polymerizable compound (B), and a solvent (D) The total amount of the solvent (D) is 20% by mass or more and less than 60% by mass.
[2]如前述[1]記載之硬化性樹脂組成物,相對於黏合劑樹脂(A)、聚合性化合物(B)及溶劑(D)之合計量,溶劑(D)之量為25質量%以上50質量%以下。[2] The curable resin composition according to the above [1], the amount of the solvent (D) is 25% by mass based on the total amount of the binder resin (A), the polymerizable compound (B), and the solvent (D). The above 50% by mass or less.
[3]如前述[1]或[2]記載之硬化性樹脂組成物,其中黏合劑樹脂(A)係為至少使選自由不飽和羧酸及不飽和羧酸酐(A-a)所成裙之至少1種化合物,與具有碳數2~4之環狀醚的單體(A-c)使聚合而成之共聚物。[3] The curable resin composition according to the above [1] or [2] wherein the binder resin (A) is at least at least selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa). A copolymer obtained by polymerizing a compound and a monomer (Ac) having a cyclic ether having 2 to 4 carbon atoms.
[4]如前述[3]記載之硬化性樹脂組成物,其中具有碳數2~4之環狀醚的單體(A-c)為具有環氧基之單體。[4] The curable resin composition according to the above [3], wherein the monomer (A-c) having a cyclic ether having 2 to 4 carbon atoms is a monomer having an epoxy group.
[5]如前述[4]記載之硬化性樹脂組成物,其中具有環氧基之單體為具有脂肪族多環式環氧基之單體。[5] The curable resin composition according to the above [4], wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group.
[6]如前述[5]記載之硬化性樹脂組成物,其中具有脂肪族多環式環氧基之單體為選自由式(I)所表示之化合物及式(II)所表之化合物所成群之至少1種化合物。[6] The curable resin composition according to the above [5], wherein the monomer having an aliphatic polycyclic epoxy group is selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II). A group of at least one compound.
[式(I)及式(II)中,R1 及R2 各自獨立表示氫原子或碳數1~4之烷基。該烷基所含之氫原子可被羥基取代。In the formulae (I) and (II), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X1 及X2 係各自獨立表示可含有單鍵或雜原子之碳數1~6之伸烷基。]X 1 and X 2 each independently represent an alkylene group having 1 to 6 carbon atoms which may have a single bond or a hetero atom. ]
[7]如前述[3]~[6]中任一項記載之硬化性樹脂組成物,其中選自由不飽和羧酸及不飽和羧酸酐(A-a)所成群之至少1種化合物為選自脂肪族不飽和羧酸及脂肪族不飽和羧酸酐所成群之至少1種的化合物。[7] The curable resin composition according to any one of the above [3], wherein at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa) is selected from the group consisting of at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa). A compound of at least one of a group consisting of an aliphatic unsaturated carboxylic acid and an aliphatic unsaturated carboxylic anhydride.
[8]如前述[6]記載之硬化性樹脂組成物,其中選自由式(I)所表示之化合物及式(II)所表示之化合物所成群之至少1種化合物係為選自由式(I’)所表示之化合物及式(II’)所表示之化合物所成群之至少1種化合物。[8] The curable resin composition according to the above [6], wherein at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) is selected from the formula ( At least one compound of the compound represented by I') and the compound represented by the formula (II').
[式(I’)及式(II’)中、R1 ’及R2 ’各自獨立表示氫原子或碳數1~4之烷基。該烷基所含之氫原子可被羥基取代。][In the formula (I') and the formula (II'), R 1 ' and R 2 ' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. ]
[9]如前述[1]~[8]中任一項記載之硬化性樹脂組成物,其中溶劑(D)其沸點為200℃以上,含有選自由酯系溶劑、醚系溶劑及醇系溶劑所成群之至少1種溶劑的溶劑。[9] The curable resin composition according to any one of the above [1], wherein the solvent (D) has a boiling point of 200 ° C or higher and contains an ester solvent, an ether solvent, and an alcohol solvent. A solvent of at least one solvent of the group.
[10]如前述[1]~[9]中任一項記載之硬化性樹脂組成物,其中更含有聚合開始劑(C)。[10] The curable resin composition according to any one of [1] to [9] further comprising a polymerization initiator (C).
[11]如前述[10]記載之硬化性樹脂組成物,其中聚合開始劑(C)係含有選自雙咪唑系化合物、苯乙酮系化合物、三嗪系化合物、醯基膦氧化物系化合物及肟系化合物所群之至少1種之化合物的聚合開始劑。[11] The curable resin composition according to the above [10], wherein the polymerization initiator (C) contains a compound selected from the group consisting of a bisimidazole compound, an acetophenone compound, a triazine compound, and a mercaptophosphine oxide compound. And a polymerization initiator for at least one compound of the group of the lanthanoid compounds.
[12]一種如前述[1]~[11]中任一項記載之硬化性樹脂組成物之使用,其係為形成塗膜或圖型用者。[12] The use of the curable resin composition according to any one of the above [1] to [11], which is to form a coating film or a pattern.
[13]一種塗膜或圖型,其係使用如前述[1]~[11]中任一項記載之硬化性樹脂組成物所形成。[13] A coating film or a pattern formed by using the curable resin composition according to any one of the above [1] to [11].
[14]一種顯示裝置,其係含有前述[13]記載之塗膜或圖型。[14] A display device comprising the coating film or pattern described in the above [13].
[15]一種塗膜或圖型之製造方法,其係具有將如前述[1]~[11]中任一項記載之硬化性樹脂組成物使用印刷法於基材上進行塗佈、乾燥、加熱而得到塗膜或圖型之步驟。[15] A method for producing a coating film or a pattern, which comprises applying the curable resin composition according to any one of the above [1] to [11] on a substrate by a printing method, and drying the composition. The step of heating to obtain a coating film or pattern.
[16]一種塗膜或圖型之製造方法,其係具有將如前述[1]~[11]中任一項記載之硬化性樹脂組成物使用印刷法於基材上進行塗佈、乾燥、曝光處理、更依據需要進行加熱而得到塗膜或圖型之步驟。[16] A method for producing a coating film or a pattern, comprising applying the curable resin composition according to any one of the above [1] to [11] on a substrate by a printing method, and drying the composition. The exposure treatment and the step of heating to obtain a coating film or a pattern are required.
本發明之硬化性樹脂組成物藉由印刷法可形成高透過率之塗膜或圖型。The curable resin composition of the present invention can form a coating film or pattern having a high transmittance by a printing method.
以下,詳細說明本發明。Hereinafter, the present invention will be described in detail.
本發明之硬化性樹脂組成物含有黏合劑樹脂(A)、聚合性化合物(B)及溶劑(D),黏合劑樹脂(A)相對於聚合性化合物(B)及溶劑(D)之合計量,溶劑(D)之量為20質量%以上未滿60質量%者。The curable resin composition of the present invention contains the binder resin (A), the polymerizable compound (B), and the solvent (D), and the total amount of the binder resin (A) relative to the polymerizable compound (B) and the solvent (D) The amount of the solvent (D) is 20% by mass or more and less than 60% by mass.
作為本發明之硬化性樹脂組成物所用之黏合劑樹脂(A),可例示黏合劑樹脂(A1)或黏合劑樹脂(A2)。黏合劑樹脂(A1)具有酸性基,黏合劑樹脂(A2)具有酸性基,且藉由光及熱之至少任一方之作用而顯示反應性。The binder resin (A) used for the curable resin composition of the present invention may, for example, be a binder resin (A1) or a binder resin (A2). The binder resin (A1) has an acidic group, and the binder resin (A2) has an acidic group and exhibits reactivity by at least one of light and heat.
黏合劑樹脂若具有酸性基,則有黏合劑樹脂之Tg及機械特性變高之傾向而為理想。又,將具有碳數2~4之環狀醚構造基的單體(A-c)作為共聚物成分而含有之情況,有硬化性升高、耐藥品性及耐熱性變高之傾向而為理想。When the binder resin has an acidic group, the Tg of the binder resin and the mechanical properties tend to be high. In addition, when the monomer (A-c) having a cyclic ether structural group having 2 to 4 carbon atoms is contained as a copolymer component, it is preferred that the curing property is increased, and chemical resistance and heat resistance are increased.
作為黏合劑樹脂(A1)可例示選自由不飽和羧酸及不飽和羧酸酐所成群之至少1種(A-a)(以下有稱為「(A-a)」之情況),與(A-a)可共聚合之單體(A-b)(但,除(A-a)以外)(以下「有稱為(A-b)」之情況)之共聚物等。The binder resin (A1) is exemplified by at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Aa) (hereinafter referred to as "(Aa)"), and may be co-produced with (Aa) A copolymer of a monomer (Ab) (other than (Aa)) (hereinafter referred to as "Ab").
(A-a)可舉出例如脂肪族不飽和羧酸及/或脂肪族不飽和羧酸酐等,具體而言,例如可舉出,丙烯酸、甲基丙烯酸、巴豆酸等之不飽和單羧酸類;馬來酸、富馬酸、檸康酸、中康酸、伊康酸等之不飽和之羧酸類;及前述之不飽和二羧酸類之無水物;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、酞酸單[2-(甲基)丙烯醯氧基乙基]酯等之2價以上之多價羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類;α-(羥基甲基)丙烯酸等之於同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。(Aa), for example, an aliphatic unsaturated carboxylic acid and/or an aliphatic unsaturated carboxylic anhydride, and the like, and specific examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; An unsaturated carboxylic acid such as acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; and an anhydrous of the aforementioned unsaturated dicarboxylic acid; succinic acid mono [2-(methyl) propylene hydride Unsaturated mono[(methyl)acryloxyalkylene group of a polyvalent carboxylic acid having two or more valences such as oxyethyl] ester and decanoic acid mono [2-(methyl) propylene methoxyethyl] ester An ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
此些之中,以丙烯酸、甲基丙烯酸或無水馬來酸等,其共聚合反應性良好、共聚物之Tg及機械特性高、無黏著(tack)性可理想使用。此些可單獨或組合使用。Among them, acrylic acid, methacrylic acid or anhydrous maleic acid is preferred because it has good copolymerization reactivity, high Tg and mechanical properties of the copolymer, and no tack property. These can be used singly or in combination.
(A-b)可舉出,(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸sec-丁基酯、(甲基)丙烯酸tert-丁基酯等之(甲基)丙烯酸烷基酯類;(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-甲基環己基酯、(甲基)丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯(該技術領域中之慣用名被稱為(甲基)丙烯酸二環戊基酯(Dicyclopentanyl Methacrylate)。)、(甲基)丙烯酸二環戊基氧基乙基酯、(甲基)丙烯酸異佛爾基酯等之(甲基)丙烯酸環狀烷基酯類;丙烯酸環己基酯、丙烯酸2-甲基環己基酯、丙烯酸三環[5.2.1.02,6 ]癸烷-8-基酯(該技術領域中之慣用名被稱丙烯酸二環戊基酯。)、丙烯酸二環戊氧基乙基酯、丙烯酸異佛爾基酯等之丙烯酸環狀烷基酯類;(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等之(甲基)丙烯酸芳香酯類;丙烯酸苯酯、丙烯酸苄酯等之丙烯酸芳香酯類;馬來酸二乙酯、富馬酸二乙酯、伊康酸二乙酯等之二羧酸二酯;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯酯等之羥基烷基酯類;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羧基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2’-羥基甲基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯酐(腐植酸酐)、5-tert-丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己基氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-二(tert-丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-二(環己基氧基羰基)雙環[2.2.1]庚-2-烯等之雙環不飽和化合物類;N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-丁二醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-馬來醯亞胺丁酸酯、N-丁二醯亞胺基-6-馬來醯亞胺己酸酯、N-丁二醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺等之二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、m-甲基苯乙烯、p-甲基苯乙烯、乙烯甲苯、p-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、氯化亞乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。(Ab), methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-(meth)acrylate Alkyl (meth)acrylates such as butyl ester; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(methyl)acrylate [5.2.1.0 2, 6 ]decane-8-yl ester (common name in the art is called Dicyclopentanyl Methacrylate), dicyclopentyloxyethyl (meth)acrylate (meth)acrylic cyclic alkyl esters such as esters, isophoryl (meth)acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.0 2,6 a decane-8-yl ester (common name in the art is called dicyclopentyl acrylate), an acrylic cyclic alkyl group such as dicyclopentyloxyethyl acrylate or isophoryl acrylate. Esters; (meth)acrylic acid aromatic esters such as phenyl (meth) acrylate, benzyl (meth) acrylate; acrylic aryl esters such as phenyl acrylate and benzyl acrylate; diethyl maleate, Fumaric acid a dicarboxylic acid diester such as ethyl ester or diethyl itaconate; a hydroxyalkyl ester such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; bicyclo[2.2 .1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1] Hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxymethyl)bicyclo[ 2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxyl Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2- Alkene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6 -diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1 Hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxyl Methyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2 .1 Hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (humic anhydride), 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tert-butoxycarbonyl) a bicyclic unsaturated compound such as bicyclo [2.2.1] hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl mala Imine, N-cyclohexylmaleimide, N-benzylmaleimide, N-butylenediamine-3-maleimide benzoate, N-butadiene Amino-4-maleimide butyrate, N-butylenediamine-6-maleimide hexanoate, N-butylenediamine-3-maleimide Dicarbonyl quinone imine derivatives such as propionate, N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methyl Styrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butyl Alkene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
此些之中,以苯乙烯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、雙環[2.2.1]庚-2-烯等由共聚合反應性及鹼溶解性之觀點為佳。Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene The viewpoint of copolymerization reactivity and alkali solubility is preferred.
(A-a)及(A-b)可單獨或組合使用。(A-a) and (A-b) may be used singly or in combination.
尚,本說明書中,(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯。In the present specification, (meth) acrylate means acrylate and/or methacrylate.
在使(A-a)及(A-b)共聚合而得之共聚物中,由各自所衍生之構成成分之比率為將構成前述之共聚物的構成成分之合計莫耳數設為100莫耳%時,以莫耳分率在以下之範圍為佳。In the copolymer obtained by copolymerizing (Aa) and (Ab), the ratio of the constituent components derived from the respective copolymers is such that the total number of moles of the constituent components constituting the copolymer is 100 mol%. The molar fraction is preferably in the range below.
由(A-a)所衍生之構成單位:2~40莫耳%Constituent units derived from (A-a): 2~40 mol%
由(A-b)所衍生之構成單位:60~98莫耳%The constituent units derived from (A-b): 60~98 mol%
又,前述之構成成分之比率在以下之範圍為更佳。Further, the ratio of the above-mentioned constituent components is more preferably in the following range.
由(A-a)所衍生之構成單位:5~35莫耳%Constituent units derived from (A-a): 5~35 mol%
由(A-b)所衍生之構成單位:65~95莫耳%Constituent units derived from (A-b): 65~95 mol%
前述之構成比率若在上述之範圍,有保存安定性及耐溶劑性變得良好之傾向。When the composition ratio is within the above range, the storage stability and the solvent resistance tend to be good.
黏合劑樹脂(Al)可參考例如文獻「高分子合成之實驗法」(大津隆行著 發行所(股)化學同人 第1版第1刷 1972年3月1日發行)所記載之方法及該文獻所記載之引用文獻進行製造。The binder resin (Al) can be referred to, for example, the method described in the literature "Experimental method for polymer synthesis" (Dazu Takashi, Institute of Chemicals, 1st edition, 1st brush, issued on March 1, 1972) and the document. The cited documents are manufactured.
具體而言,將構成共聚物之單位(A-a)及(A-b)之既定量、聚合開始劑及溶劑放入反應容器中,藉由以氮取代氧,在不存在氧下,藉由進行攪拌、加熱、保溫而得到聚合物。且,所得之共聚物可直接使用反應後之溶液,亦可使用其經濃縮或稀釋之溶液,也可使用以再沈殿等之方法以固體(粉體)所取出者。Specifically, a predetermined amount, a polymerization initiator, and a solvent of the units (Aa) and (Ab) constituting the copolymer are placed in a reaction vessel, and oxygen is replaced by nitrogen, and stirring is carried out in the absence of oxygen. The polymer is obtained by heating and keeping warm. Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution thereof, or a solid (powder) taken out by a method such as re-sinking.
黏合劑樹脂(A1)之以聚乙烯換算之重量平均分子量,較佳為3,000~100,000,更佳為5,000~50,000。具有酸性基之樹脂(A1)的重量平均分子量若在前述之範圍,有塗佈性變得良好之傾向,且有黏合劑樹脂之Tg及機械特性變高之傾向,黏著性變無之傾向,故為佳。The weight average molecular weight of the binder resin (A1) in terms of polyethylene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) having an acidic group is in the above range, the coating property tends to be good, and the Tg and mechanical properties of the binder resin tend to be high, and the adhesiveness tends to be insufficient. Therefore, it is better.
黏合劑樹脂(A1)之分子量分佈[重量平均分子量(Mw)/數平均分子量(Mn)],較佳為1.1~6.0,更佳為1.2~4.0。分子量分佈若在前述之範圍,因有塗佈性變優良之傾向,故為佳。The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A1) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the coating property tends to be excellent, which is preferable.
可使用於本發明之硬化性樹脂組成物的黏合劑樹脂(A1)之含有量,相對於硬化性樹脂組成物中之固形分以質量分率較佳為5~90質量%,更佳為10~70質量%。黏合劑樹脂(A1)之含有量若在前述之範圍,有印刷性變得良好之傾向,故為佳。The content of the binder resin (A1) to be used in the curable resin composition of the present invention is preferably 5 to 90% by mass, more preferably 10%, based on the solid content of the curable resin composition. ~70% by mass. When the content of the binder resin (A1) is within the above range, the printability tends to be good, which is preferable.
具有酸性基,且藉光及熱之任一方之作用顯示反應性之黏合劑樹脂(A2),可例示(A2-1)~(A2-3)。The binder resin (A2) which has an acidic group and exhibits reactivity by the action of either light or heat can be exemplified by (A2-1) to (A2-3).
黏合劑樹脂(A2-1)係(A-a)、(A-b),與具有碳數2~4之環狀醚構造之單體(A-c)(以下「有稱為(A-c)」之情況)的共聚物。Copolymer resin (A2-1) is a copolymer of (Aa) and (Ab) and a monomer (Ac) having a cyclic ether structure of 2 to 4 (hereinafter referred to as "Ac"). Things.
黏合劑樹脂(A2-2)係在(A-a)與(A-b)之共聚物中,藉由使源自(A-a)之羧基的一部分與源自(A-c)之碳數2~4之環狀醚構造反應而得之共聚物。The binder resin (A2-2) is a copolymer of (Aa) and (Ab) by using a part of the carboxyl group derived from (Aa) and a cyclic ether derived from (Ac) having 2 to 4 carbon atoms. The copolymer obtained by the reaction was constructed.
黏合劑樹脂(A2-3)係(A-a)與(A-c)之共聚物。The binder resin (A2-3) is a copolymer of (A-a) and (A-c).
(A-c)係指例如具有選自由碳數2~4之環狀醚構造(例如,環氧乙烷構造、氧環丁烷構造及四氫呋喃構造所成群之至少1種構造的聚合性化合物。該具有碳數2~4之環狀醚構造的單體(A-c)係以,具有選自由碳數2~4之環狀醚構造所群之至少1種構造且具有碳-碳不飽和鍵結之化合物為佳,以具有選自碳數2~4之環狀醚構造所成群之至少1種構造且具有丙烯醯基或甲基丙烯醯基之化合物為更佳。(Ac) is, for example, a polymerizable compound having at least one structure selected from the group consisting of a cyclic ether structure having 2 to 4 carbon atoms (for example, an ethylene oxide structure, an oxycyclobutane structure, and a tetrahydrofuran structure). The monomer (Ac) having a cyclic ether structure having 2 to 4 carbon atoms has at least one structure selected from the group consisting of a cyclic ether structure having 2 to 4 carbon atoms and having a carbon-carbon unsaturated bond. The compound is preferably a compound having at least one structure selected from the group consisting of a cyclic ether structure having 2 to 4 carbon atoms and having a propylene fluorenyl group or a methacryl fluorenyl group.
(A-c)例如可舉出具有環氧基之單體、具有氧環丁烷基之單體、具有四氫糠基之單體等。(A-c), for example, a monomer having an epoxy group, a monomer having an oxycyclobutane group, a monomer having a tetrahydroindenyl group, and the like can be given.
前述之具有環氧基的單體係指例如具有選自由脂肪族環氧基及脂環式環氧基所成群之至少1種之基的聚合性化合物。該具有環氧基之單體係以具有選自由脂肪族環氧基及脂環式環氧基所成群之至少1種之基,且具有碳-碳不飽和鍵結之化合物為佳,以具有選自由脂肪族環氧基及脂環式環氧基所成選之至少1種之構造,且具有丙烯醯基或甲基丙烯醯基之化合物為佳。The single system having an epoxy group as described above means, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group. The single system having an epoxy group is preferably a compound having at least one selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group, and having a carbon-carbon unsaturated bond. A compound having a structure selected from at least one selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group, and having a propylene fluorenyl group or a methacryl fluorenyl group is preferred.
在此,脂肪族環氧基係指單環之環氧乙烷基(oxiranyl),脂環式環氧基係指具有脂環式烴之環與環氧乙烷環經縮合之構造之基。Here, the aliphatic epoxy group means a monocyclic oxiranyl group, and the alicyclic epoxy group means a group having a structure in which a ring of an alicyclic hydrocarbon is condensed with an oxirane ring.
前述之具有環氧基之單體中,具有脂肪族環氧基之化合物可具體舉出環氧丙基(甲基)丙烯酸酯、β-甲基環氧丙基(甲基)丙烯酸酯、β-乙基環氧丙基(甲基)丙烯酸酯、環氧丙基乙烯醚、記載於特開平7-248625號公報中之以下述之式所示之化合物等。Among the above-mentioned monomers having an epoxy group, the compound having an aliphatic epoxy group may specifically be a glycidyl (meth) acrylate, a β-methyl propyl propyl (meth) acrylate, or a β. - Ethyl propyl propyl (meth) acrylate, a propylene propyl acrylate, and a compound represented by the following formula, which are described in JP-A-H07-248625.
(式中、R11 ~R13 各自獨立為氫原子或碳原子數1~10之烷基,m為1~5之整數)。(wherein R 11 to R 13 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 5).
前述之式所示之化合物例如可舉出o-乙烯苄基環氧丙基醚、m-乙烯苄基環氧丙基醚、p-乙烯苄基環氧丙基醚、α-甲基-o-乙烯苄基環氧丙基醚、α-甲基-m-乙烯苄基環氧丙基醚、α-甲基-p-乙烯苄基環氧丙基醚、2,3-二環氧丙基氧基甲基苯乙烯、2,4-二環氧丙基氧基甲基苯乙烯、2,5-二環氧丙基氧基甲基苯乙烯、2,6-二環氧丙基氧基甲基苯乙烯、2,3,4-三環氧丙基氧基甲基苯乙烯、2,3,5-三環氧丙基氧基甲基苯乙烯、2,3,6-三環氧丙基氧基甲基苯乙烯、3,4,5-三環氧丙基氧基甲基苯乙烯、2,4,6-三環氧丙基氧基甲基苯乙烯等。Examples of the compound represented by the above formula include o-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether, p-vinylbenzylepoxypropyl ether, and α-methyl-o. -vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether, 2,3-diepoxypropyl Hydroxymethylstyrene, 2,4-diepoxypropyloxymethylstyrene, 2,5-diepoxypropyloxymethylstyrene, 2,6-diepoxypropyloxy Methylstyrene, 2,3,4-triepoxypropyloxymethylstyrene, 2,3,5-triepoxypropyloxymethylstyrene, 2,3,6-tricyclic Oloxypropyloxymethylstyrene, 3,4,5-triepoxypropyloxymethylstyrene, 2,4,6-triepoxypropyloxymethylstyrene, and the like.
前述之具有環氧基之單體之中,具有脂環式環氧基之單體例如可舉出具有脂肪族單環式環氧基之單體、具有脂肪族多環式環氧基之單體等。Among the above-mentioned monomers having an epoxy group, the monomer having an alicyclic epoxy group may, for example, be a monomer having an aliphatic monocyclic epoxy group or a single having an aliphatic polycyclic epoxy group. Body and so on.
前述之具有脂肪族單環式環氧基之單體係指具有單環之脂環式烴之環與環氧乙烷環經縮合之構造的聚合性化合物。該具有脂肪族單環式環氧基之單體以具有單環之脂環式烴之環與環氧乙烷環經縮合之構造,且具有碳-碳不飽和鍵結的化合物為佳,以具有單環之脂環式烴之環與環氧乙烷環經縮合之構造,且具有丙烯醯基或甲基丙烯醯基的化合物為更佳。The above-mentioned single system having an aliphatic monocyclic epoxy group means a polymerizable compound having a structure in which a ring of a monocyclic alicyclic hydrocarbon is condensed with an oxirane ring. The monomer having an aliphatic monocyclic epoxy group is preferably a compound having a monocyclic alicyclic hydrocarbon ring condensed with an oxirane ring, and a compound having a carbon-carbon unsaturated bond is preferred. A compound having a monocyclic alicyclic hydrocarbon ring condensed with an oxirane ring and having a propylene fluorenyl group or a methacryl fluorenyl group is more preferable.
該單環之脂環式烴之環例如可舉出環丁烷環、環戊烷環、環己烷環、環庚烷環等,其中以碳數為4~6之環為佳。Examples of the ring of the monocyclic alicyclic hydrocarbon include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. Among them, a ring having 4 to 6 carbon atoms is preferred.
該具有脂肪族單環式環氧基之單體,具體可舉出乙烯環己烯單氧化物1,2-環氧基-4-乙烯環己烷(例如,Celloxide 2000;Daicel化學工業(股)製)、3,4-環氧基環己基甲基丙烯酸酯(例如,Cyclomer A400;Daicel化學工業(股)製)、3,4-環氧基環己基甲基甲基丙烯酸酯(例如,Cyclomer M100;Daicel化學工業(股)製)等。The monomer having an aliphatic monocyclic epoxy group, specifically, ethylenecyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel Chemical Industry Co., Ltd. ), 3,4-epoxycyclohexyl methacrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industry Co., Ltd.).
前述之具有脂肪族多環式環氧基之單體係指具有多環之脂環式烴之環與環氧乙烷環經縮合之構造的聚合性化合物。該具有多環之脂環式烴之環與環氧乙烷環經縮合之構造的單體以具有多環之脂環式烴之環與環氧乙烷環經縮合之構造,且具有碳-碳不飽和鍵結的化合物為佳,以具有多環之脂環式烴之環與環氧乙烷環經縮合之構造,且具有丙烯醯基或甲基丙烯醯基的化合物為更佳。The above-mentioned single system having an aliphatic polycyclic epoxy group means a polymerizable compound having a structure in which a ring of an alicyclic hydrocarbon having a polycyclic ring is condensed with an oxirane ring. The monomer having a structure in which a ring of a polycyclic alicyclic hydrocarbon is condensed with an oxirane ring has a structure in which a ring having a polycyclic alicyclic hydrocarbon is condensed with an oxirane ring, and has a carbon- The carbon-unsaturated bonded compound is preferred, and a compound having a polycyclic alicyclic hydrocarbon ring condensed with an oxirane ring and having a propylene fluorenyl group or a methacryl fluorenyl group is more preferable.
該多環之脂環式烴之環例如可舉出二環戊烷環、三環癸烷環、降莰烷環、異降莰烷環、雙環辛烷環、雙環壬烷環、雙環十一烷環、三環十一烷環、雙環十二烷環、三環十二烷環等,其中以碳數為8至12之化合物為佳。Examples of the ring of the polycyclic alicyclic hydrocarbon include a dicyclopentane ring, a tricyclodecane ring, a norbornane ring, an isodecane ring, a bicyclooctane ring, a bicyclodecane ring, and a bicyclo 11 An alkane ring, a tricycloundecane ring, a bicyclododecan ring, a tricyclododecane ring or the like, wherein a compound having 8 to 12 carbon atoms is preferred.
前述之具有脂肪族多環式環氧基之單體,例如可舉出選自由式(I)所表示之化合物及式(II)所表示之化合物所成群之至少1種之化合物等。The monomer having an aliphatic polycyclic epoxy group is, for example, a compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II).
式(I)及式(II)中,R1 及R2 各自獨立表示可被氫原子或羥基取代之碳數1~4之烷基。In the formulae (I) and (II), R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydrogen atom or a hydroxyl group.
X1 及X2 各自獨立表示單鍵或可含雜原子之碳數1~6之伸烷基。X 1 and X 2 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may contain a hetero atom.
R1 及R2 具體的可舉出氫原子;甲基、乙基、N-丙基、異丙基、n-丁基、sec-丁基、tert-丁基等之烷基;羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基-n-丙基、2-羥基-n-丙基、3-羥基-n-丙基、1-羥基-異丙基、2-羥基-異丙基、1-羥基-n-丁基、2-羥基-n-丁基、3-羥基-n-丁基、4-羥基-n-丁基等之含有羥基之烷基。其中,較佳可舉出氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基,更佳可舉出氫原子、甲基。Specific examples of R 1 and R 2 include a hydrogen atom; an alkyl group of a methyl group, an ethyl group, an N-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or the like; a hydroxymethyl group; , 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, 2- A hydroxy-containing alkyl group such as hydroxy-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl or the like. Among them, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a hydrogen atom or a methyl group is more preferable.
X1 及X2 具體可舉出單鍵;亞甲基、伸乙基、伸丙基等之伸烷基;氧基亞甲基、氧基伸乙基、氧基伸丙基、硫代亞甲基、硫代伸乙基、硫代伸丙基、胺基亞甲基、胺基伸乙基、胺基伸丙基等之含有雜原子之伸烷基等。其中,較佳可舉出單鍵、亞甲基、伸乙基、氧基亞甲基、氧基伸乙基,更佳可舉出單鍵、氧基伸乙基。Specific examples of X 1 and X 2 include a single bond; an alkylene group such as a methylene group, an ethyl group, and a propyl group; an oxymethylene group, an oxyethyl group, an oxypropyl group, and a thiomethylene group; And a thiol-ethyl group, a thio-propyl group, an aminomethylene group, an amine group ethyl group, an amine group propyl group, and the like, and a hetero atom-containing alkyl group. Among them, a single bond, a methylene group, an ethylidene group, an oxymethylene group, and an oxyethyl group are preferable, and a single bond or an oxyethyl group is more preferable.
作為選自式(I)所表示之化合物及式(II)所表示之化合物所成群之至少1種之化合物,以選自由下述之式(I’)所表示之化合物及式(II’)所表示之化合物所成群之至少1種之化合物為佳。The compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II), which is selected from the group consisting of the compound represented by the following formula (I') and the formula (II') It is preferred that at least one of the compounds represented by the group is a compound.
式(I’)及式(II’)中,R1 ’及R2 ’各自與前述R1 及R2 同義。In the formula (I') and the formula (II'), R 1 ' and R 2 ' are each synonymous with the above R 1 and R 2 .
式(I)所表示之化合物,具體可舉出例如式(I-1)~式(I-15)所表示之化合物等,較佳可舉出式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)、式(I-11)~式(I-15),更佳可舉出式(I-1)、式(I-7)、式(I-9)、式(I-15)。Specific examples of the compound represented by the formula (I) include a compound represented by the formula (I-1) to the formula (I-15), and the formula (I-1) and the formula (I-3) are preferred. ), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), more preferably formula (I-1), formula (I-7), formula (I-9), and formula (I-15).
式(II)所表示化合物,具體可舉出例如式(II-1)~式(II-15)所表示之化合物等,較佳可舉出式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)、式(II-11)~式(II-15),更佳可舉出式(II-1)、式(II-7)、式(II-9)、式(II-15)。Specific examples of the compound represented by the formula (II) include a compound represented by the formula (II-1) to the formula (II-15), and preferably a formula (II-1) or a formula (II-3). , formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably formula (II-1), formula ( II-7), formula (II-9), formula (II-15).
選自由式(I)所表示之化合物及式(II)所表示之化合物所成群之至少1種化合物,可各自單獨使用,亦可以任意之比率進行混合。進行混合之情況,其混合比率以莫耳比式(I):式(II)為5:95~95:5為佳,較佳為10:90~90:10,更佳為20:80~80:20。At least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in any ratio. In the case of mixing, the mixing ratio is preferably in the molar ratio (I): formula (II) is from 5:95 to 95:5, preferably from 10:90 to 90:10, more preferably from 20:80. 80:20.
前述之具有氧環丁烷基之單體係指例如具有選自由脂肪族氧環丁烷基及脂環式氧環丁烷基所成群之至少1種之基的聚合性化合物。該具有氧環丁烷基之單體係以具有選自由脂肪族氧環丁烷基及脂環式氧環丁烷基所成群之至少1種之基,且具有不飽和鍵結之化合物為佳。The above-mentioned single system having an oxycyclobutane group means, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxycyclobutane group and an alicyclic oxycyclobutane group. The single system having an oxycyclobutane group has at least one selected from the group consisting of an aliphatic oxycyclobutane group and an alicyclic oxocyclobutane group, and the compound having an unsaturated bond is good.
該具有氧環丁烷基之單體具體可舉出3-甲基-3-甲基丙烯醯氧基甲基氧環丁烷、3-甲基-3-丙烯醯氧基甲基氧環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧環丁烷、3-乙基-3-丙烯醯氧基甲基氧環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧環丁烷、3-甲基-3-丙烯醯氧基乙基氧環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧環丁烷或3-乙基-3-丙烯醯氧基乙基氧環丁烷等。Specific examples of the monomer having an oxycyclobutane group include 3-methyl-3-methylpropenyloxymethyloxycyclobutane and 3-methyl-3-propenyloxymethyloxycyclobutane. Alkane, 3-ethyl-3-methylpropenyloxymethyloxycyclobutane, 3-ethyl-3-propenyloxymethyloxycyclobutane, 3-methyl-3-methylpropene Ethoxyethyloxycyclobutane, 3-methyl-3-propenyloxyethyloxycyclobutane, 3-ethyl-3-methylpropenyloxyethyloxycyclobutane or 3- Ethyl-3-propenyloxyethyloxycyclobutane or the like.
此些可單獨或組合使用。These can be used singly or in combination.
前述之具有四氫糠基之單體係指例如具有選自由脂肪族四氫糠基及脂環式四氫糠基所成群之至少種之基的聚合性化合物。該具有四氫糠基之單體係以具有選自由脂肪族四氫糠基及脂環式四氫糠基所成之至少1種之基,且具有不飽和鍵結之化合物為佳。The above-mentioned single system having a tetrahydroindenyl group means, for example, a polymerizable compound having at least a group selected from the group consisting of an aliphatic tetrahydroindenyl group and an alicyclic tetrahydroindenyl group. The single system having a tetrahydroindenyl group is preferably a compound having at least one selected from the group consisting of an aliphatic tetrahydroindenyl group and an alicyclic tetrahydroindenyl group, and having an unsaturated bond.
該具有四氫糠基之單體具體可舉出四氫糠基丙烯酸酯、四氫糠基甲基丙烯酸酯等。Specific examples of the monomer having a tetrahydroindenyl group include tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate.
此些可單獨或將其組合使用。These may be used singly or in combination.
黏合劑樹脂(A2-1)中,由各自所衍生之構成成分之比率,相對於構成黏合劑樹脂(A2-1)之構成成分之合計莫耳數,以莫耳分率表示在以下之範圍為佳。In the binder resin (A2-1), the ratio of the constituent components derived from each of the components is expressed in the following range with respect to the total number of moles of the constituent components constituting the binder resin (A2-1). It is better.
由(A-a)所衍生之構成單位:2~40莫耳%Constituent units derived from (A-a): 2~40 mol%
由(A-b)所衍生之構成單位:1~65莫耳%Constituent units derived from (A-b): 1~65mol%
由(A-c)所衍生之構成單位:2~95莫耳%Constituent units derived from (A-c): 2~95 mol%
又,前述之構成成分之比率以在以下之範圍為更佳。Further, the ratio of the aforementioned constituent components is more preferably in the range below.
由(A-a)所衍生之構成單位:5~35莫耳%Constituent units derived from (A-a): 5~35 mol%
由(A-b)所衍生之構成單位:1~60莫耳%Constituent units derived from (A-b): 1~60 mol%
由(A-c)所衍生之構成單位:5~80莫耳%The constituent units derived from (A-c): 5~80 mol%
前述之構成比率若在上述之範圍,有保存安定性、耐溶劑性、耐熱性及機械強度變得良好之傾向。When the composition ratio is within the above range, the stability, the solvent resistance, the heat resistance, and the mechanical strength tend to be good.
黏合劑樹脂(A2-1)可參考例如文獻「高分子合成之實驗法」(大津隆行著 發行所(股)化學同人第1版第1刷1972年3月1日發行)所記載之方法及該當文獻中記載之引用文獻進行製造。The binder resin (A2-1) can be referred to, for example, the method described in the literature "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd., 1st Edition, 1st Edition, 1st March, 1972). The cited documents described in the literature are manufactured.
具體而言,可將衍生構成共聚物之單位(A-a)、(A-b)及(A-c)的化合物既定量、聚合開始劑及溶劑放入反應容器中,藉以氮將氧取代,在不存在氧下,藉由進行攪拌、加熱、保溫,得到聚合物。且,所得之共聚物係可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,也可使用以再沈殿等之方法以固體(粉體)所取出者。Specifically, the compounds derived from the units (Aa), (Ab), and (Ac) constituting the copolymer can be metered in a predetermined amount, a polymerization initiator, and a solvent, and the oxygen is substituted in the absence of oxygen. The polymer was obtained by stirring, heating, and heat preservation. Further, the obtained copolymer may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) may be used by a method such as re-sinking.
製造黏合劑樹脂(A2-2)時,首先使(A-a)及(A-b)共聚合而製造共聚物。由各個所衍生之構成成分之比率,相對於構成前述之共聚物之構成成分的合計莫耳數,其莫耳分率以在以下之範圍為佳。When the binder resin (A2-2) is produced, (A-a) and (A-b) are first copolymerized to produce a copolymer. The ratio of the constituent components derived from each of the components is preferably in the range of the following with respect to the total number of moles constituting the constituent components of the copolymer.
由(A-a)所衍生之構成單位:5~50莫耳%Constituent units derived from (A-a): 5~50 mol%
由(A-b)所衍生之構成單位:50~95莫耳%Constituent units derived from (A-b): 50~95 mol%
又,前述之構成成分之比率若在以下之範圍為更佳。Further, the ratio of the above-mentioned constituent components is more preferably in the following range.
由(A-a)所衍生之構成單位:10~45莫耳%The constituent units derived from (A-a): 10~45 mol%
由(A-b)所衍生之構成單位:55~90莫耳%Constituent units derived from (A-b): 55~90 mol%
其次,為了使其具有因光或熱之作用所成之反應性,使源自將(A-a)及(A-b)共聚合所得之共聚物的(A-a)之羧酸及羧酸酐之一部分與源自(A-c)之環氧基或氧環丁烷基反應。Next, in order to have reactivity due to the action of light or heat, a part of the carboxylic acid and the carboxylic anhydride derived from the copolymer obtained by copolymerizing (Aa) and (Ab) is derived from (Ac) an epoxy group or an oxocyclobutane group.
(A-c)之莫耳數係相對於(A-a)之莫耳數為5~80莫耳%,較佳為10~75莫耳%,更佳為15~70莫耳%。The number of moles of (A-c) is from 5 to 80 mol%, preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%, relative to the number of moles of (A-a).
構成比率若在上述之範圍,有保存安定性、耐溶劑性、耐熱性、機械強度及感度(所謂的光硬化性)之平衡變得良好之傾向。When the composition ratio is within the above range, the balance between storage stability, solvent resistance, heat resistance, mechanical strength, and sensitivity (so-called photocurability) tends to be good.
黏合劑樹脂(A2-2)可經由二階段之步驟而製造。例如可參考文獻「高分子合成之實驗法」(大津隆行著 發行所(股)化學同人第1版第1刷1972年3月1日發行)所記載之方法,或特開2001-89533號公報中記載之方法而進行製造。The binder resin (A2-2) can be produced through a two-stage process. For example, please refer to the document "Experimental method for polymer synthesis" (the method described in the first issue of the first issue of the Otsuka Ryokan, Ltd.), or the publication of the 2001-89533 Manufactured by the method described in the above.
具體而言,首先說明關於第一階段之步驟。將衍生構成(A-a)及(A-b)共聚合而得之共聚物(即,黏合劑樹脂)之單位(A-a)及(A-b)的化合物既定量、聚合開始劑及溶劑放入反應容器中,藉由以氮取代氧,在不存在氧下,藉由攪拌、加熱、保溫,得到黏合劑樹脂。且,所得之樹脂,可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,也可使用以再沈殿等之方法以固體(粉體)所取出者。前述之樹脂以聚乙烯換算之重量平均分子量,以3,000~100,000為佳,5,000~50,000為更佳。樹脂之重量平均分子量若在前述之範圍,有塗佈性變得良好之傾向,故為佳。Specifically, the steps regarding the first stage are first explained. A compound (Aa) and (Ab) of a copolymer (ie, a binder resin) obtained by copolymerizing the copolymers (Aa) and (Ab) are derivatized, a polymerization initiator, and a solvent are placed in a reaction vessel. The binder resin is obtained by substituting oxygen with nitrogen and stirring, heating, and holding in the absence of oxygen. Further, as the obtained resin, the solution after the reaction may be used as it is, or a solution which is concentrated or diluted may be used, or a solid (powder) may be used by a method such as re-sinking. The above-mentioned resin preferably has a weight average molecular weight in terms of polyethylene, preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin is within the above range, the coating property tends to be good, which is preferable.
前述之樹脂之分子量分佈[重量平均分子量(Mw)/數平均分子量(Mn)],較佳為1.1~6.0,更佳為1.2~4.0。分子量分佈若在前述之範圍,因有塗佈性變優良之傾向,故為佳。The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the above resin is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the coating property tends to be excellent, which is preferable.
其次,說明關於第二階段之步驟。接著,將燒瓶內雰圍由氮取代為空氣,將相對於構成成分(A-a)之莫耳數為5~80莫耳%之構成成分(A-c)、作為羧基與環氧基或氧環丁烷基之反應觸媒,例如使參二甲基胺基甲基酚為相對於單體(A-a)~(A-c)之合計量以質量基準為0.001~5%、及作為聚合禁止劑,例如使氫醌相對於單體(A-a)~(A-c)之合計量以質量基準為0.001~5%放入燒瓶內,藉由在60~130℃下持續1~10小時反應,可使前述之樹脂與構成成分(A-c)反應。但,與聚合條件同樣地,考慮到製造設備或聚合所生成之發熱量等,可適宜調整放入方法或反應溫度。Next, explain the steps related to the second phase. Next, the atmosphere in the flask is replaced with air by nitrogen, and the component (Ac) having a molar number of 5 to 80 mol% based on the constituent component (Aa) is used as a carboxyl group and an epoxy group or an oxycyclobutane group. The reaction catalyst, for example, dimethylaminomethylphenol is 0.001 to 5% by mass based on the total amount of the monomers (Aa) to (Ac), and is used as a polymerization inhibiting agent, for example, hydroquinone. The total amount of the monomers (Aa) to (Ac) is 0.001 to 5% by mass based on the mass basis, and the resin and constituents can be obtained by reacting at 60 to 130 ° C for 1 to 10 hours. (Ac) reaction. However, similarly to the polymerization conditions, the introduction method or the reaction temperature can be appropriately adjusted in consideration of the heat generation amount generated by the production equipment or the polymerization.
黏合劑樹脂(A2-3)中,由各自所衍生之構成成分之比率,相對於構成黏合劑樹脂(A2-3)之構成成分之合計莫耳數,以莫耳分率在以下之範圍為佳。In the binder resin (A2-3), the ratio of the constituent components derived from the respective components to the total number of moles of the constituent components constituting the binder resin (A2-3) is in the range of the following molar ratio. good.
由(A-a)所衍生之構成單位:5~95莫耳%Constituent units derived from (A-a): 5~95 mol%
由(A-c)所衍生之構成單位:5~95莫耳%Constituent units derived from (A-c): 5~95 mol%
又,前述之構成成分之比率若在以下之範圍為更佳。Further, the ratio of the above-mentioned constituent components is more preferably in the following range.
由(A-a)所衍生之構成單位:10~90莫耳%Constituent units derived from (A-a): 10~90 mol%
由(A-c)所衍生之構成單位:10~90莫耳%The constituent units derived from (A-c): 10~90 mol%
前述之構成比率若在上述之範圍,有保存安定性、耐溶劑性、耐熱性及機械強度變得良好之傾向。When the composition ratio is within the above range, the stability, the solvent resistance, the heat resistance, and the mechanical strength tend to be good.
黏合劑樹脂(A2-3)例如可參考文獻「高分子合成之實驗法」(大津隆行著發行所(股)化學同人第1版第1刷1972年3月1日發行)所記載之方法及該文獻中記載之引用文獻而製造。The binder resin (A2-3) can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd., 1st Edition, 1st Edition, 1st March, 1972). It is manufactured by reference to the documents described in the literature.
具體而言,將衍生構成共聚物之單位(A-a)及(A-c)的化合物既定量、聚合開始劑及溶劑放入反應容器中,藉由以氮取代氧,在不存在氧下,藉由攪拌、加熱、保溫,得到聚合物。且,所得之共聚物係可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,也可使用以再沈殿等之方法以固體(粉體)所取出者Specifically, a compound which derivatizes the units (Aa) and (Ac) constituting the copolymer is metered, a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by nitrogen in the absence of oxygen by stirring. Heating, heat preservation, and obtaining a polymer. Moreover, the obtained copolymer may be directly used as a solution after the reaction, or may be a solution which is concentrated or diluted, or may be used as a solid (powder) by a method such as re-sinking.
本發明之硬化性樹脂組成物所含之聚合性化合物(B),可舉出單官能單體、2官能單體或其他3官能以上之多官能單體。The polymerizable compound (B) contained in the curable resin composition of the present invention may, for example, be a monofunctional monomer, a bifunctional monomer or another trifunctional or higher polyfunctional monomer.
單官能單體之具體例可舉出壬基苯基卡必醇(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、2-乙基己基卡必醇(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十八基(甲基)丙烯酸酯、2-(2-乙氧基乙氧基)乙基(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、己內酯(甲基)丙烯酸酯、乙氧基化壬基酚(甲基)丙烯酸酯、丙氧基化壬基酚(甲基)丙烯酸酯或N-乙烯吡咯啶酮等。Specific examples of the monofunctional monomer include mercaptophenylcarbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-ethylhexylcarbitol. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, 2-(2-ethoxy ethoxy) Ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonyl phenol (meth) acrylate, propoxylated fluorenyl group Phenol (meth) acrylate or N-vinyl pyrrolidone.
又,2官能單體之具體例可舉出1,3-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚、乙氧基化雙酚A之(甲基)丙烯酸酯、丙氧基化新戊二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯或3-甲基戊二醇二(甲基)丙烯酸酯等。Further, specific examples of the bifunctional monomer include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, and 1,6-hexanediol II ( Methyl) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, triethylene glycol di(methyl) Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylated bisphenol A (methyl) Acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate or 3-methylpentanediol di(meth)acrylate .
其他之3官能以上之多官能單體之具體例可舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、參(2-羥基乙基)異氰脲酸酯三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(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、三季戊四醇四(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯與酸酐之反應物、二季戊四醇五(甲基)丙烯酸酯與酸酐之反應物、三季戊四醇七(甲基)丙烯酸酯與酸酐己內酯變性三羥甲基丙烷三(甲基)丙烯酸酯、己內酯變性季戊四醇三(甲基)丙烯酸酯、己內酯變性參(2-羥基乙基)異氰脲酸酯三(甲基)丙烯酸酯、己內酯變性季戊四醇四(甲基)丙烯酸酯、己內酯變性二季戊四醇五(甲基)丙烯酸酯、己內酯變性二季戊四醇六(甲基)丙烯酸酯、己內酯變性三季戊四醇四(甲基)丙烯酸酯、己內酯變性三季戊四醇五(甲基)丙烯酸酯、己內酯變性三季戊四醇六(甲基)丙烯酸酯、己內酯變性三季戊四醇七(甲基)丙烯酸酯、己內酯變性三季戊四醇八(甲基)丙烯酸酯、己內酯變性季戊四醇三(甲基)丙烯酸酯與酸酐之反應物、己內酯變性二季戊四醇五(甲基)丙烯酸酯與酸酐之反應物,或己內酯變性三季戊四醇五(甲基)丙烯酸酯與酸酐等。Specific examples of the other trifunctional or higher polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and gin(2-hydroxyethyl)isocyanurate. Ester tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate Reaction of ester, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate with anhydride, dipentaerythritol penta (meth) acrylate and anhydride , trimellititol hepta (meth) acrylate and anhydride caprolactone denatured trimethylolpropane tri(meth) acrylate, caprolactone denatured pentaerythritol tri (meth) acrylate, caprolactone denatured ginseng (2- Hydroxyethyl)isocyanurate tri(meth)acrylate, Ester-modified pentaerythritol tetra(meth)acrylate, caprolactone denatured dipentaerythritol penta (meth) acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol tetra(methyl) Acrylate, caprolactone denatured tripentaerythritol penta (meth) acrylate, caprolactone denatured tripentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol hepta (meth) acrylate, caprolactone denature a reaction of pentaerythritol octa (meth) acrylate, caprolactone denatured pentaerythritol tri(meth) acrylate with an acid anhydride, a reaction of caprolactone denatured dipentaerythritol penta (meth) acrylate with an acid anhydride, or caprolactone Denatured tripentaerythritol penta (meth) acrylate with an acid anhydride or the like.
尚,本說明書中,己內酯變性係指在源自(甲基)丙烯酸酯化合物之醇的部位與(甲基)丙烯醯氧基之間,導入己內酯之開環體或開環聚合物一事。Further, in the present specification, caprolactone denature means a ring-opening or ring-opening polymerization in which a caprolactone is introduced between a site derived from an alcohol of a (meth) acrylate compound and a (meth) acryloxy group. Things.
特別係使用2官能以上之多官能單體為佳。此些之聚合性化合物(B)可單獨或將二種以上併用使用。In particular, it is preferred to use a polyfunctional monomer having two or more functional groups. These polymerizable compounds (B) may be used singly or in combination of two or more.
聚合性化合物(B)之含有量,相對於黏合劑樹脂(A)及聚合性化合物(B)之合計量,以質量分率較佳為1~70質量%,更佳為5~60質量%。聚合性化合物(B)之含有量若在前述之範圍,有感度、塗膜及圖型之強度、平滑性、信頼性及機械強度變得良好之傾向,故為佳。The content of the polymerizable compound (B) is preferably from 1 to 70% by mass, and more preferably from 5 to 60% by mass, based on the total of the binder resin (A) and the polymerizable compound (B). . When the content of the polymerizable compound (B) is within the above range, the strength, smoothness, letterability, and mechanical strength of the coating film and the pattern tend to be good, which is preferable.
本發明之硬化性樹脂組成物所含之聚合開始劑(C)係為藉光或熱之作用而開始聚合之化合物,以雙咪唑系化合物、苯乙酮系化合物、三嗪系化合物、醯基膦氧化物系化合物或肟系化合物為佳,因雙咪唑系化合物感度優良為特佳。The polymerization initiator (C) contained in the curable resin composition of the present invention is a compound which starts polymerization by the action of light or heat, and is a bisimidazole compound, an acetophenone compound, a triazine compound, or a mercapto group. A phosphine oxide compound or an anthraquinone compound is preferred, and a bisimidazole compound is particularly excellent in sensitivity.
前述之雙咪唑化合物可舉出2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑(例如參考特開平6-75372號公報、特開平6-75373號公報等)、2,2’-雙(2-氯苯基)4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)雙咪唑(例如參考特公昭48-38403號公報、特開昭62-174204號公報等)、4,4’5,5’-位之苯基被烷氧羰基取代之咪唑化合物(例如參考特開平7-10913號公報等)等,較佳可舉出2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2、3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2、4-二氯苯基)-4,4’,5,5’-四苯基雙咪唑。The above biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2- Chlorophenyl) 4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Bis-imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), 4, The imidazole compound in which the phenyl group at the 4', 5'-position is substituted with an alkoxycarbonyl group (for example, JP-A-7-10913, etc.), etc., preferably 2,2'-bis(2-chlorophenyl) )-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole.
前述之苯乙酮系化合物可舉出二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙烷-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、1-羥基環己基苯基酮、2-甲基-2-嗎啉基-1-(4-甲基磺醯基)丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、2-(2-甲基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-甲基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-甲基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-乙基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-丙基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-丁基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2,3-二甲基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2、4-二甲基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-氯苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-溴苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-氯苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-氯苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-溴苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-溴苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-甲氧基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-甲氧基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-甲氧基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-甲基-4-甲氧基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-甲基-4-溴苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-溴-4-甲氧基苄基)-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮之寡聚物等。Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1. -[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionium) -benzyl]-phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl-1-(4-methyl sulfonate Mercapto)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(2-methylbenzyl) -2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-ethylbenzyl 2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4- Morpholinylphenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,3 -Dimethylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethyl Amino-1-(4-morpholinylphenyl)-butanone, 2-(2-chlorobenzyl)- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinylbenzene Butyl ketone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-chlorobenzyl)-2 -Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl) -butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methoxybenzyl)- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl 4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2- Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4- An oligomer of morpholinylphenyl)-butanone or 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.
前述之三嗪系化合物可舉出2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙炔基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙炔基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙炔基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙炔基]-1,3,5-三嗪等。The aforementioned triazine-based compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethynyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Ethynyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethynyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethynyl]-1,3,5-triazine Wait.
前述之醯基膦氧化物系開始劑可舉出2,4,6-三甲基苄醯基二苯基膦氧化物等。The above-mentioned mercaptophosphine oxide-based starter may, for example, be 2,4,6-trimethylbenzylidenediphenylphosphine oxide.
前述之肟化合物可舉出O-乙氧基羰基-α-氧基胺基-1-苯基丙烷-1-酮、式(IV)所表示之化合物、式(V)所表示之化合物等。The above-mentioned oxime compound may, for example, be O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, a compound represented by the formula (IV), a compound represented by the formula (V), or the like.
只要係不損及本發明之效果的程度,可更併用光聚合開始劑等,該光聚合開始劑可舉出例如安息香系化合物、二苯甲酮系化合物或噻吨酮系化合物等。A photopolymerization initiator or the like can be used in combination as long as the effect of the present invention is not impaired. Examples of the photopolymerization initiator include a benzoin compound, a benzophenone compound, and a thioxanthone compound.
更具體而言可舉出以下般之化合物,此些可各別單獨,或將2種以上組合使用。More specifically, the following compounds may be mentioned, and these may be used individually or in combination of 2 or more types.
前述之安息香系化合物可舉出例如安息香、安息香甲醚、安息香乙醚、安息香異丙醚或安息香異丁醚等。The aforementioned benzoin-based compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether.
前述之二苯甲酮系化合物,例如可舉出二苯甲酮、o-苄醯基安息香酸甲酯、4-苯基二苯甲酮、4-苄醯基-4’-甲基二苯基硫化物、3,3’,4,4’-四(tert-丁基過氧羰基)二苯甲酮或2,4,6-三甲基二苯甲酮等。Examples of the benzophenone-based compound include benzophenone, methyl o-benzyl benzoate, 4-phenylbenzophenone, and 4-benzylindolyl-4'-methyldiphenyl. a sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone.
前述之噻吨酮系化合物,例如可舉出2-異丙基噻吨酮、4-異丙基噻吨酮、2,4-二乙基噻吨酮、2,4-二氯噻吨酮或1-氯-4-丙氧基噻吨酮等。Examples of the aforementioned thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. Or 1-chloro-4-propoxythioxanthone and the like.
其他也可例示10-丁基-2-氯吖啶酮、2-乙基蒽醌、苄基、9,10-菲醌、莰醌、苯基乙醛酸甲酯或二茂鈦化合物等作為光聚合開始劑。Other examples thereof include 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, anthracene, methyl phenylglyoxylate or a titanocene compound. Photopolymerization initiator.
又,具有可引起鏈轉移之基的光聚合開始劑,可使用特表2002-544205號公報記載之光聚合開始劑。Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-A-2002-544205 can be used.
前述之具有可引起鏈轉移之基的光聚合開始劑,可舉出例如下述式(5)~下述式(10)之光聚合開始劑。The photopolymerization initiator having a group which can cause a chain transfer, for example, is a photopolymerization initiator of the following formula (5) to the following formula (10).
又,可使用光及/或熱陽離子聚合開始劑。Further, a light and/or thermal cationic polymerization initiator can be used.
光及/或熱陽離子聚合開始劑可使用由鎓陽離子與源自路易斯酸之陰離子所構成者。The photo-and/or thermal cationic polymerization initiator may be composed of a phosphonium cation and an anion derived from a Lewis acid.
前述鎓陽離子之具體例可舉出二苯基錪鎓、雙(p-苄基)錪鎓、雙(p-tert-丁基苯基)錪鎓、雙(p-辛基苯基)錪鎓、雙(p-十八基苯基)錪鎓、雙(p-辛基氧基苯基)錪鎓、雙(p-十八基氧基苯基)錪鎓、苯基(p-十八基氧基苯基)錪鎓、(p-苄基)(p-異丙基苯基)錪鎓、三苯基鋶、參(p-苄基)鋶、參(p-異丙基苯基)鋶、參(2,6-二甲基苯基)鋶、參(p-tert-丁基苯基)鋶、參(p-氰基苯基)鋶、參(p-氯苯基)鋶、二甲基(甲氧基)鋶、二甲基(乙氧基)鋶、二甲基(丙氧基)鋶、二甲基(丁氧基)鋶、二甲基(辛基氧基)鋶、二甲基(十八烷氧基)鋶、二甲基(異丙氧基)鋶、二甲基(tert-丁氧基)鋶、二甲基(環戊基氧基)鋶、二甲基(環己基氧基)鋶、二甲基(氟甲氧基)鋶、二甲基(2-氯乙氧基)鋶、二甲基(3-溴丙氧基)鋶、二甲基(4-氰基丁氧基)鋶、二甲基(8-硝基辛基氧基)鋶、二甲基(18-三氟甲基十八烷氧基)鋶、二甲基(2-羥基異丙氧基)鋶、或二甲基(參(三氯甲基)甲基)鋶等。Specific examples of the phosphonium cation include diphenyl hydrazine, bis(p-benzyl) fluorene, bis(p-tert-butylphenyl) fluorene, and bis(p-octylphenyl) fluorene. , bis(p-octadecylphenyl)fluorene, bis(p-octyloxyphenyl)fluorene, bis(p-octadecyloxyphenyl)fluorene, phenyl (p-eighteen (oxyphenyl) hydrazine, (p-benzyl) (p-isopropylphenyl) fluorene, triphenyl sulfonium, ginseng (p-benzyl) hydrazine, ginseng (p-isopropylphenyl)鋶, ginseng (2,6-dimethylphenyl) fluorene, ginseng (p-tert-butylphenyl) fluorene, ginseng (p-cyanophenyl) fluorene, ginseng (p-chlorophenyl) hydrazine , dimethyl (methoxy) hydrazine, dimethyl (ethoxy) hydrazine, dimethyl (propoxy) hydrazine, dimethyl (butoxy) hydrazine, dimethyl (octyloxy) Anthracene, dimethyl (octadecyloxy) hydrazine, dimethyl (isopropoxy) hydrazine, dimethyl (tert-butoxy) hydrazine, dimethyl (cyclopentyloxy) fluorene, two Methyl (cyclohexyloxy) fluorene, dimethyl (fluoromethoxy) hydrazine, dimethyl (2-chloroethoxy) hydrazine, dimethyl (3-bromopropoxy) hydrazine, dimethyl (4-cyanobutoxy)anthracene, dimethyl(8-nitrooctyloxy)anthracene, dimethyl(18-trifluoromethyloctadecyloxy)anthracene, dimethyl (2- Isopropoxy-yl) sulfonium, or dimethyl (see (trichloromethyl) methyl) sulfonium and the like.
較佳之鎓陽離子可舉出雙(p-苄基)錪鎓、(p-苄基)(p-異丙基苯基)錪鎓、雙(p-tert-丁基苯基)錪鎓、三苯基鋶或參(p-tert-丁基苯基)鋶等。Preferred ruthenium cations are bis(p-benzyl)fluorene, (p-benzyl)(p-isopropylphenyl)fluorene, bis(p-tert-butylphenyl)fluorene, and three. Phenylhydrazine or ginseng (p-tert-butylphenyl) hydrazine.
前述源自路易斯酸之陰離子之具體例可舉出六氟磷酸鹽、六氟砷酸鹽、六氟銻酸鹽或肆(五氟苯基)硼酸鹽等。較佳之源自路易斯酸之陰離子可舉出六氟銻酸鹽或肆(五氟苯基)硼酸鹽。Specific examples of the anion derived from the Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate or decyl (pentafluorophenyl) borate. Preferred examples of the anion derived from the Lewis acid include hexafluoroantimonate or quinone (pentafluorophenyl) borate.
前述之鎓陽離子及源自路易斯酸之陰離子可任意組合使用。The above cerium cation and an anion derived from a Lewis acid may be used arbitrarily in combination.
陽離子聚合開始劑之具體例,可舉出二苯基錪鎓六氟磷酸鹽、雙(p-苄基)錪鎓六氟磷酸鹽、雙(p-tert-丁基苯基)錪鎓六氟磷酸鹽、雙(p-辛基苯基)錪鎓六氟磷酸鹽、雙(p-十八基苯基)錪鎓六氟磷酸鹽、雙(p-辛基氧基苯基)錪鎓六氟磷酸鹽、雙(p-十八基氧基苯基)錪鎓六氟磷酸鹽、苯基(p-十八基氧基苯基)錪鎓六氟磷酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟磷酸鹽、甲基萘基錪鎓六氟磷酸鹽、乙基萘基錪鎓六氟磷酸鹽、三苯基鋶六氟磷酸鹽、參(p-苄基)鋶六氟磷酸鹽、參(p-異丙基苯基)鋶六氟磷酸鹽、參(2,6-二甲基苯基)鋶六氟磷酸鹽、參(p-tert-丁基苯基)鋶六氟磷酸鹽、參(p-氰基苯基)鋶六氟磷酸鹽、參(p-氯苯基)鋶六氟磷酸鹽、二甲基萘基鋶六氟磷酸鹽、二乙基萘基鋶六氟磷酸鹽、二甲基(甲氧基)鋶六氟磷酸鹽、二甲基(乙氧基)鋶六氟磷酸鹽、二甲基(丙氧基)鋶六氟磷酸鹽、二甲基(丁氧基)鋶六氟磷酸鹽、二甲基(辛基氧基)鋶六氟磷酸鹽、二甲基(十八烷氧基)鋶六氟磷酸鹽、二甲基(異丙氧基)鋶六氟磷酸鹽、二甲基(tert-丁氧基)鋶六氟磷酸鹽、二甲基(環戊基氧基)鋶六氟磷酸鹽、二甲基(環己基氧基)鋶六氟磷酸鹽、二甲基(氟甲氧基)鋶六氟磷酸鹽、二甲基(2-氯乙氧基)鋶六氟磷酸鹽、二甲基(3-溴丙氧基)鋶六氟磷酸鹽、二甲基(4-氰基丁氧基)鋶六氟磷酸鹽、二甲基(8-硝基辛基氧基)鋶六氟磷酸鹽、二甲基(18-三氟甲基十八烷氧基)鋶六氟磷酸鹽、二甲基(2-羥基異丙氧基)鋶六氟磷酸鹽、二甲基(參(三氯甲基)甲基)鋶六氟磷酸鹽;二苯基錪鎓六氟砷酸鹽、雙(p-苄基)錪鎓六氟砷酸鹽、雙(p-tert-丁基苯基)錪鎓六氟砷酸鹽、雙(p-辛基苯基)錪鎓六氟砷酸鹽、雙(p-十八基苯基)錪鎓六氟砷酸鹽、雙(p-辛基氧基苯基)錪鎓六氟砷酸鹽、雙(p-十八基氧基苯基)錪鎓六氟砷酸鹽、苯基(p-十八基氧基苯基)錪鎓六氟砷酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟砷酸鹽、甲基萘基錪鎓六氟砷酸鹽、乙基萘基錪鎓六氟砷酸鹽、三苯基鋶六氟砷酸鹽、參(p-苄基)鋶六氟砷酸鹽、參(p-異丙基苯基)鋶六氟砷酸鹽、參(2,6-二甲基苯基)鋶六氟砷酸鹽、參(p-tert-丁基苯基)鋶六氟砷酸鹽、參(p-氰基苯基)鋶六氟砷酸鹽、參(p-氯苯基)鋶六氟砷酸鹽、二甲基萘基鋶六氟砷酸鹽、二乙基萘基鋶六氟砷酸鹽、二甲基(甲氧基)鋶六氟砷酸鹽、二甲基(乙氧基)鋶六氟砷酸鹽、二甲基(丙氧基)鋶六氟砷酸鹽、二甲基(丁氧基)鋶六氟砷酸鹽、二甲基(辛基氧基)鋶六氟砷酸鹽、二甲基(十八烷氧基)鋶六氟砷酸鹽、二甲基(異丙氧基)鋶六氟砷酸鹽、二甲基(tert-丁氧基)鋶六氟砷酸鹽、二甲基(環戊基氧基)鋶六氟砷酸鹽、二甲基(環己基氧基)鋶六氟砷酸鹽、二甲基(氟甲氧基)鋶六氟砷酸鹽、二甲基(2-氯乙氧基)鋶六氟砷酸鹽、二甲基(3-溴丙氧基)鋶六氟砷酸鹽、二甲基(4-氰基丁氧基)鋶六氟砷酸鹽、二甲基(8-硝基辛基氧基)鋶六氟砷酸鹽、二甲基(18-三氟甲基十八烷氧基)鋶六氟砷酸鹽、二甲基(2-羥基異丙氧基)鋶六氟砷酸鹽、二甲基(參(三氯甲基)甲基)鋶六氟砷酸鹽;二苯基錪鎓六氟銻酸鹽、雙(p-苄基)錪鎓六氟銻酸鹽、雙(p-tert-丁基苯基)錪鎓六氟銻酸鹽、雙(p-辛基苯基)錪鎓六氟銻酸鹽、雙(p-十八基苯基)錪鎓六氟銻酸鹽、雙(p-辛基氧基苯基)錪鎓六氟銻酸鹽、雙(p-十八基氧基苯基)錪鎓六氟銻酸鹽、苯基(p-十八基氧基苯基)錪鎓六氟銻酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟銻酸鹽、甲基萘基錪鎓六氟銻酸鹽、乙基萘基錪鎓六氟銻酸鹽、三苯基鋶六氟銻酸鹽、參(p-苄基)鋶六氟銻酸鹽、參(p-異丙基苯基)鋶六氟銻酸鹽、參(2,6-二甲基苯基)鋶六氟銻酸鹽、參(p-tert-丁基苯基)鋶六氟銻酸鹽、參(p-氰基苯基)鋶六氟銻酸鹽、參(p-氯苯基)鋶六氟銻酸鹽、二甲基萘基鋶六氟銻酸鹽、二乙基萘基鋶六氟銻酸鹽、二甲基(甲氧基)鋶六氟銻酸鹽、二甲基(乙氧基)鋶六氟銻酸鹽、二甲基(丙氧基)鋶六氟銻酸鹽、二甲基(丁氧基)鋶六氟銻酸鹽、二甲基(辛基氧基)鋶六氟銻酸鹽、二甲基(十八烷氧基)鋶六氟銻酸鹽、二甲基(異丙氧基)鋶六氟銻酸鹽、二甲基(tert-丁氧基)鋶六氟銻酸鹽、二甲基(環戊基氧基)鋶六氟銻酸鹽、二甲基(環己基氧基)鋶六氟銻酸鹽、二甲基(氟甲氧基)鋶六氟銻酸鹽、二甲基(2-氯乙氧基)鋶六氟銻酸鹽、二甲基(3-溴丙氧基)鋶六氟銻酸鹽、二甲基(4-氰基丁氧基)鋶六氟銻酸鹽、二甲基(8-硝基辛基氧基)鋶六氟銻酸鹽、二甲基(18-三氟甲基十八烷氧基)鋶六氟銻酸鹽、二甲基(2-羥基異丙氧基)鋶六氟銻酸鹽、二甲基(參(三氯甲基)甲基)鋶六氟銻酸鹽;二苯基錪鎓肆(五氟苯基)硼酸鹽、雙(p-苄基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-tert-丁基苯基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-辛基苯基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-十八基苯基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-辛基氧基苯基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-十八基氧基苯基)錪鎓肆(五氟苯基)硼酸鹽、苯基(p-十八基氧基苯基)錪鎓肆(五氟苯基)硼酸鹽、(p-苄基)(p-異丙基苯基)錪鎓肆(五氟苯基)硼酸鹽、甲基萘基錪鎓肆(五氟苯基)硼酸鹽、乙基萘基錪鎓肆(五氟苯基)硼酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、參(p-苄基)鋶肆(五氟苯基)硼酸鹽、參(p-異丙基苯基)鋶肆(五氟苯基)硼酸鹽、參(2,6-二甲基苯基)鋶肆(五氟苯基)硼酸鹽、參(p-tert-丁基苯基)鋶肆(五氟苯基)硼酸鹽、參(p-氰基苯基)鋶肆(五氟苯基)硼酸鹽、參(p-氯苯基)鋶肆(五氟苯基)硼酸鹽、二甲基萘基鋶肆(五氟苯基)硼酸鹽、二乙基萘基鋶肆(五氟苯基)硼酸鹽、二甲基(甲氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(乙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(丁氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(辛基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(十八烷氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(異丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(tert-丁氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(環戊基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(環己基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(氟甲氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(2-氯乙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(3-溴丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(4-氰基丁氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(8-硝基辛基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(18-三氟甲基十八烷氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(2-羥基異丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(參(三氯甲基)甲基)鋶肆(五氟苯基)硼酸鹽等,較佳可舉出雙(p-苄基)錪鎓六氟磷酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟磷酸鹽、雙(p-tert-丁基苯基)錪鎓六氟磷酸鹽、三苯基鋶六氟磷酸鹽、參(p-tert-丁基苯基)鋶六氟磷酸鹽、雙(p-苄基)錪鎓六氟砷酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟砷酸鹽、雙(p-tert-丁基苯基)錪鎓六氟砷酸鹽、三苯基鋶六氟砷酸鹽、參(p-t-丁基苯基)鋶六氟砷酸鹽、雙(p-苄基)錪鎓六氟銻酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟銻酸鹽、雙(p-tert-丁基苯基)錪鎓六氟銻酸鹽、三苯基鋶六氟銻酸鹽、參(p-tert-丁基苯基)鋶六氟銻酸鹽、雙(p-苄基)錪鎓肆(五氟苯基)硼酸鹽、(p-苄基)(p-異丙基苯基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-tert-丁基苯基)錪鎓、三苯基鋶肆(五氟苯基)硼酸鹽、參(p-tert-丁基苯基)鋶肆(五氟苯基)硼酸鹽等,更佳可舉出雙(p-苄基)錪鎓六氟銻酸鹽、(p-苄基)(p-異丙基苯基)錪鎓六氟銻酸鹽、雙(p-tert-丁基苯基)錪鎓六氟銻酸鹽、三苯基鋶六氟銻酸鹽、參(p-tert-丁基苯基)鋶六氟銻酸鹽、雙(p-苄基)錪鎓肆(五氟苯基)硼酸鹽、(p-苄基)(p-異丙基苯基)錪鎓肆(五氟苯基)硼酸鹽、雙(p-tert-丁基苯基)錪鎓肆(五氟苯基)硼酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、或參(p-tert-丁基苯基)鋶肆(五氟苯基)硼酸鹽等。Specific examples of the cationic polymerization initiator include diphenylphosphonium hexafluorophosphate, bis(p-benzyl)phosphonium hexafluorophosphate, and bis(p-tert-butylphenyl)phosphonium hexafluorophosphate. Phosphate, bis(p-octylphenyl)phosphonium hexafluorophosphate, bis(p-octadecylphenyl)phosphonium hexafluorophosphate, bis(p-octyloxyphenyl)phosphonium Fluorophosphate, bis(p-octadecyloxyphenyl)phosphonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl)phosphonium hexafluorophosphate, (p-benzyl) P-isopropylphenyl)phosphonium hexafluorophosphate, methylnaphthylphosphonium hexafluorophosphate, ethylnaphthylphosphonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, ginseng (p- Benzyl)phosphonium hexafluorophosphate, ginseng (p-isopropylphenyl)phosphonium hexafluorophosphate, ginseng (2,6-dimethylphenyl)phosphonium hexafluorophosphate, ginseng (p-tert-butyl) Phenyl hexafluorophosphate, ginseng (p-cyanophenyl)phosphonium hexafluorophosphate, ginseng (p-chlorophenyl)phosphonium hexafluorophosphate, dimethylnaphthylphosphonium hexafluorophosphate, Diethylnaphthylphosphonium hexafluorophosphate, dimethyl(methoxy)phosphonium hexafluorophosphate, dimethyl(ethoxy)phosphonium hexafluorophosphate, dimethyl(propoxy)phosphonium hexafluorophosphate Phosphate , dimethyl(butoxy)phosphonium hexafluorophosphate, dimethyl(octyloxy)phosphonium hexafluorophosphate, dimethyl(octadecyloxy)phosphonium hexafluorophosphate, dimethyl ( Isopropoxy)phosphonium hexafluorophosphate, dimethyl(tert-butoxy)phosphonium hexafluorophosphate, dimethyl(cyclopentyloxy)phosphonium hexafluorophosphate, dimethyl (cyclohexyloxy) Hexafluorophosphate, dimethyl(fluoromethoxy)phosphonium hexafluorophosphate, dimethyl(2-chloroethoxy)phosphonium hexafluorophosphate, dimethyl (3-bromopropoxy)鋶 hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18- Trifluoromethyloctadecyloxy)phosphonium hexafluorophosphate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluorophosphate, dimethyl (xyl (trichloromethyl)methyl) fluorene Fluorophosphate; diphenylphosphonium hexafluoroarsenate, bis(p-benzyl)phosphonium hexafluoroarsenate, bis(p-tert-butylphenyl)phosphonium hexafluoroarsenate, double (p-octylphenyl)phosphonium hexafluoroarsenate, bis(p-octadecylphenyl)phosphonium hexafluoroarsenate, bis(p-octyloxyphenyl)phosphonium hexafluoroarsenate Acid salt, double (p-octadecyl) Phenyl phenyl) hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) ruthenium hexafluoroarsenate, (p-benzyl) (p-isopropylphenyl) hydrazine Hexafluoroarsenate, methylnaphthylphosphonium hexafluoroarsenate, ethylnaphthylphosphonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, ginseng (p-benzyl)phosphonium hexafluorophosphate Arsenate, ginseng (p-isopropylphenyl)phosphonium hexafluoroarsenate, ginseng (2,6-dimethylphenyl)phosphonium hexafluoroarsenate, ginseng (p-tert-butylphenyl)鋶 hexafluoroarsenate, ginseng (p-cyanophenyl) hexafluoroarsenate, ginseng (p-chlorophenyl) hexafluoroarsenate, dimethylnaphthyl fluorene hexafluoroarsenate , diethylnaphthylphosphonium hexafluoroarsenate, dimethyl(methoxy)phosphonium hexafluoroarsenate, dimethyl(ethoxy)phosphonium hexafluoroarsenate, dimethyl (propoxy) Hexafluoroarsenate, dimethyl(butoxy)phosphonium hexafluoroarsenate, dimethyl(octyloxy)phosphonium hexafluoroarsenate, dimethyl(octadecyloxy)phosphonium Hexafluoroarsenate, dimethyl(isopropoxy)phosphonium hexafluoroarsenate, dimethyl(tert-butoxy)phosphonium hexafluoroarsenate, dimethyl(cyclopentyloxy)fluorene Hexafluoroarsenate, dimethyl(cyclohexyloxy)phosphonium hexafluoroarsenate, Dimethyl(fluoromethoxy)phosphonium hexafluoroarsenate, dimethyl(2-chloroethoxy)phosphonium hexafluoroarsenate, dimethyl(3-bromopropoxy)phosphonium hexafluoroarsenate Salt, dimethyl(4-cyanobutoxy)phosphonium hexafluoroarsenate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroarsenate, dimethyl (18-trifluoromethyl) Octadecyloxy)phosphonium hexafluoroarsenate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluoroarsenate, dimethyl(xyl(trichloromethyl)methyl)phosphonium hexafluorophosphate Arsenate; diphenylphosphonium hexafluoroantimonate, bis(p-benzyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, double (p-octylphenyl)phosphonium hexafluoroantimonate, bis(p-octadecylphenyl)phosphonium hexafluoroantimonate, bis(p-octyloxyphenyl)phosphonium hexafluoroantimonate Acid salt, bis(p-octadecyloxyphenyl)phosphonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl)phosphonium hexafluoroantimonate, (p-benzyl) (p-isopropylphenyl)phosphonium hexafluoroantimonate, methylnaphthylphosphonium hexafluoroantimonate, ethylnaphthylphosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate , ginseng (p-benzyl) hexafluoroantimonate, ginseng (p-isopropylphenyl) hexafluoroantimonate Reference (2,6-dimethylphenyl)phosphonium hexafluoroantimonate, ginseng (p-tert-butylphenyl)phosphonium hexafluoroantimonate, ginseng (p-cyanophenyl)phosphonium hexafluoroantimonate Acid salt, ginseng (p-chlorophenyl) hexafluoroantimonate, dimethylnaphthyl hydrazine hexafluoroantimonate, diethyl naphthyl fluorene hexafluoroantimonate, dimethyl (methoxy) Hexafluoroantimonate, dimethyl(ethoxy)phosphonium hexafluoroantimonate, dimethyl(propoxy)phosphonium hexafluoroantimonate, dimethyl(butoxy)phosphonium hexafluoroantimonate Salt, dimethyl(octyloxy)phosphonium hexafluoroantimonate, dimethyl(octadecyloxy)phosphonium hexafluoroantimonate, dimethyl(isopropoxy)phosphonium hexafluoroantimonate , dimethyl (tert-butoxy) hexafluoroantimonate, dimethyl (cyclopentyloxy) hexafluoroantimonate, dimethyl (cyclohexyloxy) hexafluoroantimonate , dimethyl (fluoromethoxy) hexafluoroantimonate, dimethyl (2-chloroethoxy) hexafluoroantimonate, dimethyl (3-bromopropoxy) hexafluoroantimony Acid salt, dimethyl(4-cyanobutoxy)phosphonium hexafluoroantimonate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroantimonate, dimethyl (18-trifluoro) Methyl octadecyloxy) hexafluoroantimonate, dimethyl (2-hydroxyiso) Oxy) hexafluoroantimonate, dimethyl (paras(trichloromethyl)methyl) hexafluoroantimonate; diphenyl sulfonium (pentafluorophenyl) borate, double (p- Benzyl)phosphonium (pentafluorophenyl)borate, bis(p-tert-butylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octadecylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octyloxyphenyl)phosphonium (pentafluorophenyl) Borate, bis(p-octadecyloxyphenyl)phosphonium (pentafluorophenyl)borate, phenyl (p-octadecyloxyphenyl)phosphonium (pentafluorophenyl) Borate, (p-benzyl) (p-isopropylphenyl) ruthenium (pentafluorophenyl) borate, methylnaphthyl fluorene (pentafluorophenyl) borate, ethyl naphthyl錪鎓肆(pentafluorophenyl)borate, triphenylsulfonium (pentafluorophenyl)borate, ginseng (p-benzyl)phosphonium (pentafluorophenyl)borate, ginseng (p-isopropyl Phenyl) quinone (pentafluorophenyl) borate, ginseng (2,6-dimethylphenyl) ruthenium (pentafluorophenyl) borate, ginseng (p-tert-butylphenyl) hydrazine Bis(pentafluorophenyl)borate, ginseng (p-cyanophenyl)indole (pentafluorophenyl)borate, ginseng (p-chlorophenyl)indole (pentafluorophenyl)borate, dimethylnaphthyl fluorene (pentafluorophenyl) borate, diethylnaphthyl fluorene (pentafluorophenyl) borate, Dimethyl(methoxy)phosphonium (pentafluorophenyl)borate, dimethyl(ethoxy)phosphonium (pentafluorophenyl)borate, dimethyl(propoxy)phosphonium (five Fluorophenyl)borate, dimethyl(butoxy)phosphonium (pentafluorophenyl)borate, dimethyl(octyloxy)phosphonium (pentafluorophenyl)borate, dimethyl ( Octadecyloxy)phosphonium (pentafluorophenyl)borate, dimethyl(isopropoxy)phosphonium (pentafluorophenyl)borate, dimethyl(tert-butoxy)hydrazine Pentafluorophenyl)borate, dimethyl(cyclopentyloxy)phosphonium (pentafluorophenyl)borate, dimethyl(cyclohexyloxy)phosphonium (pentafluorophenyl)borate, two Methyl (fluoromethoxy) ruthenium (pentafluorophenyl) borate, dimethyl (2-chloroethoxy) ruthenium (pentafluorophenyl) borate, dimethyl (3-bromopropoxy) (鋶肆)(pentafluorophenyl)borate, dimethyl(4-cyanobutoxy)indole (pentafluorophenyl)borate, dimethyl(8-nitrooctyloxy)anthracene Bis(pentafluorophenyl)borate, dimethyl (18-trifluoro) Octadecyloxy)indole (pentafluorophenyl)borate, dimethyl(2-hydroxyisopropoxy)phosphonium (pentafluorophenyl)borate, dimethyl (parasyl (trichloromethane) Preference is given to bis(p-benzyl)phosphonium hexafluorophosphate or (p-benzyl) (p-isopropylphenyl).錪鎓 hexafluorophosphate, bis(p-tert-butylphenyl)phosphonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, ginseng (p-tert-butylphenyl)phosphonium hexafluorophosphate Salt, bis(p-benzyl)phosphonium hexafluoroarsenate, (p-benzyl)(p-isopropylphenyl)phosphonium hexafluoroarsenate, bis(p-tert-butylphenyl錪鎓 hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, ginseng (pt-butylphenyl)phosphonium hexafluoroarsenate, bis(p-benzyl)phosphonium hexafluoroantimonate, (p-benzyl)(p-isopropylphenyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Salt, ginseng (p-tert-butylphenyl) hexafluoroantimonate, bis(p-benzyl)phosphonium (pentafluorophenyl)borate, (p-benzyl) (p-isopropyl) Phenyl) quinone (pentafluorophenyl) borate, bis(p-tert-butylphenyl) fluorene, triphenyl sulfonium (five More preferably, fluorophenyl) borate, ginseng (p-tert-butylphenyl) ruthenium (pentafluorophenyl) borate, etc., more preferably bis(p-benzyl)phosphonium hexafluoroantimonate, (p-benzyl)(p-isopropylphenyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Salt, ginseng (p-tert-butylphenyl) hexafluoroantimonate, bis(p-benzyl)phosphonium (pentafluorophenyl)borate, (p-benzyl) (p-isopropyl) Phenyl)phosphonium (pentafluorophenyl)borate, bis(p-tert-butylphenyl)phosphonium (pentafluorophenyl)borate, triphenylsulfonium (pentafluorophenyl) Borate or ginseng (p-tert-butylphenyl) ruthenium (pentafluorophenyl) borate.
又,在不損及本發明之效果的程度下,可在聚合開始劑(C)中組合使用聚合開始助劑(C-1),亦可複數組合使用聚合開始助劑。Further, the polymerization start aid (C-1) may be used in combination with the polymerization initiator (C), and the polymerization start aid may be used in combination, to the extent that the effects of the present invention are not impaired.
聚合開始助劑(C-1)可舉出胺化合物、羧酸化合物、多官能硫醇化合物、式(III)所表示之化合物、式(A-1)或式(A-2)所表示之化合物等。The polymerization initiation aid (C-1) may, for example, be an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, a compound represented by the formula (III), or a formula (A-1) or a formula (A-2). Compounds, etc.
前述之胺化合物可舉出三乙醇胺、甲基二乙醇胺、三異丙醇胺等之脂肪族胺化合物、4-二甲基胺基安息香酸甲酯、4-二甲基胺基安息香酸乙酯、4-二甲基胺基安息香酸異戊酯、4-二甲基胺基安息香酸2-乙基己酯、安息香酸2-二甲基胺基乙酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮(通稱;米希勒酮)或4,4’-雙(二乙基胺基)二苯甲酮等之芳香族胺化合物。Examples of the amine compound include an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate. , 4-dimethylamino benzoic acid isoamyl ester, 4-dimethylamino benzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N, N-dimethyl pair Aromatic amines such as toluidine, 4,4'-bis(dimethylamino)benzophenone (general name; Michlerone) or 4,4'-bis(diethylamino)benzophenone Amine compound.
前述之羧酸化合物可舉出苯基硫代乙酸、甲基苯基硫代乙酸、乙基苯基硫代乙酸、甲基乙基苯基硫代乙酸、二甲基苯基硫代乙酸、甲氧基苯基硫代乙酸、二甲氧基苯基硫代乙酸、氯苯基硫代乙酸、二氯苯基硫代乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘胺酸或萘氧基乙酸等之芳香族雜乙酸類。The above carboxylic acid compound may, for example, be phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, or Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio An aromatic heteroacetic acid such as acetic acid, N-naphthylglycine or naphthyloxyacetic acid.
前述之多官能硫醇化合物係於分子內具有2個以上之磺醯基的化合物。其中,以具有2個以上之與2個以上脂肪族烴基之碳原子相鍵結之磺醯基的化合物,因可使本發明之硬化性樹脂組成物之感度變高為更佳。The above polyfunctional thiol compound is a compound having two or more sulfonyl groups in the molecule. In particular, a compound having two or more sulfonyl groups bonded to a carbon atom of two or more aliphatic hydrocarbon groups is more preferable because the sensitivity of the curable resin composition of the present invention can be increased.
多官能硫醇化合物具體可舉出己烷二硫醇、癸烷二硫醇、1,4-二甲基硫醇基苯、丁二醇雙硫代丙酸酯、丁二醇雙巰基乙酸酯、乙二醇雙巰基乙酸酯、三羥甲基丙烷參巰基乙酸酯、丁二醇雙硫代丙酸酯、三羥甲基丙烷參硫代丙酸酯、三羥甲基丙烷參巰基乙酸酯、季戊四醇肆硫代丙酸酯、季戊四醇肆巰基乙酸酯、參羥基乙基參硫代丙酸酯、季戊四醇肆(3-巰基丁酸酯)或1,4-雙(3-巰基丁醯基氧基)丁烷等。Specific examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylthiolbenzene, butanediol dithiopropionate, butanediol bis-mercaptoacetic acid. Ester, ethylene glycol bis-mercaptoacetate, trimethylolpropane decyl acetate, butanediol dithiopropionate, trimethylolpropane thiopropionate, trimethylolpropane Mercaptoacetate, pentaerythritol thiopropionate, pentaerythritol thioacetate, hydroxyethyl thiopropionate, pentaerythritol bismuth (3-mercaptobutyrate) or 1,4-bis (3- Mercaptobutyloxy)butane and the like.
多官能硫醇化合物之含有量,相對於聚合開始劑(C),以質量分率較佳為0.5~20質量%,更佳為1~15質量%。多官能硫醇化合物之含有量若在前述之範圍,有感度變高之傾向,故為佳。The content of the polyfunctional thiol compound is preferably from 0.5 to 20% by mass, and more preferably from 1 to 15% by mass, based on the polymerization initiator (C). When the content of the polyfunctional thiol compound is in the above range, the sensitivity tends to be high, which is preferable.
聚合開始助劑(C-1)亦可使用下述式(III)所表示之化合物。A compound represented by the following formula (III) can also be used as the polymerization initiation aid (C-1).
式(III)中,X所示之點線係表示亦可被鹵素原子所取代之碳數6~12之芳香環。In the formula (III), the dotted line represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom.
Y表示氧原子、硫原子。Y represents an oxygen atom or a sulfur atom.
R21 表示碳數1~6之烷基。R 21 represents an alkyl group having 1 to 6 carbon atoms.
R22 表示可被鹵素原子取代之碳數1~12之烷基或亦可被鹵素原子取代之芳香基。R 22 represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom or an aromatic group which may be substituted by a halogen atom.
鹵素原子可舉出氟原子、氯原子、溴原子等。Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
碳數6~12之芳香環可舉出苯環、萘環等。Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.
可被鹵素原子取代之碳數6~12之芳香環可舉出苯環、甲基苯環、二甲基苯環、乙基苯環、丙基苯環、丁基苯環、戊基苯環、己基苯環、環己基苯環、氯苯環、二氯苯環、溴苯環、二溴苯環、苯基苯環、氯苯基苯環、溴苯基苯環、萘環、氯萘環、溴萘環等。The aromatic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom may, for example, be a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring or a pentylbenzene ring. , hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene Ring, bromine naphthalene ring, and the like.
碳數1~6之烷基可舉出甲基、乙基、n-丙基、異丙基、n-丁基、1-甲基-n-丙基、2-甲基-n-丙基、tert-丁基、n-戊基基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、n-己基、環己基等。The alkyl group having 1 to 6 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group or a 2-methyl-n-propyl group. , tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl- N-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl and the like.
可被鹵素原子取代之碳數1~12之烷基可舉出甲基、乙基、n-丙基、異丙基、n-丁基、1-甲基-n-丙基、2-甲基-n-丙基、tert-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、n-己基、環己基基、1-氯-n-丁基、2-氯-n-丁基、3-氯-n-丁基等。The alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group or a 2-methyl group. Base-n-propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1 - dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n- Butyl, 2-chloro-n-butyl, 3-chloro-n-butyl and the like.
可被鹵素原子取代之芳香基可舉出苯基、氯苯基、二氯苯基、溴苯基、二溴苯基、氯溴苯基、聯苯基、氯聯苯基、二氯聯苯基、溴苯基、二溴苯基、萘基、氯萘基、二氯萘基、溴萘基、二溴萘基等。The aromatic group which may be substituted by a halogen atom may, for example, be phenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorobromophenyl, biphenyl, chlorobiphenyl or dichlorobiphenyl. Base, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl and the like.
式(III)所表示之合物,具體而言可舉出2-苄醯基亞甲基-3-甲基-苯并噻唑啉、2-苄醯基亞甲基-3-甲基-萘并[2,1-d]噻唑啉、2-苄醯基亞甲基-3-甲基-萘并[1,2-d]噻唑啉、2-苄醯基亞甲基-3-甲基-萘并[2,3-d]噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基苯并噻唑啉、2-(1-萘甲醯基亞甲基)-3-甲基苯并噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-苯基苯并噻唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-苯基苯并噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-氟苯并噻唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-氟苯并噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-氯苯并噻唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-氯苯并噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-溴苯并噻唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-溴苯并噻唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基苯并噻唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基-5-苯基苯并噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-萘并[2,1-d]噻唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-萘并[1,2-d]噻唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基-萘并[2,1-d]噻唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基-萘并[1,2-d]噻唑啉、2-(p-氟苄醯基亞甲基)-3-甲基-萘并[2,1-d]噻唑啉、2-(p-氟苄醯基亞甲基)-3-甲基-萘并[1,2-d]噻唑啉、2-苄醯基亞甲基-3-甲基-萘并[2,1-d]噁唑啉、2-苄醯基亞甲基-3-甲基-萘并[1,2-d]噁唑啉、2-苄醯基亞甲基-3-甲基-萘并[2,3-d]噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基苯并噁唑啉、2-(1-萘甲醯基亞甲基)-3-甲基苯并噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-苯基苯并噁唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-苯基苯并噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-氟苯并噁唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-氟苯并噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-氯苯并噁唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-氯苯并噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-5-溴苯并噁唑啉、2-(1-萘甲醯基亞甲基)-3-甲基-5-溴苯并噁唑啉、2-(4-聯苯二甲醯基(biphenoyl)亞甲基)-3-甲基苯并噁唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基-5-苯基苯并噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-萘并[2,1-d]噁唑啉、2-(2-萘甲醯基亞甲基)-3-甲基-萘并[1,2-d]噁唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基-萘并[2,1-d]噁唑啉、2-(4-聯苯二甲醯基亞甲基)-3-甲基-萘并[1,2-d]噁唑啉、2-(p-氟苄醯基亞甲基)-3-甲基-萘并[2,1-d]噁唑啉、2-(p-氟苄醯基亞甲基)-3-甲基-萘并[1,2-d]噁唑啉等。Specific examples of the compound represented by the formula (III) include 2-benzylindolyl-3-methyl-benzothiazoline and 2-benzylidenemethylene-3-methyl-naphthalene. And [2,1-d]thiazoline, 2-benzylindolyl-3-methyl-naphtho[1,2-d]thiazoline, 2-benzylbenzylidene-3-methyl -naphtho[2,3-d]thiazoline, 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline, 2-(1-naphthylmethylidene methylene)- 3-methylbenzothiazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-5-phenylbenzothiazoline, 2-(1-naphthylmethylidene methylene) 3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-fluorobenzothiazoline, 2-(1-naphthoquinone) Benzylmethyl)-3-methyl-5-fluorobenzothiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-chlorobenzothiazoline, 2-(1 -naphthylmethylidenemethyl)-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-bromobenzothiazoline, 2-(1-naphthylmethylidene methylene)-3-methyl-5-bromobenzothiazoline, 2-(4-biphenyldimethylbenzylidene)-3-methylbenzothiazole Porphyrin, 2-(4-biphenyldimethylbenzylidene)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthoquinone) Benzylmethyl)-3-methyl-naphtho[2,1-d]thiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-naphtho[1,2-d Thiazoline, 2-(4-biphenyldimethylbenzylidene)-3-methyl-naphtho[2,1-d]thiazoline, 2-(4-biphenyldimethylene) 3-methyl-naphtho[1,2-d]thiazoline, 2-(p-fluorobenzylidenemethylene)-3-methyl-naphtho[2,1-d]thiazoline , 2-(p-Fluorobenzylidene methylene)-3-methyl-naphtho[1,2-d]thiazoline, 2-benzylbenzylidene-3-methyl-naphtho[2] , 1-d]oxazoline, 2-benzylindolyl-3-methyl-naphtho[1,2-d]oxazoline, 2-benzylindenylmethylene-3-methyl- Naphtho[2,3-d]oxazoline, 2-(2-naphthylmethylidenemethyl)-3-methylbenzoxazoline, 2-(1-naphthylmethylidene) 3-methylbenzoxazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzoxazoline, 2-(1-naphthylmethyl) Methyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-fluorobenzoxazoline, 2-( 1-naphthylmethylidene methylene)-3-methyl-5-fluorobenzoxazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-chlorobenzoxan Oxazoline, 2-(1-naphthylmethylidene methylene)-3-methyl-5-chlorobenzoxime Oxazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-5-bromobenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl- 5-bromobenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenyldimethylphenyl) Methyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-naphtho[2,1-d]oxazoline , 2-(2-naphthylmethylidene methylene)-3-methyl-naphtho[1,2-d]oxazoline, 2-(4-biphenyldimethylbenzylidene)-3 -methyl-naphtho[2,1-d]oxazoline, 2-(4-biphenyldimethylidene methylene)-3-methyl-naphtho[1,2-d]oxazoline , 2-(p-fluorobenzylidene methylene)-3-methyl-naphtho[2,1-d]oxazoline, 2-(p-fluorobenzylidenemethylene)-3-methyl Alkyl-naphtho[1,2-d]oxazoline and the like.
其中,以式(III-1)所表示之2-(2-萘甲醯基亞甲基)-3-甲基苯并噻唑啉、式(III-2)所表示之2-苄醯基亞甲基-3-甲基-萘并[1,2-d]噻唑啉及式(III-3)所表示之2-(4-聯苯二甲醯基亞甲基)-3-甲基-萘并[1,2-d]噻唑啉、2-苄醯基亞甲基-3-甲基-苯并噻唑啉為佳。Wherein 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline represented by formula (III-1), 2-benzylindenyl represented by formula (III-2) Methyl-3-methyl-naphtho[1,2-d]thiazoline and 2-(4-biphenyldimethylbenzylidene)-3-methyl- represented by formula (III-3) Naphtho[1,2-d]thiazoline and 2-benzylindolyl-3-methyl-benzothiazoline are preferred.
聚合開始助劑(C-1)亦可使用選自由式(A-1)及式(A-2)所成群之至少1種所表示之化合物。The polymerization initiation aid (C-1) may be a compound selected from at least one selected from the group consisting of the formula (A-1) and the formula (A-2).
[式(A-1)及式(A-2)中,環X31 及環X32 各自獨立表示碳數6~12之芳香環。Y31 及Y32 表示氧原子或硫原子。In the formula (A-1) and the formula (A-2), the ring X 31 and the ring X 32 each independently represent an aromatic ring having 6 to 12 carbon atoms. Y 31 and Y 32 represent an oxygen atom or a sulfur atom.
R31 及R32 表示碳數1~12之烷基或碳數6~12之芳香基。R 31 and R 32 represent an alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms.
該芳香環、該烷基或芳香基所含之碳原子亦可被氧原子、氮原子、硫原子或鹵素原子取代。]The carbon atom contained in the aromatic ring, the alkyl group or the aromatic group may be substituted by an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ]
鹵素原子可舉出氟原子、氯原子、溴原子等。Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
碳數6~12之芳香環可舉出苯環、甲基苯環、二甲基苯環、乙基苯環、丙基苯環、丁基苯環、戊基苯環、己基苯環、環己基苯環、氯苯環、二氯苯環、溴苯環、二溴苯環、苯基苯環、氯苯基苯環、溴苯基苯環、萘環、氯萘環、溴萘環、菲環、屈(chrysene)環、芙環、苯并[a]芘環、苯并[e]芘環、苝環及彼等之衍生物等。The aromatic ring having 6 to 12 carbon atoms may, for example, be a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring or a ring. Hexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromine ring, A phenanthrene ring, a chrysene ring, a fluorenyl ring, a benzo[a]anthracene ring, a benzo[e]fluorene ring, an anthracene ring, and derivatives thereof.
碳數1~12之烷基可舉出甲基、乙基、n-丙基、異丙基、n-丁基、1-甲基-n-丙基、2-甲基-n-丙基、tert-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、n-己基、環己基基、1-氯-n-丁基、2-氯-n-丁基、3-氯-n-丁基等。The alkyl group having 1 to 12 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group or a 2-methyl-n-propyl group. , tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n -propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro -n-butyl, 3-chloro-n-butyl and the like.
碳數6~12之芳香基可舉出苯基、氯苯基、二氯苯基、溴苯基、二溴苯基、氯溴苯基、羥基苯基、烷氧基苯基、聯苯基、氯聯苯基、二氯聯苯基、溴苯基、二溴苯基、萘基、氯萘基、二氯萘基、溴萘基、二溴萘基、羥基萘基等。Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a hydroxyphenyl group, an alkoxyphenyl group, and a biphenyl group. , chlorobiphenyl, dichlorobiphenyl, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl, hydroxynaphthyl and the like.
式(A-1)或式(A-2)所表示之化合物,具體可舉出二甲氧基萘、二乙氧基萘、二丙氧基萘、二異丙氧基萘、二丁氧基萘等之二烷氧基萘類二甲氧基蒽、二乙氧基蒽、二丙氧基蒽、二異丙氧基蒽、二丁氧基蒽、二戊氧基蒽、二己氧基蒽、甲氧基乙氧基蒽、甲氧基丙氧基蒽、甲氧基異丙氧基蒽、甲氧基丁氧基蒽、乙氧基丙氧基蒽、乙氧基異丙氧基蒽、乙氧基丁氧基蒽、丙氧基異丙氧基蒽、丙氧基丁氧基蒽、異丙氧基丁氧基蒽等之二烷氧基蒽類二甲氧基稠四苯、二乙氧基稠四苯、二丙氧基稠四苯、二異丙氧基稠四苯、二丁氧基稠四苯等之二烷氧基稠四苯類等,但不受限於此等。Specific examples of the compound represented by the formula (A-1) or the formula (A-2) include dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, and dibutoxy Di-alkoxy naphthalene dimethoxy hydrazine, diethoxy hydrazine, dipropoxy hydrazine, diisopropoxy fluorene, dibutoxy fluorene, dipentyl oxy fluorene, dihexyloxy Base, methoxyethoxy oxime, methoxypropoxy oxime, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxy isopropyloxy a dialkoxy oxime dimethoxy thick four based on ruthenium, ethoxybutoxy oxime, propoxy oxime oxime, propoxy oxy oxime, isopropoxy butyl oxime or the like Benzene, diethoxy condensed tetraphenyl, dipropoxy fused tetraphenyl, diisopropoxy fused tetraphenyl, dibutoxy fused tetraphenyl, etc., but not limited This is the case.
聚合開始劑(C)之含有量,相對於黏合劑樹脂(A)及聚合性化合物(B)之合計量,以質量分率較佳為0.1~40質量%,更佳為1~30質量%。The content of the polymerization initiator (C) is preferably 0.1 to 40% by mass, and more preferably 1 to 30% by mass, based on the total amount of the binder resin (A) and the polymerizable compound (B). .
又,聚合開始助劑(C-1)之含有量,與前述相同之基準下,較佳為0.01~50質量%,更佳為0.1~40質量%。Further, the content of the polymerization initiation aid (C-1) is preferably from 0.01 to 50% by mass, and more preferably from 0.1 to 40% by mass, based on the same criteria as described above.
選自由式(A-1)及式(A-2)所成群之至少1種所表示之化合物之含有量,相對於聚合開始助劑(C-1)之含有量,以50~100%為佳,較佳為60~100%,更佳為65~100%。選自由式(A-1)及式(A-2)所成之至少1種所表示之化合物之含有量若在前述之範圍,使用含有此之硬化性樹脂組成物形成塗膜時,塗膜之透明性變得良好,故為佳。The content of the compound represented by at least one of the groups of the formula (A-1) and the formula (A-2) is 50 to 100% based on the content of the polymerization initiation aid (C-1). Preferably, it is preferably 60 to 100%, more preferably 65 to 100%. When the content of the compound represented by at least one of the formulas (A-1) and (A-2) is within the above range, when a coating film is formed using the curable resin composition containing the coating film, the coating film is formed. The transparency is good, so it is preferable.
聚合開始劑(C)之合計量若在前述之範圍,硬化性樹脂組成物成為高感度,有使用前述之硬化性樹脂組成物形成之塗膜或圖型之強度、前述之塗膜或圖型之表面中之平滑性變得良好之傾向,故為佳。前述以外,聚合開始助劑(C-1)之量若在前述之範圍,所得之硬化性樹脂組成物之感度變得更高,有使用前述之硬化性樹脂組成物形成之圖型之生產性提升之傾向,故為佳。When the total amount of the polymerization initiator (C) is within the above range, the curable resin composition has high sensitivity, and the strength of the coating film or pattern formed using the above-mentioned curable resin composition, the above-mentioned coating film or pattern The smoothness in the surface tends to be good, so it is preferable. In addition, when the amount of the polymerization start aid (C-1) is within the above range, the sensitivity of the obtained curable resin composition is higher, and the productivity of the pattern formed using the above-described curable resin composition is obtained. It is better to promote the tendency.
本發明之硬化性樹脂組成物含有溶劑(D)。前述之溶劑(D)可舉出硬化性樹脂組成物之領域中所使用之各種的有機溶劑,其具體例可舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚及乙二醇單丁基醚般之乙二醇單烷基醚類;二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇乙基甲基醚、二乙二醇二丙基醚、二乙二醇二丁基醚等之二乙二醇二烷基醚類;甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙基醚乙酸酯等之乙二醇烷基醚乙酸酯類;丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯等之伸烷基二醇烷基醚乙酸酯類;丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等之丙二醇單烷基醚類;丙二醇二甲基醚、丙二醇二乙基醚、丙二醇乙基甲基醚、丙二醇二丙基醚丙二醇丙基甲基醚、丙二醇乙基丙基醚等之丙二醇二烷基醚類丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等之丙二醇烷基醚丙酸酯類;甲氧基丁基醇、乙氧基丁基醇、丙氧基丁基醇、丁氧基丁基醇等之丁基二醇單烷基醚類;甲氧基丁基乙酸酯、乙氧基丁基乙酸酯、丙氧基丁基乙酸酯、丁氧基丁基乙酸酯等之丁二醇單烷基醚乙酸酯類;甲氧基丁基丙酸酯、乙氧基丁基丙酸酯、丙氧基丁基丙酸酯、丁氧基丁基丙酸酯等之丁二醇單烷基醚丙酸酯類;二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇甲基乙基醚等之二丙二醇二烷基醚類;苯、甲苯、茬、對稱三甲苯等之芳香族烴類;甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮、環己酮等之酮類;乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙三醇等之醇類;乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁基、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁基、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等之酯類;四氫呋喃、哌喃等之環狀醚基類;γ-丁內酯等之環狀酯類等。The curable resin composition of the present invention contains a solvent (D). The solvent (D) is exemplified by various organic solvents used in the field of the curable resin composition, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol. Monopropyl ether and ethylene glycol monoalkyl ether like ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, ethylene Glycol alkyl ether acetates such as alcohol monobutyl ether acetate, ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Alkyl glycol alkyl ether acetates such as monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.; propylene glycol monomethyl ether, propylene glycol monoethyl ether Propylene glycol monoalkyl ethers such as propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol Propylene glycol dialkyl ether propylene glycol methyl ether propionate such as methyl ether or propylene glycol ethyl propyl ether, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate a propylene glycol alkyl ether propionate; a butyl glycol monoalkyl ether of methoxybutyl alcohol, ethoxybutyl alcohol, propoxy butyl alcohol, butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxy butyl acetate, butoxybutyl acetate; methoxy Butanediol monoalkyl ether propionates such as butyl propionate, ethoxybutyl propionate, propoxy butyl propionate, butoxybutyl propionate; dipropylene glycol II a dipropylene glycol dialkyl ether such as methyl ether, dipropylene glycol diethyl ether or dipropylene glycol methyl ethyl ether; an aromatic hydrocarbon such as benzene, toluene, hydrazine or symmetrical trimethylbenzene; methyl ethyl ketone; a ketone such as acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone; an alcohol such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerin; Acetic acid , ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, glycolic acid Ester, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate Ethyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, Butyl propoxyacetate, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxyl Propyl propionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, An ester of methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate; tetrahydrofuran, piperane, etc. Cyclic ether groups; cyclic esters such as γ-butyrolactone.
上述之溶劑之中,由塗佈性、印刷性、溶解性、乾燥性之觀點,沸點為200℃以上,較佳為200~300℃之酯系溶劑、醚系溶劑及醇系溶劑為佳。Among the above-mentioned solvents, an ester solvent having a boiling point of 200 ° C or higher, preferably 200 to 300 ° C, an ether solvent, and an alcohol solvent are preferred from the viewpoints of coatability, printability, solubility, and drying property.
酯系溶劑係指具有酯鍵結,不具有羥基之有機溶劑。The ester solvent means an organic solvent having an ester bond and having no hydroxyl group.
酯系溶劑之具體例,例如可舉出二乙二醇單乙基醚乙酸酯(沸點217℃)、二乙二醇單丙基醚乙酸酯(232℃)、二乙二醇單丁基醚乙酸酯(沸點247℃)、甘油三乙酸酯(沸點260℃),較佳可舉出二乙二醇單丁基醚乙酸酯(沸點247℃)、甘油三乙酸酯(沸點260℃)。Specific examples of the ester solvent include diethylene glycol monoethyl ether acetate (boiling point: 217 ° C), diethylene glycol monopropyl ether acetate (232 ° C), and diethylene glycol monobutyl Alkyl ether acetate (boiling point: 247 ° C), triacetin (boiling point: 260 ° C), preferably diethylene glycol monobutyl ether acetate (boiling point: 247 ° C), triacetin ( Boiling point 260 ° C).
醚系溶劑係指具有醚鍵結,不具有酯鍵結及羥基之有機溶劑。The ether solvent refers to an organic solvent having an ether bond and having no ester bond and a hydroxyl group.
上述醚系溶劑之具體例,例如可舉出二乙二醇丁基甲基醚(沸點212℃)、三丙二醇二甲基醚(沸點215℃)、三乙二醇二甲基醚(沸點216℃)、二乙二醇二丁基醚(沸點256℃)、三乙二醇丁基甲基醚(沸點261℃)、四乙二醇二甲基醚(沸點275℃),較佳可舉出二乙二醇二丁基醚(沸點256℃)、三乙二醇丁基甲基醚(沸點261℃)。Specific examples of the ether solvent include diethylene glycol butyl methyl ether (boiling point: 212 ° C), tripropylene glycol dimethyl ether (boiling point: 215 ° C), and triethylene glycol dimethyl ether (boiling point: 216 ° C). , diethylene glycol dibutyl ether (boiling point 256 ° C), triethylene glycol butyl methyl ether (boiling point 261 ° C), tetraethylene glycol dimethyl ether (boiling point 275 ° C), preferably exemplified Alcohol dibutyl ether (boiling point 256 ° C), triethylene glycol butyl methyl ether (boiling point 261 ° C).
醇系溶劑係指具有羥基之有機溶劑。The alcohol solvent means an organic solvent having a hydroxyl group.
上述醇系溶劑之具體例,例如可舉出乙二醇單己基醚(沸點208℃)、乙二醇單2-乙基己基醚(沸點229℃)、乙二醇單苯基醚(沸點245℃)、乙二醇單苄基醚(沸點256℃)、二乙二醇單異丙基醚(沸點207℃)、二乙二醇單異丁基醚(沸點220℃)、二乙二醇單丁基醚(沸點230℃)、二乙二醇單戊基醚、二乙二醇單己基醚(沸點259℃)、二乙二醇單2-乙基己基醚(272℃)、二乙二醇單苯基醚(沸點283℃)、三乙二醇單甲基醚(沸點249℃)、三乙二醇單丁基醚(沸點271℃)、聚乙二醇單甲基醚(沸點295℃)、三丙二醇單甲基醚(沸點242℃)、二丙二醇單丙基醚(沸點212℃)、二丙二醇單丁基醚(沸點231℃)、丙二醇單苯基醚(沸點243℃),較佳可舉出乙二醇單苯基醚(沸點245℃)、乙二醇單苄基醚(沸點256℃)、二乙二醇單戊基醚、二乙二醇單己基醚(沸點259℃)、丙二醇單苯基醚(沸點243℃)。Specific examples of the above alcohol-based solvent include ethylene glycol monohexyl ether (boiling point: 208 ° C), ethylene glycol monoethyl 2-ethylhexyl ether (boiling point: 229 ° C), and ethylene glycol monophenyl ether (boiling point 245). °C), ethylene glycol monobenzyl ether (boiling point 256 ° C), diethylene glycol monoisopropyl ether (boiling point 207 ° C), diethylene glycol monoisobutyl ether (boiling point 220 ° C), diethylene glycol Monobutyl ether (boiling point 230 ° C), diethylene glycol monopentyl ether, diethylene glycol monohexyl ether (boiling point 259 ° C), diethylene glycol mono 2-ethylhexyl ether (272 ° C), two Glycol monophenyl ether (boiling point 283 ° C), triethylene glycol monomethyl ether (boiling point 249 ° C), triethylene glycol monobutyl ether (boiling point 271 ° C), polyethylene glycol monomethyl ether (boiling point 295 ° C), tripropylene glycol monomethyl ether (boiling point 242 ° C), dipropylene glycol monopropyl ether (boiling point 212 ° C), dipropylene glycol monobutyl ether (boiling point 231 ° C), propylene glycol monophenyl ether (boiling point 243 ° C) Preferably, ethylene glycol monophenyl ether (boiling point 245 ° C), ethylene glycol monobenzyl ether (boiling point 256 ° C), diethylene glycol monopentyl ether, diethylene glycol monohexyl ether (boiling point) 259 ° C), propylene glycol monophenyl ether (boiling point 243 ° C).
此些之溶劑(D)可各自單獨亦可2種類以上混合使用。These solvents (D) may be used alone or in combination of two or more kinds.
本發明之硬化性樹脂組成物中,相對於黏合劑樹脂(A)、聚合性化合物(B)及溶劑(D)之合計量,溶劑(D)之量例如以質量分率以20質量%以上未滿60質量%,較佳為20質量%以上未滿50質量%,更佳為25質量%以上50質量%以下。溶劑(D)之含有量若未滿20質量%之情況,因硬化性組成物之黏度變得過高,印刷法中之轉印性變得拙劣。另一方面,若為80質量%以上,因硬化性組成物之黏度過得過低,於凹版上容易殘留硬化性組成物,變得難以適用於印刷法。In the curable resin composition of the present invention, the amount of the solvent (D) is, for example, 20% by mass or more based on the mass fraction of the total amount of the binder resin (A), the polymerizable compound (B), and the solvent (D). It is less than 60% by mass, preferably 20% by mass or more and less than 50% by mass, more preferably 25% by mass or more and 50% by mass or less. When the content of the solvent (D) is less than 20% by mass, the viscosity of the curable composition is too high, and the transfer property in the printing method is deteriorated. On the other hand, when the viscosity is 80% by mass or more, the viscosity of the curable composition is too low, and the curable composition tends to remain on the intaglio plate, which makes it difficult to apply to the printing method.
本發明之硬化性樹脂組成物實質上不含有顏料及染料等之著色劑。即,本發明之硬化性樹脂組成物中,相對於組成物全體而著色劑之含量為例如以質量分率為未滿1質量%,較佳為未滿0.5質量%。The curable resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. In the curable resin composition of the present invention, the content of the coloring agent is, for example, less than 1% by mass, preferably less than 0.5% by mass, based on the total mass of the composition.
例如,本發明之硬化性樹脂組成物實質上不含有該領域所使用之以下之著色劑。For example, the curable resin composition of the present invention does not substantially contain the following coloring agents used in the field.
以Color index(The Society of Dyers and Colourists出版)被分類為顏料(Pigment)之化合物,具體而言,C.I. Pigment Yellow 1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等之黃色顏料;C.I. Pigment Orange 13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等之橙色之顏料;C.I. Pigment Red 9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等之紅色顏料;C.I. Pigment Blue 15、15:3、15:4、15:6、60等之藍色顏料;C.I. Pigment Violet 1、19、23、29、32、36、38等之紫色顏料;C.I. Pigment Green 7、36等之綠色顏料;C.I. Pigment Brown 23、25等之棕色顏料;C.I. Pigment Black 1、7等之黑色顏料。A compound classified as a pigment by Color Index (published by The Society of Dyers and Colourists), specifically, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31 Yellow pigments of 53, 53, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. orange pigment; CI Pigment Red 9, 97, 105, 122, 123, Red pigments of 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; CI Pigment Blue 15, 15:3, 15:4 , 15:6, 60, etc. blue pigment; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. purple pigment; CI Pigment Green 7, 36, etc. green pigment; CI Pigment Brown 23, 25 Such as brown pigment; CI Pigment Black 1, 7 and other black pigments.
本發明之硬化性樹脂組成物,依據需要可併用充填劑、其他高分子化合物、均染劑、密著促進劑、抗氧化劑、紫外線吸收劑、光安定劑、防凝集材、鏈轉移劑等之添加劑。The curable resin composition of the present invention may be used in combination with a filler, other polymer compound, leveling agent, adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, anti-agglomerate, chain transfer agent, etc., as needed. additive.
充填劑具體可舉出玻璃、二氧化矽、氧化鋁等。Specific examples of the filler include glass, cerium oxide, and aluminum oxide.
其他高分子化合物具體可舉出環氧樹脂、馬來醯亞胺樹脂等之硬化性樹脂或聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟烷基丙烯酸酯、聚酯、聚胺基甲酸酯等之熱可塑性樹脂等。Specific examples of the other polymer compound include curable resins such as epoxy resins and maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and polyester. A thermoplastic resin such as a polyurethane or the like.
均染劑可使用市售之界面活性劑,例如可舉出聚矽氧系、氟系、酯系、陽離子系、陰離子系、非離子系、兩性等之界面活性劑等,其可各自單獨亦可2種以上組合使用。前述之界面活性劑可舉出例如聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚乙二醇二酯類、山梨醇酐脂肪酸酯類、脂肪酸變性聚酯類、3級胺變性聚胺基甲酸酯類、聚乙烯胺類等以外,尚有商品名為KP(信越化學工業(股)製)、Polyflow(共榮社化學(股)製)、Eftop(三菱Material電子化成(股))、Megafac(DIC(股)製)、Fluorad(住友3M(股)製)、Asahiguide(旭硝子(股)製)、Surflon(AGC SEIMI CHEMICAL(股)製)、Solsperse(Zeneca(股)製)、EFKA(CIBA公司製)、Ajisper PB821(味之素(股)製)等。A commercially available surfactant can be used as the leveling agent, and examples thereof include a surfactant such as a polyfluorene-based, a fluorine-based, an ester-based, a cationic-based, an anionic-based, nonionic-based or amphoteric surfactant, and the like. It can be used in combination of 2 or more types. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and grade 3 In addition to amine-denatured polyurethanes and polyvinylamines, there are also commercially available products such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), and Eftop (Mitsubishi Material Electronic Formation). (share)), Megafac (DIC), Fluorad (Sumitomo 3M (share) system), Asahiguide (Asahi (produced) system), Surflon (AGC SEIMI CHEMICAL), Solsperse (Zeneca) )), EFKA (made by CIBA), Ajisper PB821 (made by Ajinomoto).
密著促進劑以矽烷系化合物為佳,具體可舉出乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯參(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。The adhesion promoter is preferably a decane-based compound, and specific examples thereof include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene ginseng (2-methoxyethoxy) decane, and N-(2-amino group B. 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc. .
抗氧化劑具體可舉出2-tert-丁基-6-(3-tert-丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二-tert-戊基苯基)乙基]-4,6-二-tert-戊基苯基丙烯酸酯、6-[3-(3-tert-丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-tert-丁基二苯并[d、f][1,3,2]dioxaphosphepine、3,9-雙[2-{3-(3-tert-丁基-4-羥基-5-甲基苯基)丙醯基氧基}-1,1-二甲基乙基]-2,4,8,10-四氧螺環[5.5]十一烷、2,2’-亞甲基雙(6-tert-丁基-4-甲基酚)、4,4’-亞丁基雙(6-tert-丁基-3-甲基酚)、4,4’-硫代雙(2-tert-丁基-5-甲基酚)、2,2’-硫代雙(6-tert-丁基-4-甲基酚)、二月桂基3,3’-硫代二丙酸酯、二肉豆蔻基3,3’-硫代二丙酸酯、貳十八烷基3,3’-硫代二丙酸酯、季戊四醇肆(3-月桂基硫代丙酸酯)、1,3,5-參(3,5-二-tert-丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、3,3’,3”,5,5’,5”-六-tert-丁基-a,a’,a”-(對稱三甲苯-2,4,6-三基)三-p-甲酚、季戊四醇肆[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、2,6-二-tert-丁基-4-甲基酚等。Specific examples of the antioxidant include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-( 2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4) -hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine,3,9- Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy}-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylene bis(6-tert- Butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4 -methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, octadecyl 3,3'-thiodi Propionate, pentaerythritol bismuth (3-lauryl thiopropionate), 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5- Triazine-2,4,6(1H,3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"- (symmetric trimethyl-2,4,6-triyl)tri-p-cresol, penta Alcohols store [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionate], 2,6-di -tert- butyl-4-methylphenol and the like.
紫外線吸收劑具體可舉出、2-(2-羥基-5-tert-丁基苯基)-2H-苯並三唑、辛基-3-[3-tert-丁基-4-羥基-5-(5-氯-2H-苯並三唑-2-基)苯基]丙酸酯、2-[4-[(2-羥基-3-十二基氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-[4-[(2-羥基-3-(2’-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,4-雙(2-羥基-4-丁基氧基苯基)-6-(2,4-雙-丁基氧基苯基)-1,3,5-三嗪、2-(2-羥基-4-[1-辛基氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三嗪、2-(2H-苯並三唑-2-基)-4,6-雙(1-甲基-1-苯基乙基)酚、2-(2H-苯並三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)酚、2-(3-tert-丁基-2-羥基-5-甲基苯基)-5-氯苯並三唑或烷氧基二苯甲酮等。Specific examples of the ultraviolet absorber include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole and octyl-3-[3-tert-butyl-4-hydroxy-5. -(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2 -hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-B) Hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxyl -4-Butoxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-xin Benzyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl) -4-(1,1,3,3-tetramethylbutyl)phenol, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole or Alkoxybenzophenone and the like.
光安定劑具體可舉出由琥珀酸與(4-羥基-2,2,6,6-四甲基哌啶-1-基)乙醇構成之高分子、N,N’,N”,N’’’-肆(4,6-雙(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)胺基)三嗪-2-基)-4,7-二吖癸烷-1,10-二胺、癸二酸與雙(2,2,6,6-四甲基-1-(辛基氧基)-4-哌啶基)酯與1,1-二甲基乙基氫過氧化物之反應物、雙(1,2,2,6,6-戊基甲基-4-哌啶基)-[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]丁基丙二酸酯、2,4-雙[N-丁基-N-(1-環己基氧基-2,2,6,6-四甲基哌啶-4-基)胺基]-6-(2-羥基乙基胺)-1,3,5-三嗪、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯或甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯等。Specific examples of the photosensitizer include a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethanol, N,N',N",N'. ''-肆(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4 , 7-dioxane-1,10-diamine, sebacic acid and bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester 1,1-Dimethylethylhydroperoxide reactant, bis(1,2,2,6,6-pentylmethyl-4-piperidinyl)-[[3,5-bis(1) ,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2 ,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, bis(1,2,2,6,6 - pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.
防凝集材可舉出聚丙烯酸鈉等。The anti-agglomerate aggregate may, for example, be sodium polyacrylate.
且,鏈轉移劑可舉出十二基硫醇、2,4-二苯基-4-甲基-1-戊烯等。Further, examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.
本發明之硬化性樹脂組成物,乾燥性為低,不易發生溶劑揮發所成之乾燥異物,既使在高固形分下其保存安定性亦為良好,特別適合於印刷法。The curable resin composition of the present invention has a low drying property and is less likely to cause dry foreign matter formed by solvent volatilization, and is excellent in storage stability even under high solid content, and is particularly suitable for a printing method.
作為前述之印刷法,可使適用於該領域中既知之印刷法,例如,噴墨印刷法、橡皮凸板印刷法、凹板印刷法、平板印刷法、網板印刷法等。As the printing method described above, it can be applied to a printing method known in the art, for example, an inkjet printing method, a rubber plate printing method, a gravure printing method, a lithography method, a screen printing method, or the like.
又,將本發明之硬化性樹脂組成物填充於光徑長度為1cm之石英晶胞,若使用分光光度計在測定波長400~700nm之條件下測定透過率,其平均透過率為70%以上,較佳為75%以上。藉此,可形成透明之圖型或塗膜。Further, the curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and the average transmittance is 70% or more when the transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm. It is preferably 75% or more. Thereby, a transparent pattern or a coating film can be formed.
本發明之硬化性樹脂組成物之硬化條件可依據組成物之各成分之種類、含有量等適宜選擇,通常為使用紫外線等之光硬化、使用烤箱等之加熱硬化。The curing conditions of the curable resin composition of the present invention can be appropriately selected depending on the type and content of each component of the composition, and are usually cured by light curing using an ultraviolet ray or the like, and heat curing using an oven or the like.
又,對本發明之硬化性樹脂組成物在加熱硬化(例如,150~250℃、0.1~3小時)後之3μm之厚度之塗膜,若使用分光光度計在測定波長400~700nm之條件下測定透過率,透過率為90%以上,較佳為95%以上。藉此,可形成透明之圖型或塗膜。Further, the coating film having a thickness of 3 μm after heat curing (for example, 150 to 250 ° C for 0.1 to 3 hours) of the curable resin composition of the present invention is measured by using a spectrophotometer at a measurement wavelength of 400 to 700 nm. The transmittance is preferably 90% or more, preferably 95% or more. Thereby, a transparent pattern or a coating film can be formed.
本發明之硬化性樹脂組成物可例如如下般進行,可在已形成玻璃基板或薄膜基板、濾色器或驅動回路的基材上,藉由印刷法進行塗佈、進行光硬化或加熱硬化,形成塗膜或圖型。The curable resin composition of the present invention can be carried out, for example, by coating, photocuring or heat curing on a substrate on which a glass substrate or a film substrate, a color filter or a drive circuit has been formed, by a printing method. Form a coating film or pattern.
又,將此硬化性樹脂組成物在基板(通常為玻璃)或預先形成之由硬化性樹脂組成物之固形分構成之層上藉由印刷法進行塗佈,由經塗佈之硬化性樹脂組成物層藉由進行預烘烤去除溶劑等之揮發成分,得到平滑之未硬化塗膜(包含圖型)。此時之未硬化塗膜之厚度為約1~6μm。亦可對如此般所得之未硬化塗膜照射由水銀燈或發光二極體所產生之紫外線。Further, the curable resin composition is applied by a printing method on a substrate (usually glass) or a layer formed of a solid component of a curable resin composition which is formed in advance, and is composed of a coated curable resin. The material layer is subjected to prebaking to remove volatile components such as a solvent to obtain a smooth unhardened coating film (including a pattern). The thickness of the unhardened coating film at this time is about 1 to 6 μm. The uncured coating film thus obtained may also be irradiated with ultraviolet rays generated by a mercury lamp or a light-emitting diode.
又,圖型形成中,其線幅可依據凹版尺寸適宜控制。Moreover, in the formation of the pattern, the line width can be appropriately controlled according to the gravure size.
更進一步依據需要,可施予在150~230℃下10~180分之後烘烤。Further, according to the need, it can be baked at 150 to 230 ° C for 10 to 180 minutes.
使用本發明之硬化性樹脂組成物,經過如以上般之各步驟,可在基板上或濾色器基板上形成塗膜或圖型。此塗膜或圖型可用作為液晶顯示裝置所使用之光刻型間隔器或液晶配向用突起、隔壁、保護層。Using the curable resin composition of the present invention, a coating film or pattern can be formed on the substrate or on the color filter substrate through the above steps. This coating film or pattern can be used as a photolithographic spacer or a liquid crystal alignment protrusion, a partition wall, and a protective layer used in a liquid crystal display device.
藉由將如此般所得之塗膜或圖型嵌入液晶顯示裝置等之顯示裝置,可高產率地製造優良品質之顯示裝置。By embedding the coating film or pattern thus obtained in a display device such as a liquid crystal display device, it is possible to manufacture a display device of excellent quality at a high yield.
實施例Example
以下,藉由實施例詳細說明本發明,但本發明並非係受此些實施例所限定者。例中,含有量乃至使用量所表示之%及份,若無特別限定則係為質量基準。Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited. In the examples, the content and the % and the parts expressed by the amount used are based on the mass basis unless otherwise specified.
[合成例1][Synthesis Example 1]
對具備有還流冷卻器、滴下漏斗及攪拌機之1L之燒瓶內將氮以0.02L/分進行流通使其成為氮環境,放入3-甲氧基丁基乙酸酯305質量份,一邊攪拌一邊加熱至70℃。其次,將甲基丙烯酸55質量份、3,4-環氧基三環[5.2.1.02.6 ]癸基丙烯酸酯(式(I-1)所表示之化合物及式(II-1)所表示化合物以莫耳比50:50混合)175質量份及N-環己基馬來醯亞胺70質量份溶解於3-甲氧基丁基乙酸酯140質量份調製成溶液,將該溶解液使用滴入泵經時4小時滴下於保溫在70℃之燒瓶內。另一方面,將聚合開始劑2,2’-偶氮雙(2,4-二甲基戊腈)45質量份溶解於3-甲氧基丁基乙酸酯225質量份之溶液使用其它的滴入泵經時5小時滴入於燒瓶內。聚合開始劑之溶液的滴下結束後,保持4小時、70℃中,其後冷卻至室溫,得到固形分32.6質量%、酸價34.3mg-KOH/g之共聚物的樹脂溶液。所得之樹脂Aa之重量平均分子量Mw為9,000、分散度為2.01。對此樹脂溶液245質量份放入二乙二醇n-丁基醚乙酸酯45質量份,使用旋轉蒸發器在減壓下90℃中將3-甲氧基丁基乙酸酯濃縮餾除,得到固形分64.0質量%之樹脂Aa之二乙二醇n-丁基醚乙酸酯溶液。酸價、重量平均分子量Mw、及分散度與濃縮前相同。In a flask of 1 L equipped with a reflow cooler, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of 3-methoxybutyl acetate was added thereto while stirring. Heat to 70 ° C. Next, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) 175 parts by mass of a molar ratio of 50:50 and 70 parts by mass of N-cyclohexylmaleimine were dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was used dropwise. The pump was dropped in a flask maintained at 70 ° C for 4 hours. On the other hand, 45 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and other solutions are used. The dropwise addition pump was dropped into the flask over 5 hours. After the completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 4 ° C and 70 ° C, and then cooled to room temperature to obtain a resin solution of a copolymer having a solid content of 32.6% by mass and an acid value of 34.3 mg-KOH/g. The obtained resin Aa had a weight average molecular weight Mw of 9,000 and a degree of dispersion of 2.01. 45 parts by mass of diethylene glycol n-butyl ether acetate was placed in 245 parts by mass of the resin solution, and 3-methoxybutyl acetate was concentrated and distilled off at 90 ° C under reduced pressure using a rotary evaporator. A solution of the resin Aa diethylene glycol n-butyl ether acetate having a solid content of 64.0% by mass was obtained. The acid value, the weight average molecular weight Mw, and the degree of dispersion are the same as those before concentration.
[合成例2][Synthesis Example 2]
對具備有還流冷卻器、滴下漏斗及攪拌機之1L之燒瓶內將氮以0.02L/分進行流通使其成為氮環境,放入3-甲氧基丁基乙酸酯305質量份,一邊攪拌一邊加熱至70℃。其次,將甲基丙烯酸60質量份、3,4-環氧基三環[5.2.1.02.6 ]癸基丙烯酸酯(式(I-1)所表示之化合物及式(II-1)所表示之化合物以莫耳比50:50混合)240質量份及溶解於3-甲氧基丁基乙酸酯140質量份調製成溶液,將該溶解液使用滴下漏斗經時4小時,滴入於保溫在70℃中之燒瓶內。另一方面,將聚合開始劑2,2’-偶氮雙(2,4-二甲基戊腈)45質量份溶解於3-甲氧基丁基乙酸酯225質量份之溶液使用其他的滴下漏斗經時4小時滴入於燒瓶內。聚合開始劑之溶液之滴入結束後,保持4小時、70℃中,其後冷卻至室溫,得到固形分32.3質量%、酸價35.6mg-KOH/g之共聚物的樹脂溶液。所得之樹脂Ab之重量平均分子量Mw為9,100,分散度為2.02。對此樹脂溶液245質量份加入二乙二醇n-丁基醚乙酸酯45質量份,使用旋轉蒸發器在減壓下90℃中將3-甲氧基丁基乙酸酯濃縮餾除,得到固形分64.0質量%之樹脂Ab的二乙二醇n-丁基醚乙酸酯溶液。酸價、重量平均分子量Mw、及分散度與濃縮前相同。In a flask of 1 L equipped with a reflow cooler, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of 3-methoxybutyl acetate was added thereto while stirring. Heat to 70 ° C. Next, 60 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1)) The compound was mixed with 240 parts by mass of a molar ratio of 50:50 and dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a funnel for 4 hours, and then added dropwise thereto. In a flask at 70 ° C. On the other hand, 45 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and other solutions are used. The dropping funnel was dropped into the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 4 hours and 70 ° C, and then cooled to room temperature to obtain a resin solution of a copolymer having a solid content of 32.3 mass% and an acid value of 35.6 mg-KOH/g. The obtained resin Ab had a weight average molecular weight Mw of 9,100 and a degree of dispersion of 2.02. 45 parts by mass of diethylene glycol n-butyl ether acetate was added to 245 parts by mass of the resin solution, and 3-methoxybutyl acetate was concentrated and distilled off at 90 ° C under reduced pressure using a rotary evaporator. A diethylene glycol n-butyl ether acetate solution of a resin Ab of 64.0% by mass of solid was obtained. The acid value, the weight average molecular weight Mw, and the degree of dispersion are the same as those before concentration.
(分子量之測定)(Measurement of molecular weight)
關於樹脂Aa及Ab之重量平均分子量(Mw)及數平均分子量(Mn)的測定係使用GPC法在以下的條件下進行。The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins Aa and Ab was carried out under the following conditions using a GPC method.
裝置:K2479((股)島津製作所製)Device: K2479 (made by Shimadzu Corporation)
管柱:SHIMADZU Shim-pack GPC-80MColumn: SHIMADZU Shim-pack GPC-80M
管柱溫度:40℃Column temperature: 40 ° C
溶劑:THF(四氫呋喃)Solvent: THF (tetrahydrofuran)
流速:1.0ml/minFlow rate: 1.0ml/min
檢驗器;RIVerifier; RI
將上述所得之以聚乙烯換算之重量平均分子量及數平均分子量之比作為分散度(Mw/Mn)。The ratio of the weight average molecular weight and the number average molecular weight in terms of polyethylene obtained above was defined as the degree of dispersion (Mw/Mn).
[實施例1][Example 1]
對含有合成例1所得之樹脂Aa的樹脂溶液94份(固形分換算60份)混合二季戊四醇六丙烯酸酯(日本化藥(股)製KAYARAD DPHA)40份、2-甲基-2-嗎啉基-1-(4-甲基磺醯基)丙烷-1-酮1份、二乙二醇n-丁基醚乙酸酯34份而得到硬化性樹脂組成物1。94 parts of a resin solution containing the resin Aa obtained in Synthesis Example 1 (60 parts in terms of solid content), 40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-2-morpholine were mixed. One part of keto-1-(4-methylsulfonyl)propan-1-one and 34 parts of diethylene glycol n-butyl ether acetate were used to obtain a curable resin composition 1.
其次,使硬化性樹脂組成物1如以下般進行而形成圖型。參考圖1進行說明此方法。Next, the curable resin composition 1 is formed into the following pattern as follows. This method will be described with reference to FIG. 1.
首先,由供給裝置(1),將硬化性樹脂組成物1(2)滴入設置於實驗印刷機之凹版(3)上(步驟a)。使滴入之硬化性樹脂組成物1以供給刀(4)一邊均平,一邊以刮墨刀(5)將殘餘之硬化性樹脂組成物1刮取(步驟b)。其次,使轉印薄片(6)裝著於外周面之轉印筒體(7)在凹版(3)上轉動,將硬化性樹脂組成物1轉印於轉印薄片(6)面(步驟c)。其次,將轉印薄片(6)面之硬化性樹脂組成物1轉印於基材(8)面(步驟d)。First, the curable resin composition 1 (2) is dropped from the supply device (1) onto the intaglio plate (3) provided in the experimental printing machine (step a). The hardened resin composition 1 to be dropped is scraped off while the supply blade (4) is level, and the remaining curable resin composition 1 is scraped by the doctor blade (5) (step b). Next, the transfer cylinder (7) on which the transfer sheet (6) is attached to the outer peripheral surface is rotated on the intaglio plate (3), and the curable resin composition 1 is transferred onto the transfer sheet (6) surface (step c ). Next, the curable resin composition 1 on the surface of the transfer sheet (6) is transferred onto the surface of the substrate (8) (step d).
轉印於基材(8)後,進行在100℃/10分鐘乾燥、曝光100mJ/cm2 (I線)、220℃/20分加熱硬化,得到圖型1。After transfer to the substrate (8), the film was dried at 100 ° C for 10 minutes, exposed to 100 mJ/cm 2 (I line), and heated at 220 ° C / 20 minutes to obtain a pattern of 1.
[實施例2][Embodiment 2]
於實施例1中,除了省略曝光步驟以外,進行與實施例1同様之操作,由硬化性樹脂組成物1得到圖型2。In the first embodiment, the same operation as in the first embodiment was carried out except that the exposure step was omitted, and the pattern 2 was obtained from the curable resin composition 1.
[實施例3][Example 3]
以如表1所示之組成,與實施例1相同様地進行,得到硬化性樹脂組成物2及圖型3。The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 2 and a pattern 3.
[實施例4][Example 4]
以如表1所示之組成,與實施例1相同様地進行,得到硬化性樹脂組成物3及圖型4。The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 3 and a pattern 4.
[實施例5][Example 5]
以如表1所示之組成,與實施例1相同様地進行,得到硬化性樹脂組成物4及圖型5。The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 4 and a pattern 5.
[比較例1][Comparative Example 1]
以如表1所示之組成,與實施例1相同様地進行,得到硬化性樹脂組成物5。硬化性樹脂組成物5在與實施例1同様地使用印刷法之情況時,因凹版上殘留大量硬化性組成物,而無法形成圖型。The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 5. In the case where the curable resin composition 5 is used in the same manner as in the first embodiment, a large amount of the curable composition remains on the intaglio plate, and the pattern cannot be formed.
對如上述般所得之硬化性樹脂組成物1~5及圖型1~6,進行以下之評價。其結果如表1所示。The following evaluations were performed on the curable resin compositions 1 to 5 and the patterns 1 to 6 obtained as described above. The results are shown in Table 1.
<組成物之平均透過率><Average transmittance of the composition>
關於各硬化性樹脂組成物,使用紫外線可視近紅外分光光度計(V-650;日本分光(股)製)(石英晶胞、光徑長度;1cm),測定在400~700nm中之平均透過率(%)。For each of the curable resin compositions, an ultraviolet visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length; 1 cm) was used to measure the average transmittance in the range of 400 to 700 nm. (%).
<膜之平均透過率><Average transmittance of film>
使用各硬化性樹脂組成物,使硬化後之膜厚成為3μm,如以下般進行製作硬化膜。Each of the curable resin compositions was used to have a film thickness after curing of 3 μm, and a cured film was produced as follows.
將硬化性樹脂組成物以二乙二醇N-丁基醚乙酸酯使其成為固形分20質量%進行稀釋。以旋轉塗佈法使硬化後膜厚成為3μm進行塗佈,100℃×10分預烘烤後、在220℃×20分下加熱硬化。The curable resin composition was diluted with diethylene glycol N-butyl ether acetate to have a solid content of 20% by mass. The film thickness after hardening was set to 3 μm by a spin coating method, and after prebaking at 100 ° C × 10 minutes, the film was heat-cured at 220 ° C × 20 minutes.
關於所得之各硬化膜,使用顯微分光測光裝置(OSP-SP200;OLYMPUS公司製),測定400~700nm中之平均透過率(%)。With respect to each of the obtained cured films, an average transmittance (%) in a range of 400 to 700 nm was measured using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS).
透過率變高則係指吸收變小。A higher transmittance means less absorption.
<圖型之形狀><Shape shape>
將各圖型之形狀以三次元非接觸表面形狀測量系統(Micromap MM527N(股)菱化系統製)進行測量。The shape of each pattern was measured by a three-dimensional non-contact surface shape measuring system (manufactured by Micromap MM527N (manufacturing) system).
由如表1所示之實施例1~5之結果,得知含有所定量之溶劑的本發明之硬化性樹脂組成物,使用印刷法,可形成高透過率之塗膜及圖型。另一方面,比較例1並無法使用印刷法。As a result of Examples 1 to 5 shown in Table 1, it was found that the curable resin composition of the present invention containing a predetermined amount of solvent can form a coating film and a pattern having a high transmittance by a printing method. On the other hand, in Comparative Example 1, the printing method could not be used.
產業上之可利用性Industrial availability
本發明之硬化性樹脂組成物使用印刷法可形成透過率優良之塗膜及圖型。因此,可適宜用於用以配合覆蓋塗層、光刻型間隔器、絶緣膜、液晶配向控制用突起、著色圖型之膜厚的塗膜層等、顯示裝置所用之塗膜或圖型之形成。The curable resin composition of the present invention can form a coating film and a pattern having excellent transmittance by a printing method. Therefore, it can be suitably used for a coating film or pattern for use in a display device, such as a coating layer, a photolithographic spacer, an insulating film, a projection for liquid crystal alignment control, a coating film layer of a coloring pattern, and the like. form.
1‧‧‧供給裝置1‧‧‧Supply device
2‧‧‧樹脂組成物2‧‧‧Resin composition
3‧‧‧凹版3‧‧‧gravure
4‧‧‧供給刀(supply blade)4‧‧‧supply blade
5‧‧‧刮墨刀(scraping blade)5‧‧‧scraping blade
6‧‧‧轉印薄片6‧‧‧Transfer sheet
7‧‧‧轉印胴7‧‧‧Transfer胴
8‧‧‧基材8‧‧‧Substrate
[圖1]表示使用印刷法由樹脂組成物形成圖型之方法。Fig. 1 shows a method of forming a pattern from a resin composition using a printing method.
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JP6047885B2 (en) * | 2011-03-08 | 2016-12-21 | 住友化学株式会社 | Colored photosensitive resin composition |
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JP5949097B2 (en) * | 2012-04-25 | 2016-07-06 | Jsr株式会社 | Thermosetting resin composition, protective film for display element, and method for forming protective film for display element |
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