TWI656406B - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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TWI656406B
TWI656406B TW102103672A TW102103672A TWI656406B TW I656406 B TWI656406 B TW I656406B TW 102103672 A TW102103672 A TW 102103672A TW 102103672 A TW102103672 A TW 102103672A TW I656406 B TWI656406 B TW I656406B
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monomer
meth
structural unit
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TW201335715A (en
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井上勝治
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日商住友化學股份有限公司
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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
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • 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
    • 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
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

一種包含(A)、(B)及(C)的光敏性樹脂組成物：(A)一種共聚物，包含來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元，其中，來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是，相對於該共聚物的所有構造單元的0.01質量%以上5質量%以下；(B)不含矽原子的聚合性化合物；(C)聚合起始劑。 A photosensitive resin composition comprising (A), (B), and (C): (A) a copolymer including a structure derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride Unit, a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond, Among them, the content of the structural unit derived from the monomer having a siloxane structure and an ethylenically unsaturated bond is 0.01% by mass or more and 5% by mass or less with respect to all the structural units of the copolymer; (B) does not include Polymerizable compound of silicon atom; (C) Polymerization initiator.

Description

光敏性樹脂組成物 Photosensitive resin composition

本發明是關於光敏性樹脂組成物。 The present invention relates to a photosensitive resin composition.

在近年的液晶顯示平板等，有使用光間隔物、外保護膜(overcoat)及噴墨用的分割牆等的構件，就這些構件而言，有使用由光敏性樹脂組成物所形成的樹脂圖案、硬化膜。 In recent years, liquid crystal display panels and the like include members using a photo spacer, an overcoat, a partition wall for inkjet, and the like, and these members include a resin pattern formed using a photosensitive resin composition. , Hardened film.

就這種光敏性樹脂組成物而言，例如，就樹脂而言，已知包含甲基丙烯酸與丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯的共聚物的光敏性樹脂組成物(JP2009-139932-A)。 For such a photosensitive resin composition, for example, as the resin, a photosensitive resin containing a copolymer of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl acrylate is known. Composition (JP2009-139932-A).

當使用由光敏性樹脂組成物所形成的樹脂圖案作為光間隔物時，該樹脂圖案係希望獲得除去荷重時會恢復到原來形狀的機械特性，即柔軟性。這個機械特性是以恢復率表示，該恢復率係將光間隔物除去時而恢復到原來形狀的變化量(彈性變化量)對於將其加上荷重時的變化量(總變化量)的比率。 When a resin pattern formed of a photosensitive resin composition is used as a photo spacer, the resin pattern is desired to obtain mechanical properties, that is, flexibility, which is restored to the original shape when the load is removed. This mechanical characteristic is expressed by a recovery rate, which is a ratio of a change amount (elastic change amount) of the original shape when the photo spacer is removed to a change amount (total change amount) when a load is added thereto.

以往所知的上述由光敏性樹脂組成物所得的樹脂圖案並非恢復率一定可充分満足者。 Conventionally known resin patterns obtained from the above-mentioned photosensitive resin composition are not necessarily those whose recovery rate is sufficient.

本發明包含以下的發明。 The present invention includes the following inventions.

[1]一種光敏性樹脂組成物，係含有(A)、(B)，及(C)： [1] A photosensitive resin composition containing (A), (B), and (C):

(A)一種共聚物，係包含來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元，其中，來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是相對於該共聚物的所有構造單元的0.01質量%以上5質量%以下 (A) A copolymer comprising at least one structural unit derived from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure derived from a carbon number of 2 to 4, and ethylenicity The structural unit of a monomer having an unsaturated bond and the structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond, among which the monomer is derived from a monomer having a siloxane structure and an ethylenically unsaturated bond The content of the structural unit is 0.01 mass% or more and 5 mass% or less with respect to all the structural units of the copolymer

(B)不含矽原子的聚合性化合物 (B) Polymerizable compound containing no silicon atom

(C)聚合起始劑 (C) Polymerization initiator

[2]如[1]所述的光敏性樹脂組成物，其中，具有矽氧烷構造及乙烯性不飽和鍵的單體的重量平均分子量是300至50000。 [2] The photosensitive resin composition according to [1], wherein the weight average molecular weight of the monomer having a siloxane structure and an ethylenically unsaturated bond is 300 to 50,000.

[3]一種由[1]或[2]所述的光敏性樹脂組成物所形成的樹脂圖案。 [3] A resin pattern formed from the photosensitive resin composition according to [1] or [2].

[4]一種包含[3]所述的樹脂圖案的顯示裝置。 [4] A display device including the resin pattern according to [3].

[5]一種共聚物，係包含來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元 [5] A copolymer comprising at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a cyclic ether structure derived from a carbon number of 2 to 4 and ethylenicity A structural unit of an unsaturated bond monomer and a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond

其中，來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是相對於該共聚物的所有構造單元的0.01質量%以上5質量%以下。 Here, the content of the structural unit derived from the monomer having a siloxane structure and an ethylenically unsaturated bond is 0.01% by mass or more and 5% by mass or less with respect to all the structural units of the copolymer.

若使用本發明的光敏性樹脂組成物時，由該光敏性樹脂組成物所形成的樹脂圖案因除去所加荷重時的恢復率高，所 以有優異的機械特性。 When the photosensitive resin composition of the present invention is used, the resin pattern formed from the photosensitive resin composition has a high recovery rate when the applied load is removed. To have excellent mechanical properties.

在本說明書中，作為各成分之例示化合物無特別註明時，可單獨或組合多種而使用。 In the present specification, unless specified otherwise, the exemplified compounds of the respective components may be used alone or in combination.

本發明的光敏性樹脂組成物包含(A)、(B)及(C)： The photosensitive resin composition of the present invention includes (A), (B), and (C):

(A)一種共聚物，係包含來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元， 其中，來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是相對於該共聚物的所有構造單元的0.01質量%以上5質量%以下(以下有時稱為「樹脂(A)」)。 (A) A copolymer comprising at least one structural unit derived from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure derived from a carbon number of 2 to 4, and ethylenicity A structural unit of an unsaturated bond monomer and a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond, The content of the structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond is 0.01% by mass or more and 5% by mass or less (hereinafter sometimes referred to as " Resin (A) ").

(B)不含矽原子的聚合性化合物(以下有時稱為「聚合性化合物(B)」 (B) a polymerizable compound containing no silicon atom (hereinafter sometimes referred to as "polymerizable compound (B)"

(C)聚合起始劑(以下有時稱為「聚合起始劑(C)」 (C) Polymerization initiator (hereinafter sometimes referred to as "polymerization initiator (C)"

再者，本發明的光敏性樹脂組成物較佳為包含選自由溶劑(E)及界面活性劑(H)所成群組中的至少1種。 Moreover, it is preferable that the photosensitive resin composition of this invention contains at least 1 sort (s) chosen from the group which consists of a solvent (E) and a surfactant (H).

又，本發明的光敏性樹脂組成物亦可包含選自由硫醇化合物(T)、抗氧化劑(F)、及聚合起始助劑(C1)所成之群中的至少1種。 The photosensitive resin composition of the present invention may include at least one selected from the group consisting of a thiol compound (T), an antioxidant (F), and a polymerization initiator (C1).

<樹脂> <Resin>

樹脂(A)包含來源於至少1種選自由不飽和羧酸及不 飽和羧酸酐所成群組中(以下有時稱為「(a)」)的構造單元，與來源於據碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體(以下有時稱為「(b)」)的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體(以下有時稱為「(x)」)的構造單元。該共聚物亦可復包含來源於可與(a)聚合而與(b)及(x)不同的單體(以下有時稱為「(c)」)的構造單元。 The resin (A) contains at least one selected from the group consisting of unsaturated carboxylic acids and A structural unit in a group of saturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), and a monomer derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter referred to as It is called a "(b)" structural unit, and a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(x)"). The copolymer may further include a structural unit derived from a monomer (hereinafter sometimes referred to as "(c)") which is polymerizable with (a) and different from (b) and (x).

就樹脂(A)而言，例如，可列舉樹脂[K1]及樹脂[K2]。 Examples of the resin (A) include resin [K1] and resin [K2].

樹脂[K1]：由來源於(a)的構造單元、來源於(b)的構造單元、與來源於(x))的構造單元所組成的共聚物；樹脂[K2]：由來源於(a)的構造單元、來源於(b)的構造單元、來源於(x)的構造單元、與來源於(c)的構造單元所組成的共聚物。 Resin [K1]: a copolymer composed of a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (x)); resin [K2]: a copolymer derived from (a ), A structural unit derived from (b), a structural unit derived from (x), and a copolymer composed of a structural unit derived from (c).

樹脂(A)是將(a)、(b)及(x)，以及視需要與(c)共聚合的共聚物。 Resin (A) is a copolymer in which (a), (b), and (x), and (c) are copolymerized as necessary.

就(a)而言，例如，可列舉丙烯酸、甲基丙烯酸、巴豆酸(crotonic acid)、鄰-乙烯基安息香酸、間-乙烯基安息香酸、對-乙烯基安息香酸等的不飽和單羧酸類；馬來酸、富馬酸、檸康酸(citraconic acid)、中康酸(mesaconic acid)、衣康酸(itaconic acid)、3-乙烯基酞酸、4-乙烯基酞酸、3,4,5,6-四氫酞酸、1,2,3,6-四氫酞酸、二甲基四氫酞酸、1,4-環己烯二羧酸等的不飽和二羧酸類；甲基-5-降崁基-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[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-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-烯等的含有羧基的雙環不飽和化合物類；馬來酸酐、檸康酸酐、衣康酸酐、3-乙烯基酞酸酐、4-乙烯基酞酸酐、3,4,5,6-四氫酞酸酐、1,2,3,6-四氫酞酸酐、二甲基四氫酞酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯無水物等的不飽和二羧酸酐類；琥珀酸單[2-(甲基)丙烯醯基氧基乙基]酯、酞酸單[2-(甲基)丙烯醯基氧基乙基]酯等的2價以上的多元羧酸不飽和單[(甲基)丙烯醯基氧基烷基]酯類；含有α-(羥甲基)丙烯酸等在分子內含有羥基及羧基的不飽和丙烯酸酯類等。 Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid. Acids; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3, Unsaturated dicarboxylic acids such as 4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornyl-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [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-carboxy-6-methylbicyclo [ 2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3- Vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6- Unsaturated dicarboxylic anhydrides such as dicarboxybicyclo [2.2.1] hept-2-ene anhydride; succinate mono [2- (meth) acrylfluorenyloxyethyl] ester, phthalic acid mono [2- (Meth) acrylfluorenyloxyethyl] esters and other polyvalent unsaturated carboxylic acid unsaturated mono [(meth) acrylfluorenyloxyalkyl] esters; containing α- (hydroxymethyl) acrylic acid Such as unsaturated acrylates containing a hydroxyl group and a carboxyl group in the molecule.

在這些之中，在共聚合反應性、對鹼水溶液的樹脂溶解性之點，較佳為(甲基)丙烯酸及馬來酸酐等，更佳為(甲基)丙烯酸。 Among these, (meth) acrylic acid, maleic anhydride, and the like are preferable from the viewpoints of copolymerization reactivity and resin solubility in an alkali aqueous solution, and (meth) acrylic acid is more preferable.

此外，本說明書中的「(甲基)丙烯醯基」表示至少1種選自由丙烯醯基及甲基丙烯醯基所成群組的基。「(甲基)丙烯酸」及「(甲基)丙烯酸酯」等的表述也有同樣的意思。 The "(meth) acrylfluorenyl group" in this specification means at least one group selected from the group consisting of acrylfluorenyl group and methacrylfluorenyl group. The expressions "(meth) acrylic acid" and "(meth) acrylate" have the same meaning.

就(b)的碳數2至4的環狀醚構造而言，例如，可列舉環氧乙烷環、環氧丙烷環及四氫呋喃環。(b)較佳為具有碳數2至4的環狀醚與(甲基)丙烯醯氧基的單體。 Examples of the cyclic ether structure having 2 to 4 carbon atoms in (b) include an ethylene oxide ring, a propylene oxide ring, and a tetrahydrofuran ring. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

就(b)而言，例如，可列舉具有環氧乙烷基與乙烯性不飽和鍵的單體(b1)(以下有時稱為「(b1)」)、具有環氧丙烷基與乙烯性不飽和鍵的單體(b2)(以下有時稱為「(b2)」)及具有四氫呋喃基與乙烯性不飽和鍵的單體(b3)(以下有時稱為「(b3)」)。 Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a propylene oxide group and an ethylenic group. An unsaturated bond monomer (b2) (hereinafter sometimes referred to as "(b2)") and a monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

就(b1)而言，例如，可列舉具有直鏈狀或支鏈狀的不飽和脂肪族烴經環氧化的構造的單體(b1-1)(以下有時稱為「(b1-1)」)、及具有不飽和脂環式烴經環氧化的構造的單體(b1-2))(以下有時稱為「(b1-2)」)。 As for (b1), for example, a monomer (b1-1) having an epoxidized structure of a linear or branched unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as "(b1-1) "), And a monomer (b1-2)) having an epoxidized structure of an unsaturated alicyclic hydrocarbon (hereinafter sometimes referred to as" (b1-2) ").

就(b1-1)而言，例如，可列舉(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸β-甲基環氧丙酯、(甲基)丙烯酸β-乙基環氧丙酯、環氧丙基乙烯基醚、鄰-乙烯基苄基環氧丙基醚、間-乙烯基苄基環氧丙基醚、對-乙烯基苄基環氧丙基醚、α-甲基-鄰-乙烯基苄基環氧丙基醚、α-甲基-間-乙烯基苄基環氧丙基醚、α-甲基-對-乙烯基苄基環氧丙基醚、2,3-雙(環氧丙基氧基甲基)苯乙烯、2,4-雙(環氧丙基氧基甲基)苯乙烯、2,5-雙(環氧丙基氧基甲基)苯乙烯、2,6-雙(環氧丙基氧基甲基)苯乙烯、2,3,4-參(環氧丙基氧基甲基)苯乙烯、2,3,5-參(環氧丙基氧基甲基)苯乙烯、2,3,6-參(環氧丙基氧基甲基)苯乙烯、3,4,5-參(環氧丙基氧基甲基)苯乙烯、2,4,6-參(環氧丙基氧基甲基)苯乙烯等。 Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and β-ethylglycidyl (meth) acrylate. , Glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl- O-vinyl benzyl epoxy propyl ether, α-methyl-m-vinyl benzyl epoxy propyl ether, α-methyl-p-vinyl benzyl epoxy propyl ether, 2,3- Bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-gins (glycidyloxymethyl) styrene, 2,3,5-gins (glycidyl (Oxymethyl) styrene, 2,3,6-ginsyl (epoxypropyloxymethyl) styrene, 3,4,5-ginseng (epoxypropyloxymethyl) styrene, 2, 4,6-ginsyl (epoxypropyloxymethyl) styrene and the like.

就(b1-2)而言，例如，可列舉乙烯基環己烯單氧化物、1,2-環氧基-4-乙烯基環己烷(例如，CELLOXIDE 2000(商品名)；DAICEL股份有限公司製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如，CYCLOMER A400(商品名)；DAICEL股份有限公司製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如，CYCLOMER-M100(商品名)；DAICEL股份有限公司製)、式(I)表示的單體、式(II)表示的單體等。 As for (b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000 (trade name); DAICEL shares are limited (Manufactured by the company), 3,4-epoxycyclohexyl methyl (meth) acrylate (for example, CYCLOMER A400 (trade name); manufactured by DAICEL Co., Ltd.), 3,4-epoxy (meth) acrylate Hexyl methyl ester (for example, CYCLOMER-M100 (trade name); manufactured by DAICEL Co., Ltd.), a monomer represented by formula (I), a monomer represented by formula (II), and the like.

[式(I)及式(II)中，Rb1及Rb2表示氫原子、或碳數1至4的烷基，該烷基所包含的氫原子可經羥基取代。 [In formulae (I) and (II), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

Xb1及Xb2表示單鍵、-Rb3-、*-Rb3-O-、*-Rb3-S-或*-Rb3-NH-。 X b1 and X b2 represents a single bond, -R b3 -, * - R b3 -O -, * - R b3 -S- or * -R b3 -NH-.

Rb3表示碳數1至6的烷二基。 R b3 represents an alkanediyl group having 1 to 6 carbon atoms.

*表示與O鍵結的鍵。] * Indicates a bond to O bond. ]

就碳數1至4的烷基而言，可列舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.

就氫原子經羥基取代的烷基而言，可列舉羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the alkyl group having a hydrogen atom substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

就Rb1及Rb2而言，較佳為可列舉氫原子、甲基、羥基甲基、1-羥基乙基及2-羥基乙基，更佳為可列舉氫原子及甲基。 R b1 and R b2 include preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

就烷二基而言，可列舉亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1, 5-diyl, hexane-1,6-diyl, and the like.

就Xb1及Xb2而言，較佳為可列舉單鍵、亞甲基、伸乙基、*-CH2-O-及*-CH2CH2-O-，更佳為可列舉單鍵、*-CH2CH2-O-(*表示與O鍵結的鍵)。 For X b1 and X b2 , a single bond, methylene, ethylidene, * -CH 2 -O- and * -CH 2 CH 2 -O- are preferred, and a single bond is more preferred. , * -CH 2 CH 2 -O- (* represents a bond to O).

就式(I)所示的單體而言，可列舉式(I-1)至式(I-15)的 任一者所示的單體等。其中，較佳為式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)或式(I-11)至式(I-15)所示的單體，更佳為式(I-1)、式(I-7)、式(I-9)或式(I-15)所示的單體。 As for the monomer represented by the formula (I), those having the formula (I-1) to the formula (I-15) Either a monomer or the like. Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I) are preferred. The monomer represented by -15) is more preferably a monomer represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

就式(II)所示的單體而言，可列舉式(II-1)至式(II-I5)的任一者所示的單體等。其中，較佳為式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)至式(II-15)所示的單體，更佳為式(II-1)、式(II-7)、式(II-9)或式(II-15)所示的單體。 Examples of the monomer represented by the formula (II) include monomers represented by any of the formula (II-1) to the formula (II-I5). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II) are preferred The monomer represented by -15) is more preferably a monomer represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

式(I)所表的單體及式(II)所示的單體是可各別單獨使用，亦可將式(I)所示的單體與式(II)所示的單體併用。要併用這些單體時，式(I)所示的單體及式(II)所示的單體的含有比率以莫耳基準，較佳為5：95至95：5，更佳為10：90至90：10，再更佳為20：80至80：20。 The monomer represented by the formula (I) and the monomer represented by the formula (II) may be used individually, or a monomer represented by the formula (I) and a monomer represented by the formula (II) may be used in combination. When these monomers are used in combination, the content ratio of the monomer represented by the formula (I) and the monomer represented by the formula (II) is on a molar basis, preferably 5:95 to 95: 5, and more preferably 10: 90 to 90:10, and more preferably 20:80 to 80:20.

就(b2)而言，更佳為具有氧雜環丁基與(甲基)丙烯醯氧基的單體。就(b2)而言，可列舉3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲 基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯基氧基乙基氧雜環丁等。 As for (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3 -Ethyl-3-form Allyloxymethyloxetane, 3-ethyl-3-propoxymethyloxetane, 3-methyl-3-methoxyethyloxetane Butane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3-ethyl-3- Propenyloxyethyloxetane and the like.

就(b3)而言，更佳為具有四氫呋喃基與(甲基)丙烯醯氧基的單體。就(b3)而言，具體而言，可列舉丙烯酸四氫呋喃酯(例如，VISCOAT V#150(商品名)，大阪有機化學工業股份有限公司製)、甲基丙烯酸四氫呋喃酯等。 As for (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofuran acrylate (for example, VISCOAT V # 150 (trade name), manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methacrylate, and the like.

就(b)而言，在可更提高所得的樹脂圖案、硬化膜的耐熱性、耐藥品性等的信頼性之點，較佳為(b1)。再者，在光敏性樹脂組成物的保存安定性優異之點，更佳為(b1-2)。 (B) is preferably (b1) from the viewpoint that the reliability of the obtained resin pattern, cured film, heat resistance, and chemical resistance can be further improved. Furthermore, the point which is excellent in the storage stability of a photosensitive resin composition is (b1-2).

(x)的矽氧烷構造是例如式(x1)所示的構造。 The siloxane structure of (x) is a structure represented by Formula (x1), for example.

[式(x1)中，A1及A2是互相單獨表示1價的有機基。] [In the formula (x1), A 1 and A 2 are each independently a monovalent organic group. ]

就1價的有機基而言，例如，可列舉1價的烴基。1價的烴基較佳為碳數1至10的1價的脂肪族烴基、碳數3至10的1價的脂環式烴基及碳數6至10的1價的芳香族烴基，更佳為碳數1至4的烷基或碳數6至10的1價的芳香族烴基，再更佳為甲基或苯基。 Examples of the monovalent organic group include a monovalent hydrocarbon group. The monovalent hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably The alkyl group having 1 to 4 carbon atoms or the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is still more preferably a methyl group or a phenyl group.

(x)的乙烯性不飽和鍵較佳為(甲基)丙烯基。 The (x) ethylenically unsaturated bond is preferably a (meth) propenyl group.

就(x)而言，例如，可列舉式(x2)所示的單體。 Examples of (x) include a monomer represented by formula (x2).

[式(x2)中，Q1表示氫原子或甲基。 [In formula (x2), Q1 represents a hydrogen atom or a methyl group.

L1表示-(CH2)r-、-O-(CH2)r-或-C(=O)-O-(CH2)r-，這些基所含的至少1個-CH2-亦可經雜原子取代。 L 1 represents-(CH 2 ) r- , -O- (CH 2 ) r -or -C (= O) -O- (CH 2 ) r- , and at least one of these groups -CH 2 -also Can be substituted by heteroatoms.

r表示0至8的整數。 r represents an integer from 0 to 8.

A3至A11表示各別單獨表示碳數1至12的脂肪族烴基、碳數6至12的芳基或碳數7至12的芳基烷基。 A 3 to A 11 each independently represent an aliphatic hydrocarbon group having 1 to 12 carbons, an aryl group having 6 to 12 carbons or an arylalkyl group having 7 to 12 carbons.

s、t及u各別單獨表示0至200的整數。] s, t, and u each independently represent an integer from 0 to 200. ]

就A3至A11的脂肪族烴而言，例如，可列舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、辛基及十二烷基等。 Examples of the aliphatic hydrocarbons of A 3 to A 11 include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, octyl, and twelve Alkyl, etc.

就A3至A11的芳基而言，例如，可列舉苯基、甲苯基、二甲苯基、均三甲苯基(mesityl)、聯苯基及萘基。 Examples of the aryl group of A 3 to A 11 include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a biphenyl group, and a naphthyl group.

就A3至A11的芳基烷基而言，例如，可列舉苄基及苯基乙基。 Examples of the arylalkyl group of A 3 to A 11 include a benzyl group and a phenylethyl group.

就式(x2)所示的單體而言，較佳為式(x 3)所示的單體及式(x4)所示的單體，更佳為式(x3)所示的單體。 The monomer represented by formula (x2) is preferably a monomer represented by formula (x 3) and a monomer represented by formula (x4), and more preferably a monomer represented by formula (x3).

[式(x3)及式(x4)中，Q2及Q3表示氫原子或甲基。 [In formulae (x3) and (x4), Q 2 and Q 3 represent a hydrogen atom or a methyl group.

A12表示碳數1至12的脂肪族烴基、碳數6至12的芳基或碳數7至12的芳基烷基。 A 12 represents an aliphatic hydrocarbon group having 1 to 12 carbons, an aryl group having 6 to 12 carbons, or an arylalkyl group having 7 to 12 carbons.

v表示0至200的整數。 v represents an integer from 0 to 200.

w及y各別單獨表示0至30的整數。] w and y each independently represent an integer from 0 to 30. ]

就A12而言，可列舉與A3至A11的同樣的基，較佳為甲基或苯基。 As for A 12 , the same groups as A 3 to A 11 may be listed, and a methyl group or a phenyl group is preferred.

v較佳表示0至100的整數。 v preferably represents an integer from 0 to 100.

就(x)而言，例如，可列舉甲基丙烯酸三甲基矽烷基甲酯、甲基丙烯酸(苯基二甲基矽烷基)甲酯、第三丁基二甲基乙烯基矽烷、烯丙基二甲基矽烷、烯丙基三甲基矽烷、三苯基乙烯基矽烷、甲基丙烯酸三甲基矽烷基甲酯、乙烯基二乙基甲基矽烷、乙烯基參(三甲基矽氧烷基)矽烷、乙烯基三甲基矽烷、乙烯甲基雙(三甲基矽氧烷基)矽烷、苯基二甲基乙烯基矽烷、苯基甲基乙烯基矽烷及下述式所示的單體。在下述式中，Q4表示氫原子或甲基，z是表示2至200。 Examples of (x) include trimethylsilyl methacrylate, (phenyldimethylsilyl) methacrylate, tert-butyldimethylvinylsilane, and allyl Dimethyl silane, allyl trimethyl silane, triphenyl vinyl silane, trimethyl silane methacrylate, vinyl diethyl methyl silane, vinyl ginseng (trimethyl siloxane (Alkyl) silane, vinyltrimethylsilane, vinylmethylbis (trimethylsilyloxy) silane, phenyldimethylvinylsilane, phenylmethylvinylsilane, and monomer. In the following formula, Q4 represents a hydrogen atom or a methyl group, and z represents 2 to 200.

就(x)而言，例如，亦可使用SILAPLANE FM-0711(商品名)(重量平均分子量(以下有時稱為「Mw」)：1000，式(x3-2)所示的單體，Q4=甲基)、SILAPLANE FM-0721(Mw：5000，式(x3-2)所示的單體，Q4=甲基)、SILAPLANE FM-0725(Mw：10000，式(x3-2)所示的單體，Q4=甲基)、SILAPLANE FM-0701(Mw：420，式(x3-1)所示的單體，Q4=甲基)、SILAPLANE FM-0701T(Mw：420，式(x4-2)所示的單體，Q4=甲基)(均為JNC股份有限公司製)、X-22-2475(Mw：420，式(x3-1)所示的單體，Q4=甲基)、X-22-174DX(Mw：4600，式(x3-2)所示的單體，Q4=甲基)、X-24-8201(Mw：2100)、X-22-2426(Mw：12000，式(x3-2)所示的單體，Q4=甲基)、X-22-2404(Mw：420，式(x4-2)所示的單體，Q4=甲基)、X-22-2406(均為信越化學工業股份有限公司製)等的市售品。 As for (x), for example, SILAPLANE FM-0711 (trade name) (weight average molecular weight (hereinafter sometimes referred to as “Mw”): 1000, a monomer represented by the formula (x3-2), Q 4 = methyl), SILAPLANE FM-0721 (Mw: 5000, monomer shown by formula (x3-2), Q 4 = methyl), SILAPLANE FM-0725 (Mw: 10000, formula (x3-2)) Monomer shown, Q 4 = methyl), SILAPLANE FM-0701 (Mw: 420, monomer shown by formula (x3-1), Q 4 = methyl), SILAPLANE FM-0701T (Mw: 420, formula A monomer represented by (x4-2), Q 4 = methyl) (both manufactured by JNC Corporation), X-22-2475 (Mw: 420, monomer represented by formula (x3-1), Q 4 = methyl), X-22-174DX (Mw: 4600, monomer represented by formula (x3-2), Q 4 = methyl), X-24-8201 (Mw: 2100), X-22- 2426 (Mw: 12000, monomer represented by formula (x3-2), Q 4 = methyl), X-22-2404 (Mw: 420, monomer represented by formula (x4-2), Q 4 = (Methyl), X-22-2406 (both manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.

(x)的重量平均分子量較佳為300至50000，更佳為350至7000，再更佳為2000至6000。(x)的重量平均分子量在前述的範圍內時，樹脂圖案的機械特性及與水、有機溶劑的接觸角有 變高的傾向。 The weight-average molecular weight of (x) is preferably 300 to 50,000, more preferably 350 to 7000, and even more preferably 2,000 to 6,000. (x) When the weight-average molecular weight is within the aforementioned range, the mechanical characteristics of the resin pattern and the contact angle with water and organic solvents are different. The tendency to get higher.

就(c)而言，例如，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-酯(在本技術領域中，慣用名是「甲基丙烯酸二環戊酯(dicyclopentanyl methacrylate)」。又，有時稱為「(甲基)丙烯酸三環癸酯(tricyclodecyl methacrylate)。」、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-酯(在本技術領域中，慣用名是「(甲基)丙烯酸二環戊烯酯」。)、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異降崁酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等的(甲基)丙烯酸酯類；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等的含有羥基的(甲基)丙烯酸酯類；馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等的二羧酸二乙酯；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-羥基甲基雙環[2.2.1]庚-2-烯、5-(2-羥基乙基)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(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-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[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-雙(第三丁基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己基氧基羰基)雙環[2.2.1]庚-2-烯等的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-琥珀醯亞胺基-3-馬來醯亞胺安息酸酯、N-琥珀醯亞胺-4-馬來醯亞胺丁酸酯、N-琥珀醯亞胺-6-馬來醯亞胺癸酸酯、N-琥珀醯亞胺-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺等的二羰基醯亞胺衍生物類；苯乙烯、α-甲基苯乙烯、鄰-乙烯基甲苯、間-乙烯基甲苯、對-乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、氯亞乙烯、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。 Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) Tertiary butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Cyclopentyl, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-ester (in this In the technical field, the common name is "dicyclopentanyl methacrylate". Also, it is sometimes called "tricyclodecyl methacrylate.", (Meth) acrylic acid Cyclo [5.2.1.0 2,6 ] decene-8-ester (In the technical field, the common name is "dicyclopentenyl (meth) acrylate".), Dicyclopentyloxy (meth) acrylate Ethyl ester, isonorbornyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, ( Naphthyl (meth) acrylate, (meth) acrylic (Meth) acrylates such as benzyl esters; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid di Diethyl dicarboxylates such as ethyl acetate, diethyl fumarate, diethyl itaconic acid, etc .; 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-hydroxymethylbicyclo [2.2.1] hept-2-ene , 5- (2-hydroxyethyl) 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-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 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-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-third butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl Bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene 5,6-bis (third butylcarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide Benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide decanoate, N-succinimide-3-mar Dicarbonylimine derivatives such as lyme imine propionate and N- (9-acridyl) maleimide; styrene, α-methylstyrene, o-vinyltoluene, m- -Vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

在這些單體之中，從共聚反應性及耐熱性之點來看，較佳為苯乙烯、乙烯基甲苯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺及雙環[2.2.1]庚-2-烯。 Among these monomers, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N -Benzylmaleimide and bicyclo [2.2.1] hept-2-ene.

在樹脂(A)中，來源於(x)的構造單元的含有量是相對於樹脂(A)的所有構造單元的0.01質量%以上5質量%以下，較佳為0.01質量%以上3質量%以下，更佳為0.02質量%以上1質量%以下。 In the resin (A), the content of the structural unit derived from (x) is 0.01 mass% or more and 5 mass% or less with respect to all the structural units of the resin (A), and preferably 0.01 mass% or more and 3 mass% or less. , More preferably 0.02% by mass or more and 1% by mass or less.

在樹脂[K1]中，來源於各別的單體的構造單元的比率是較佳為相對於構成樹脂[K1]的所有構造單元， 來源於(a)的構造單元為5至60莫耳%，來源於(b)的構造單元為40至98莫耳%，來源於(x)的構造單元為0.01至5莫耳%，更佳為來源於(a)的構造單元為10至50莫耳%，來源於(b)的構造單元為50至90莫耳%，來源於(x)的構造單元為0.01至3莫耳%。 In the resin [K1], the ratio of the structural units derived from the respective monomers is preferably relative to all the structural units constituting the resin [K1], The construction unit derived from (a) is 5 to 60 mol%, the construction unit derived from (b) is 40 to 98 mol%, and the construction unit derived from (x) is 0.01 to 5 mol%, more preferably The structural unit derived from (a) is 10 to 50 mol%, the structural unit derived from (b) is 50 to 90 mol%, and the structural unit derived from (x) is 0.01 to 3 mol%.

構成樹脂[K1]的構造單元的比率在上述的範圍內時，樹脂圖案形成時的顯影速度高，所得樹脂圖案的機械特性及與水、有機溶劑的接觸角、與基板的密著性優異。 When the ratio of the structural unit constituting the resin [K1] is within the above range, the development speed when the resin pattern is formed is high, and the mechanical characteristics of the obtained resin pattern, the contact angle with water and organic solvents, and the adhesion to the substrate are excellent.

樹脂[K1]，例如，可參考文獻「高分子合成的實驗法」(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)所述的方法及該文獻所述的引用文獻而製造。 Resin [K1], for example, refer to the document "Experimental Methods for Polymer Synthesis" (by Otsu Takayuki, Issuing Office (Stock)), Chemical Associates, First Edition, First Brush, Issued March 1, 1972) Manufactured by the method and the references cited in this document.

具體而言，可舉例將規定量的(a)及(b)、聚合起始劑及溶劑等放入反應容器中，例如，藉由以氮氣取代氧氣而使其成為脫氧氣環境，在攪拌下，加熱及保溫的方法。此外，這裏所用的聚合起始劑及溶劑等無特別的限定，可使用該領域通常使用者。例如，就聚合起始劑而言，可舉例偶氮化合物(2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)等)、有機過氧化物(過氧化苯甲醯等)，就溶劑而言，可溶解各單體的溶劑即可，可列舉後述的用於本發明的光敏性樹脂組成物的溶劑等。 Specifically, for example, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like can be placed in a reaction container. For example, by replacing oxygen with nitrogen to make it a deoxygenated environment, under stirring , Heating and insulation methods. In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and ordinary users in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.), The organic peroxide (such as benzamidine peroxide) may be a solvent capable of dissolving each monomer, and examples thereof include a solvent for the photosensitive resin composition of the present invention described later.

此外，所得的樹脂係可直接使用反應後的溶液，亦可使用經濃縮或稀釋的溶液，亦可使用經再沈殿等的方法而成為固體(粉體)所取出的樹脂。特別是，作為聚合溶劑，藉由使用用 於本發明的光敏性樹脂組成物的溶劑，因可將反應後的溶液直接使用於光敏性樹脂組成物的製造，而可簡化光敏性樹脂組成物的製造步驟。 In addition, the obtained resin can be used directly as a solution after the reaction, a concentrated or diluted solution can also be used, or a resin taken out as a solid (powder) by a method such as re-sinking can be used. In particular, as a polymerization solvent, by using Since the solvent used in the photosensitive resin composition of the present invention can directly use the solution after the reaction for manufacturing the photosensitive resin composition, the manufacturing steps of the photosensitive resin composition can be simplified.

在樹脂[K2]中，來源於各別的構造單元的比率較佳為構成樹脂[K2]的所有構造單元中，來源於(a)的構造單元為2至40莫耳%，來源於(b)的構造單元為2至96莫耳%，來源於(c)的構造單元為1至65莫耳%，來源於(x)的構造單元為0.01至5莫耳%，更佳為來源於(a)的構造單元為5至35莫耳%，來源於(b)的構造單元為5至80莫耳%，來源於(c)的構造單元為1至60莫耳%，來源於(x)的構造單元為0.01至3莫耳%。 In the resin [K2], the ratio derived from the respective structural units is preferably that of all the structural units constituting the resin [K2], the structural unit derived from (a) is 2 to 40 mol% and derived from (b ) From 2 to 96 mol%, from (c) to 1 to 65 mol%, and from (x) to 0.01 to 5 mol%, more preferably from ( The construction unit of a) is 5 to 35 mol%, the construction unit derived from (b) is 5 to 80 mol%, and the construction unit derived from (c) is 1 to 60 mol%, derived from (x) The building blocks are 0.01 to 3 mole%.

樹脂[K2]的構造單元的比率在上述的範圍內時，樹脂圖案形成時的顯影速度高，所得的樹脂圖案的機械特性、與水及有機溶劑的接觸角、與基板的密著性優異。 When the ratio of the structural unit of the resin [K2] is within the above range, the development speed when the resin pattern is formed is high, and the mechanical characteristics of the obtained resin pattern, the contact angle with water and organic solvents, and the adhesion to the substrate are excellent.

樹脂[K2]可與樹脂[K1]同樣的方法製造。 The resin [K2] can be produced in the same manner as the resin [K1].

就構成樹脂[K1]的單體的組合而言，例如，可列舉(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-2)所示的單體、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x3-2)所示的單體、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x3-2)所示的單體、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x4-2)所示的單體、(甲基)丙烯酸/(甲基)丙烯 酸3,4-環氧基環己基甲酯/式(x4-2)所示的單體、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x4-2)表示的單體、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-1)所示的單體、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x3-1)所示的單體、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x3-1)所示的單體等，其中，特佳為(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-2)所示的單體、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-1)所示的單體、以及，(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x4-2)所示的單體。 The combination of monomers constituting the resin [K1] includes, for example, (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1) ] / Monomer represented by formula (x3-2), (meth) acrylic acid / (meth) acrylic 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x3-2), ( (Meth) acrylic acid / glycidyl (meth) acrylate / monomer represented by formula (x3-2), (meth) acrylic acid / [monomer represented by formula (I-1) and / or formula ( II-1) Monomer] / monomer represented by formula (x4-2), (meth) acrylic acid / (meth) propylene Acid 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x4-2), (meth) acrylic acid / glycidyl (meth) acrylate / monomer represented by formula (x4-2) Body, (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x3-1), (a (Meth) acrylic acid / (meth) acrylic acid 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x3-1), (meth) acrylic acid / (meth) acrylic acid propylene oxide / formula The monomer represented by (x3-1) is particularly preferably (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / Monomer represented by formula (x3-2), (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x3 -1) and (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x4-2 ).

就構成樹脂[K2]的單體的組合而言，例如，可列舉(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-2)所示的單體/苯乙烯、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x3-2)所示的單體/苯乙烯、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x3-2)所示的單體/苯乙烯、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x4-2)所示的單體/苯乙烯、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x4-2)所示的單體/苯乙烯、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x4-2)所示的單體/苯乙烯、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-1)所示的單體/苯乙烯、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x3-1)所示的單體/苯乙烯、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x3-1)所示的單體/苯乙烯、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x 3-2)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x3-2)所示的單體/N-環己基馬來醯亞胺、 (甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x3-2)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-1)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧環己基甲酯/式(x3-1)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x3-1)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x4-2)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/(甲基)丙烯酸3,4-環氧基環己基甲酯/式(x4-2)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/(甲基)丙烯酸環氧丙酯/式(x4-2)所示的單體/N-環己基馬來醯亞胺等，其中，特佳為(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-2)所示的單體/N-環己基馬來醯亞胺、(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x3-1)所示的單體/N-環己基馬來醯亞胺、以及，(甲基)丙烯酸/[式(I-1)所示的單體及/或式(II-1)所示的單體]/式(x4-2)所示的單體/N-環己基馬來醯亞胺。 A combination of monomers constituting the resin [K2] includes, for example, (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1) ] / Monomer represented by formula (x3-2) / styrene, (meth) acrylic acid / (meth) acrylic 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x3-2) Body / styrene, (meth) acrylic acid / glycidyl (meth) acrylate / monomer represented by formula (x3-2) / styrene, (meth) acrylic acid / [formula (I-1) Monomer represented by formula and / or monomer represented by formula (II-1)] / monomer represented by formula (x4-2) / styrene, (meth) acrylic acid / (meth) acrylic acid 3,4- Epoxy cyclohexyl methyl ester / monomer represented by formula (x4-2) / styrene, (meth) acrylic acid / glycidyl (meth) acrylate / monomer represented by formula (x4-2) / Styrene, (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x3-1) / Styrene, (meth) acrylic acid / (meth) acrylic 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x3-1) / styrene, (meth) acrylic acid / (methyl ) Glycidyl acrylate / monomer represented by formula (x3-1) / styrene, (meth) acrylic acid / (monomer represented by formula (I-1) And / or monomer represented by formula (II-1)] / monomer represented by formula (x 3-2) / N-cyclohexylmaleimide, (meth) acrylic acid / (meth) acrylic acid 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x3-2) / N-cyclohexylmaleimide, (Meth) acrylic acid / glycidyl (meth) acrylate / monomer represented by formula (x3-2) / N-cyclohexylmaleimide, (meth) acrylic acid / [formula (I-1 ) And / or a monomer represented by the formula (II-1)] / monomer represented by the formula (x3-1) / N-cyclohexylmaleimide, (meth) acrylic acid / (Meth) acrylic acid 3,4-epoxycyclohexyl methyl ester / monomer represented by formula (x3-1) / N-cyclohexylmaleimide, (meth) acrylic acid / (meth) acrylic acid ring Oxypropyl ester / monomer represented by formula (x3-1) / N-cyclohexylmaleimide, (meth) acrylic acid / [monomer represented by formula (I-1) and / or formula (II -1) Monomer] / Monomer represented by formula (x4-2) / N-cyclohexylmaleimide, (meth) acrylic acid / (meth) acrylic 3,4-epoxy group Cyclohexyl methyl ester / monomer represented by formula (x4-2) / N-cyclohexylmaleimide, (meth) acrylic acid / glycidyl (meth) acrylate / formula (x4-2) The monomer / N-cyclohexylmaleimide and the like are particularly preferred, of which (meth) acrylic acid / [monomer represented by formula (I-1) and / or formula (II-1) Monomer] / monomer represented by formula (x3-2) / N-cyclohexylmaleimide, (meth) acrylic acid / [monomer represented by formula (I-1) and / or formula ( II-1) Monomer] / Monomer represented by formula (x3-1) / N-cyclohexylmaleimide and (meth) acrylic acid / [Formula (I-1) Monomer and / or monomer represented by formula (II-1)] / monomer represented by formula (x4-2) / N-cyclohexylmaleimide.

樹脂(A)的聚苯乙烯換算的重量平均分子量較佳為3,000至100,000，更佳為5,000至50,000，再更佳為5,000至20,000。樹脂(A)的重量平均分子量在前述的範圍內時，光敏性樹脂組成物的塗布性有良好的傾向。 The polystyrene equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 20,000. When the weight average molecular weight of the resin (A) is within the aforementioned range, the coatability of the photosensitive resin composition tends to be good.

樹脂(A)的分子量分布[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1至6.0，更佳為1.2至4.0。分子量分佈在前述的範圍內時，樹脂圖案及硬化膜的耐藥品性有優良的傾向。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the aforementioned range, the resin pattern and the cured film tend to have excellent chemical resistance.

樹脂(A)的酸價較佳為30mg-KOH/g以上180mg-KOH/g 以下，更佳為40mg-KOH/g以上150mg-KOH/g以下。於此，酸價是作為中和樹脂1g所需要的氫氧化鉀的量(mg)而測定的值，可由使用氫氧化鉀水溶液滴定而求得。樹脂(A)的酸價在前述的範圍內時，樹脂圖案製作時的顯影性及樹脂圖案、硬化膜與基板的密着性有優異的傾向。 The acid value of the resin (A) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g Hereinafter, it is more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the aforementioned range, the developability at the time of resin pattern production and the adhesion between the resin pattern, the cured film and the substrate tend to be excellent.

樹脂(A)的含有量是相對於本發明的光敏性樹脂組成物的固體成分較佳為30至90質量%，更佳為35至80質量%，再更佳為40至70質量%。樹脂(A)的含有量在前述的範圍內時，樹脂圖案、硬化膜的耐熱性優異，且與基板的密着性及耐藥性有優異的傾向。於此，光敏性樹脂組成物的固體成分是指本發明的光敏性樹脂組成物的總量減去溶劑(E)的含有量的量而言。 The content of the resin (A) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and still more preferably 40 to 70% by mass based on the solid content of the photosensitive resin composition of the present invention. When the content of the resin (A) is within the aforementioned range, the resin pattern and the cured film are excellent in heat resistance, and tend to be excellent in adhesion to a substrate and chemical resistance. Here, the solid content of the photosensitive resin composition means the total amount of the photosensitive resin composition of the present invention minus the content of the solvent (E).

本發明的光敏性樹脂組成物亦可包含與樹脂(A)不同的樹脂。就與樹脂(A)不同的樹脂而言，例如，可列舉：樹脂[K1']：由來源於(a)的構造單元與來源於(b)的構造單元所組成的共聚物；樹脂[K2']：由來源於(a)的構造單元、來源於(b)的構造單元與來源於(c)的構造單元所組成的共聚物；樹脂[K3]：由來源於(a)構造單元與來源於(c)的構造單元所組成的共聚物。 The photosensitive resin composition of the present invention may contain a resin different from the resin (A). Examples of the resin different from the resin (A) include resin [K1 ']: a copolymer composed of a structural unit derived from (a) and a structural unit derived from (b); and resin [K2 ']: A copolymer composed of a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (c); resin [K3]: composed of a structural unit derived from (a) and A copolymer composed of a structural unit derived from (c).

<聚合性化合物(B)> <Polymerizable Compound (B)>

聚合性化合物(B)是藉由聚合起始劑(C)所產生的活性自由基而可聚合的化合物，例如，具有聚合性的乙烯性不飽和鍵的化合物等，較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (B) is a compound that can be polymerized by living radicals generated from the polymerization initiator (C), and for example, a compound having a polymerizable ethylenically unsaturated bond, etc., is preferably (methyl) Acrylate compounds.

就具有1個乙烯性不飽和鍵的聚合性化合物(B)而 言，可列舉與前述(a)，(b)及(c)所列舉的化合物同樣的共聚物，其中，較佳為(甲基)丙烯酸酯類。 For a polymerizable compound (B) having one ethylenically unsaturated bond, In other words, the same copolymers as those exemplified for the compounds (a), (b), and (c) are mentioned, and among them, (meth) acrylates are preferred.

就具有2個乙烯性不飽和鍵的聚合性化合物而言，可列舉二(甲基)丙烯酸1,3-丁烷二醇酯、(甲基)丙烯酸1,3-丁烷二醇酯、二(甲基)丙烯酸1,6-己烷二醇酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸二乙二醇酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸三乙二醇酯、二(甲基)丙烯酸四乙二醇酯、二丙烯酸聚乙二醇酯、雙酚A的雙(丙烯醯氧基乙基)醚、乙氧基化二丙烯酸雙酚A酯、丙氧基化二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸3-甲基戊烷二醇酯等。 Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,6-hexanediol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloxyethyl) ether of bisphenol A, ethoxy Bisphenol A diacrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate Esters, etc.

就具有3個以上的乙烯性不飽和鍵的聚合性化合物而言，可列舉三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸季戊四醇酯、參(2-羥基乙基)異氰脲酸三(甲基)丙烯酸酯、乙氧基化三(甲基)丙烯酸三羥甲基丙烷酯、丙氧基化三(甲基)丙烯酸三羥甲基丙烷酯、四(甲基)丙烯酸季戊四醇酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、四(甲基)丙烯酸三季戊四醇酯、五(甲基)丙烯酸三季戊四醇酯、六(甲基)丙烯酸三季戊四醇酯、七(甲基)丙烯酸三季戊四醇酯、八(甲基)丙烯酸三季戊四醇酯、三(甲基)丙烯酸季戊四醇酯與酸酐的反應物、五(甲基)丙烯酸二季戊四醇酯與酸酐的反應物、七(甲基)丙烯酸三季戊四醇酯與酸酐的反應物、己內酯改質三(甲基)丙烯酸三羥甲基丙烷酯、己內酯改質三(甲基)丙烯酸季戊四醇酯、己內酯改質三(2-羥基乙基)異氰脲酸酯三(甲基)丙烯酸酯、己內酯改質四(甲基)丙烯酸季戊四醇酯、己內酯改質五(甲基)丙烯酸二季戊四醇酯、己內酯改質六(甲基)丙烯酸 二季戊四醇酯、己內酯改質四(甲基)丙烯酸三季戊四醇酯、己內酯改質五(甲基)丙烯酸三季戊四醇酯、己內酯改質六(甲基)丙烯酸三季戊四醇酯、己內酯改質七(甲基)丙烯酸三季戊四醇酯、己內酯改質八(甲基)丙烯酸三季戊四醇酯、己內酯改質三(甲基)丙烯酸季戊四醇酯與酸酐的反應物、己內酯改質五(甲基)丙烯酸二季戊四醇酯與酸酐的反應物、己內酯改質七(甲基)丙烯酸三季戊四醇酯與酸酐的反應物。 Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and ginseng (2-hydroxyethyl). Isocyanuric acid tri (meth) acrylate, ethoxylated tri (meth) acrylate trimethylolpropane, propoxylated trimethylol propane, tetra (methyl) ) Pentaerythritol acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, hexa (methyl) Tripentaerythritol acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reactant of pentaerythritol tri (meth) acrylate and anhydride, dipentaerythritol penta (meth) acrylate and anhydride Reactants, reactants of tripentaerythritol hepta (meth) acrylate and anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate Tricaprolactone modified tris (2-hydroxyethyl) isocyanuric acid Tri (meth) acrylate, caprolactone-modified tetra (meth) acrylate, pentaerythritol, caprolactone-modified penta (meth) acrylate, dipentaerythritol, caprolactone-modified hexa (meth) acrylate, Dipentaerythritol ester, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythritol hexa (meth) acrylate, caprolactone Lactone modified tripentaerythritol hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified reactant of pentaerythritol tri (meth) acrylate and anhydride, caprolactone Ester modification reacts with dipentaerythritol penta (meth) acrylate and anhydride, and caprolactone modifies reactants with tripentaerythritol hepta (meth) acrylate and anhydride.

其中，較佳為具有3個以上的乙烯性不飽和鍵的聚合性化合物，更佳為六(甲基)丙烯酸二季戊四醇酯。 Among these, a polymerizable compound having three or more ethylenically unsaturated bonds is preferred, and dipentaerythritol hexa (meth) acrylate is more preferred.

又，聚合性化合物(C)的重量平均分子量較佳為150以上2,900以下，更佳為250至1,500以下。 The weight-average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, and more preferably from 250 to 1,500.

聚合性化合物(B)的含有量是相對於樹脂(A)及聚合性化合物(B)的總計量，較佳為5至95質量%，更佳為20至80質量%。聚合性化合物(B)的含有量在前述的範圍內時，樹脂圖案製作時的敏感度、所得的樹脂圖案、硬化膜的強度、平滑性及信頼性有良好的傾向。 The content of the polymerizable compound (B) is preferably 5 to 95% by mass, and more preferably 20 to 80% by mass based on the total amount of the resin (A) and the polymerizable compound (B). When the content of the polymerizable compound (B) is within the above range, the sensitivity at the time of resin pattern production, the obtained resin pattern, the strength, smoothness, and reliability of the cured film tend to be good.

<聚合起始劑(C)> <Polymerization initiator (C)>

聚合起始劑(C)只要是經由光或熱的作用產生活性自由基，酸等而能開始聚合的化合物便無特別的限定，可使用公知的聚合起始劑。 The polymerization initiator (C) is not particularly limited as long as it is a compound that can generate active radicals through the action of light or heat, such as an acid, and can start polymerization, and a known polymerization initiator can be used.

就聚合起始劑(C)而言，例如，可列舉苯烷基酮(alkylphenone)化合物、三化合物、醯基氧化膦(acylphosphine oxide)化合物、O-醯基肟(O-acyloxime)化合物及雙咪唑(biimidazole)化合物。 The polymerization initiator (C) includes, for example, an alkylphenone compound, Compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

前述O-醯基肟化合物是具有式(d1)所示的部分構造的化合物。以下，*表示鍵合鍵。 The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * indicates a bonding bond.

就前述O-醯基肟化合物而言，例如，可列舉N-苄醯基氧基-1-(4-苯基巰基苯基)丁烷-1-酮-2-亞胺、N-苄醯基氧基-1-(4-苯基巰基苯基)辛烷-1-酮-2-亞胺、N-苄醯基氧基-1-(4-苯基巰基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲基氧基)苄醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苄醯氧基-1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。亦可使用IRGACURE(登錄商標)OXE 01、OXE 02(以上，BASF公司製)、N-1919(ADEKA公司製)等的市售品。 Examples of the O-fluorenyl oxime compound include N-benzylfluorenyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzylhydrazone. Phenyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzylfluorenyloxy-1- (4-phenylmercaptophenyl) -3-ring Amylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] ethyl Alkane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolane Methylmethyloxy) benzylfluorenyl} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxymethyl-1- [9-ethyl-6- (2-methyl Benzylfluorenyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzylfluorenyloxy-1- [9-ethyl-6- (2-methylbenzyl Fluorenyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as IRGACURE (registered trademark) OXE 01, OXE 02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used.

前述苯烷基酮化合物是具有式(d2)所示的部分構造或式(d3)所示的部分構造的化合物。這些部分構造中，苯環可以具有取代基。 The phenanthone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

就具有式(d2)所示的部分構造的化合物而言，例如，可列舉2-甲基-2-嗎啉基-1-(4-甲基巰基苯基)丙烷-1-酮、2-甲基 胺基-1-(4-嗎啉基苯基)-2-苄基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮等。亦可使用IRGACURE(登錄商標)369、907及379(以上，BASF公司製)等的市售品。又，亦可使用日本特表第2002-544205號公報所述的具有可引起鏈轉移(chain transfer)的基的聚合起始劑。 Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholinyl-1- (4-methylmercaptophenyl) propane-1-one, 2-methyl methyl Amino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercial products such as IRGACURE (registered trademark) 369, 907, and 379 (above, manufactured by BASF) can also be used. In addition, a polymerization initiator having a group capable of causing chain transfer as described in Japanese Patent Application Publication No. 2002-544205 can also be used.

就具有式(d3)表示的部分構造的化合物而言，例如，可列舉2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基-]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙基苯基)丙烷-1-酮的寡聚物、α,α-二乙氧基-苯乙酮、苄基二甲基縮酮等。 Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl-] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propane Oligomers of 1-one, α, α-diethoxy-acetophenone, benzyldimethylketal and the like.

在敏感度的點，就苯烷基酮化合物而言，較佳為具有式(d2)所示的部分構造的化合物。 From the point of sensitivity, a compound having a partial structure represented by the formula (d2) is preferred as the benzoalkyl ketone compound.

就前述三化合物而言，例如，可列舉2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基(piperonyl)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。 Just three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

就前述醯基氧化膦而言，可列舉2,4,6-三甲基苄醯基二苯基氧化膦等。亦可使用IRGACURE(登錄商標)819(BASF公司製)等的市售品。 Examples of the fluorenylphosphine oxide include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercially available products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can also be used.

就前述雙咪唑化合物而言，例如，可列舉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，參照JPH06-75372-A、JPH06-75373-A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(三烷氧苯基)雙咪唑(例如，參照JPS48-38403-B、JPS62-174204-A等。)、4,4',5,5'-位的苯基經羰基烷氧基(carboalkoxy)所取代的咪唑化合物(例如，參照JPH07-10913-A等)等。 Examples of the bisimidazole compound include 2,2-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetrabenzene Bisimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2, '-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl Bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (alkoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) ) -4,4 ', 5,5'-tetra (dialkoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( Trialkoxyphenyl) bisimidazole (see, for example, JPS48-38403-B, JPS62-174204-A, etc.), 4,4 ', 5,5'-phenyl group through carboalkoxy Substituted imidazole compounds (for example, refer to JPH07-10913-A, etc.) and the like.

再者，就聚合起始劑而言，可列舉安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚等的安息香化合物；二苯基酮、鄰-苄醯基安息香酸甲酯、4-苯基二苯基酮、4-苄醯基-4'-甲基二苯基硫化物、3,3',4,4'-四(第三丁基過氧化羰基)二苯基酮、2,4,6-三甲基二苯基酮等的二苯基酮化合物；9,10-菲醌、2-乙基蒽醌、樟腦醌等的醌化合物；10-丁基-2-氯吖啶酮、苄基、苯基乙醛酸甲酯、二茂鈦(titanocene)化合物等。較佳為將此等聚合起始劑與後述的聚合起始助劑(C1)(特別是胺類)組合使用。 Examples of the polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone and o-benzidine Methyl benzoate, 4-phenyldiphenyl ketone, 4-benzylfluorenyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetrakis (third butyl peroxide (Carbonyl) diphenyl ketone compounds such as diphenyl ketone, 2,4,6-trimethyldiphenyl ketone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10 -Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, and the like. These polymerization initiators are preferably used in combination with a polymerization initiation aid (C1) (particularly, amines) described later.

就酸產生劑而言，例如，可列舉對-甲苯磺酸4-羥基苯基二甲基鋶、六氟銻酸4-羥基苯基二甲基鋶、對-甲苯磺酸4-乙醯氧基苯基二甲基鋶、六氟銻酸4-乙醯氧基苯基‧甲基‧苄基鋶、對-甲苯磺酸三苯基鋶、六氟銻酸三苯基鋶、對-甲苯磺酸二苯基錪鎓、六氟銻酸二苯基錪鎓等的鎓鹽類、甲苯磺醯酸硝基苄酯類、甲苯磺醯酸安息香酯類等。 Examples of the acid generator include p-toluenesulfonic acid 4-hydroxyphenyldimethylsulfonium, hexafluoroantimonic acid 4-hydroxyphenyldimethylfluorene, and p-toluenesulfonic acid 4-acetamidine Phenylphenyldimethylfluorene, hexafluoroantimonic acid 4-ethoxyphenylphenyl, methyl, benzylfluorene, triphenylphosphonium p-toluenesulfonate, triphenylphosphonium hexafluoroantimonate, p-toluene Onium salts such as diphenylphosphonium sulfonate, diphenylphosphonium hexafluoroantimonate, nitrobenzyl tosylate, benzoyl tosylate, and the like.

就聚合起始劑(C)而言，較佳為包含至少1種選自由 苯烷基酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及雙咪唑化合物所成群組的聚合起始劑，更佳為包含雙咪唑化合物的聚合起始劑。如是這些聚合起始劑，則有高敏感度，且在可視光領域種的透過率變高的傾向。 The polymerization initiator (C) preferably contains at least one selected from the group consisting of A polymerization initiator comprising a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a bisimidazole compound is more preferably a polymerization initiator containing a bisimidazole compound. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light field.

聚合起始劑(C)的含有量是相對於樹脂(A)與聚合性化合物(B)的合計含有量100質量份，較佳為0.1至30質量份，更佳為0.5至15質量份，再更佳為1至8質量份。聚合起始劑(C)的含有量在前述範圍內時，高敏感度化且曝光時間有縮短的傾向，因而提高生產性，復有所得的樹脂圖案的可視光透過率高的傾向。 The content of the polymerization initiator (C) is 100 parts by mass with respect to the total content of the resin (A) and the polymerizable compound (B), preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass, Still more preferably, it is 1 to 8 parts by mass. When the content of the polymerization initiator (C) is within the above range, the sensitivity is increased and the exposure time tends to be shortened. Therefore, productivity is improved, and the visible light transmittance of the obtained resin pattern tends to be high.

<聚合起始助劑(C1)> <Polymerization starter (C1)>

聚合起始助劑(C1)是與聚合起始劑(C)一起使用，為了促進因聚合起始劑(C)開始之化合物(例如，聚合性化合物(B))的聚合而使用的化合物，或者是增感劑。 The polymerization initiator (C1) is a compound used together with the polymerization initiator (C) to promote the polymerization of a compound (for example, a polymerizable compound (B)) started by the polymerization initiator (C), Or a sensitizer.

就聚合起始助劑(C1)而言，例如，可列舉噻唑啉化合物、胺化合物、烷氧基蒽化合物、噻吨酮(thioxanthone)化合物及羧酸化合物。 Examples of the polymerization initiation aid (C1) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

就前述噻唑啉化合物而言，可列舉式(III-1)至式(III-3)所示的化合物、JP2008-65319-A所述的化合物等。 Examples of the thiazoline compound include compounds represented by formulae (III-1) to (III-3), compounds described in JP2008-65319-A, and the like.

就前述胺化合物而言，可列舉三乙醇胺、甲基二乙醇胺、三異丙醇胺、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、安息香酸2-二甲基胺基乙酯、4-二甲基胺基安息香酸2-乙基己酯、N,N-二甲基對甲苯胺(paratoluidine)、4,4'-雙(二甲基胺基)二苯基酮(通稱米希勒氏酮(Michler's ketone)、4,4'-雙(二乙基胺基)二苯基酮、4,4'-雙(乙基甲基胺基)二苯基酮等，其中，較佳為4,4'-雙(二乙基胺基)二苯基酮。亦可使用EAB-F(保土谷化學工業股份有限公司製)等的市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-diamine Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine ), 4,4'-bis (dimethylamino) diphenyl ketone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) diphenyl ketone, 4 , 4'-bis (ethylmethylamino) diphenyl ketone, etc. Among them, 4,4'-bis (diethylamino) diphenyl ketone is preferred. EAB-F (Manufactured by Tsuchiya Chemical Industry Co., Ltd.).

就前述烷氧基蒽化合物而言，可列舉9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl Group-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

就前述噻吨酮化合物而言，可列舉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、1-氯-4-丙氧基噻吨酮等。 Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

就前述羧酸化合物而言，可列舉苯基巰基乙酸、 甲基苯基巰基乙酸、乙基苯基巰基乙酸、甲基乙基苯基巰基乙酸、二甲基苯基巰基乙酸、甲氧基苯基巰基乙酸、二甲氧基苯基巰基乙酸、氯苯基巰基乙酸、二氯苯基巰基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫乙酸、N-萘基甘胺酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylmercaptoacetic acid, Methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioglycolic acid, methoxyphenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorobenzene Thioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthyloxyacetic acid, and the like.

本發明的光敏性樹脂組成物包含聚合起始助劑(C1)時，其含有量是相對於樹脂(A)與聚合性化合物(B)的合計含有量100質量份，較佳為0.1至30質量份，更佳為0.2至10質量份。聚合起始助劑(C1)的量在前述的範圍內時，在形成樹脂圖案時，復有高敏感度的傾向。 When the photosensitive resin composition of the present invention contains a polymerization initiation aid (C1), its content is 100 parts by mass based on the total content of the resin (A) and the polymerizable compound (B), and preferably from 0.1 to 30 Part by mass, more preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiation aid (C1) is within the aforementioned range, the resin pattern tends to have a high sensitivity when the resin pattern is formed.

<硫醇化合物(T)> <Thiol compound (T)>

硫醇化合物(T)是分子內具有巰基(-SH)的化合物。 The thiol compound (T) is a compound having a mercapto group (-SH) in the molecule.

其中，較佳為具有2個以上的巰基的化合物，更佳為具有2個以上與脂肪族烴構造之碳原子鍵結的巰基的化合物。較佳為硫醇化合物(T)與聚合起始劑(D)一起使用。 Among them, a compound having two or more mercapto groups is preferred, and a compound having two or more mercapto groups bonded to a carbon atom of an aliphatic hydrocarbon structure is more preferred. The thiol compound (T) is preferably used together with the polymerization initiator (D).

就硫醇化合物(T)而言，例如，可列舉己烷二硫醇、癸烷二硫醇、1,4-雙(甲基巰基)苯、丁烷二醇雙(3-巰基丙酸酯)、丁烷二醇雙(3-巰基乙酸酯)，乙二醇雙(3-巰基乙酸酯)、三羥甲基丙烷參(3-巰基乙酸酯)、丁烷二醇雙(3-巰基丙酸酯)、三羥甲基丙烷參(3-巰基丙酸酯)、三羥甲基丙烷參(3-巰基乙酸酯)、肆(3-巰基丙酸)季戊四醇酯、肆(3-巰基乙酸)季戊四醇酯、參羥基乙基參(3-巰基丙酸酯)、肆(3-巰基丁酸)季戊四醇酯、1,4-雙(3-巰基丁氧基)丁烷等。 Examples of the thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylmercapto) benzene, and butanediol bis (3-mercaptopropionate). ), Butanediol bis (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane ginseng (3-mercaptoacetate), butanediol bis ( (3-mercaptopropionate), trimethylolpropane (3-mercaptopropionate), trimethylolpropane (3-mercaptoacetate), (3-mercaptopropionic acid) pentaerythritol ester, (3-Mercaptoacetic acid) pentaerythritol ester, p-hydroxyethyl ginseng (3-mercaptopropionate), (3-mercaptobutyric acid) pentaerythritol ester, 1,4-bis (3-mercaptobutoxy) butane, etc. .

本發明的光敏性樹脂組合物包含硫醇化合物(T) 時，其含有量是相對於聚合起始劑(C)的含有量100質量份，較佳為10至90質量份，更佳為15至70質量份。硫醇化合物(T)的含有量在前述的範圍內時，敏感度變高，又顯影性有良好的傾向。 The photosensitive resin composition of the present invention contains a thiol compound (T) In this case, the content is 100 parts by mass with respect to the content of the polymerization initiator (C), preferably 10 to 90 parts by mass, and more preferably 15 to 70 parts by mass. When the content of the thiol compound (T) is within the aforementioned range, the sensitivity becomes high and the developability tends to be good.

<抗氧化劑(F)> <Antioxidant (F)>

就抗氧化劑(F)而言，例如，可列舉酚系抗氧化劑、硫系抗氧化劑、磷系抗氧化劑及胺系抗氧化劑。其中，尤在硬化膜的著色少之點，較佳為酚系抗氧化劑。 Examples of the antioxidant (F) include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among them, a phenol-based antioxidant is particularly preferred because the color of the cured film is small.

就酚系抗氧化劑而言，例如，可列舉2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二第三戊基苯基)乙基]-4,6-二第三戊基苯基丙烯酸酯、3,9-雙[2-{3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基}-1,1-二甲基乙基]-2,4,8,10-四雜氧螺[5,5]十一烷、2,2’-亞甲基雙(6-第三丁基-4-甲基酚)、4,4’-亞丁基雙(6-第三丁基-3-甲基酚)、4,4-硫雙(2-第三丁基-5-甲基酚)、2,2-硫雙(6-第三丁基-4-甲基酚)、1,3,5-參(3,5-二第三丁基-4-羥基苄基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮、3,3’,3”,5,5’,5”-六第三丁基-a,a’,a”-(均三甲苯-2,4,6-三基)三-對-甲酚(cresol)、肆[3-(3,5-二第三丁基-4-羥基苯基)丙酸]季戊四醇、2,6-二第三丁基-4-甲基酚、6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四第三丁基苯并[d,f][1,3,2]二磷環庚烷(dioxaphosphepine)等。 Examples of the phenol-based antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-third-pentylphenyl) ethyl] -4,6-di-third-pentylphenyl acrylate, 3,9-bis [2- {3 -(3-Third-butyl-4-hydroxy-5-methylphenyl) propoxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 , 5] undecane, 2,2'-methylenebis (6-thirdbutyl-4-methylphenol), 4,4'-butylenebis (6-thirdbutyl-3-methyl Phenol), 4,4-thiobis (2-third butyl-5-methylphenol), 2,2-thiobis (6-third butyl-4-methylphenol), 1,3, 5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-tri -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-third-butyl-a, a ', a "-(Junior Toluene-2,4,6-triyl) tri-p-cresol, cresol [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol, 2,6 -Di-tert-butyl-4-methylphenol, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Tetra-tert-butylbenzo [d, f] [1,3,2] di Dicyclophosphepine and the like.

就前述酚系抗氧化劑而言，亦可使用市售品。就市售的酚系抗氧化劑而言，例如，可列舉SUMILIZER(登錄商標)BHT、GM、GS、GP(以上均為住友化學股份有限公司製)、IRGANOX(登錄商標)1010、1076、1330、3114(以上均為BASF公 司製)等。 As the phenol-based antioxidant, a commercially available product may be used. Examples of commercially available phenolic antioxidants include SUMILIZER (registered trademark) BHT, GM, GS, GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1076, 1330, 3114 (The above are all BASF Secretary) and so on.

就硫系抗氧化劑而言，例如，可列舉3,3’-硫二丙酸二月桂酯、3,3’-硫二丙酸二肉豆蔻酯、3,3’-硫二丙酸二硬脂酯、四(3-月桂基硫丙酸)季戊四醇酯等。就前述硫系抗氧化劑而言，亦可使用市售品。就市售品的硫系抗氧化劑而言，例如，可列舉SUMILIZER(登錄商標)TPL-R、TP-D(以上，均為住友化學股份有限公司製)等。 Examples of the sulfur-based antioxidant include dilauryl 3,3'-dithiopropionate, dimyristyl 3,3'-dithiopropionate, and dihard 3,3'-dithiopropionate Fatty esters, tetrakis (3-laurylthiopropionic acid) pentaerythritol esters, and the like. The sulfur-based antioxidant may be a commercially available product. Commercially available sulfur-based antioxidants include, for example, SUMILIZER (registered trademark) TPL-R, TP-D (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

就磷系抗氧化劑而言，例如，可列舉亞鄰酸三辛酯、亞鄰酸三月桂酯、亞鄰酸十三烷酯、亞鄰酸參(壬基苯酯)、二亞磷酸二硬脂基季戊四醇酯、二亞鄰酸四(十三烷基)-1,1,3-參(2-甲基-5-第三丁基-4-羥基苯基)丁烷酯等。就前述磷系抗氧化劑而言，亦可使用市售品。就市售品的磷系抗氧化劑而言，例如，可列舉IRGAFOS(登錄商標)168、12、38(以上均為BASF公司製)、ADEKA STAB 329K、ADEKA STAB PEP36(以上均為ADEKA製)等。 Examples of the phosphorus-based antioxidant include trioctyl phthalate, trilauryl phthalate, tridecyl phthalate, ginsenolate (nonylphenyl), and diphosphite Aliphatic pentaerythritol ester, tetrakis (tridecyl) -1,1,3-ginsenoate (2-methyl-5-third butyl-4-hydroxyphenyl) butane ester, and the like. As the phosphorus-based antioxidant, a commercially available product may be used. Examples of commercially available phosphorus-based antioxidants include IRGAFOS (registered trademark) 168, 12, 38 (all of which are manufactured by BASF), ADEKA STAB 329K, ADEKA STAB PEP36 (all of which are manufactured by ADEKA), etc. .

就胺系抗氧化劑而言，例如，可列舉N,N’-二-第二丁基-對-苯二胺、N,N’-二異丙基-對-苯二胺、N,N’-二環己基-對-苯二胺、N,N’-二苯基-對-苯二胺、N,N’-雙(2-萘基)-對-苯二胺等。就前述胺系抗氧化劑而言，亦可使用市售品。就市售品的胺系抗氧化劑而言，例如，可列舉SUMILYER(登録商標)BPA、BPA-M1、4ML(以上均為住友化學股份有限公司製)等。 Examples of the amine-based antioxidant include N, N'-di-second-butyl-p-phenylenediamine, N, N'-diisopropyl-p-phenylenediamine, and N, N ' -Dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, and the like. As the amine-based antioxidant, a commercially available product may be used. Examples of commercially available amine antioxidants include SUMILYER (registered trademark) BPA, BPA-M1, 4ML (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

本發明的硬化性樹脂組成物包含抗氧化劑(F)時，其含有量是相對於樹脂(A)與聚合性化合物(B)的合計含有量100質量份，較佳為0.1質量份以上5質量份以下，更佳為0.5質量份以上3質量份以下。抗氧化劑(F)的含有量在前述的範圍內時，樹脂 圖案、硬化膜的耐熱性及鉛筆硬度有優異的傾向。 When the curable resin composition of the present invention contains an antioxidant (F), its content is 100 parts by mass relative to the total content of the resin (A) and the polymerizable compound (B), and preferably 0.1 part by mass or more and 5 parts by mass It is preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the aforementioned range, the resin Patterns and cured films tend to have excellent heat resistance and pencil hardness.

<界面活性劑(H)> <Surfactant (H)>

就界面活性劑(H)而言，例如，可列舉矽氧樹脂系界面活性劑、氟系界面活性劑、具有氟原子的矽氧樹脂系界面活性劑等。 Examples of the surfactant (H) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom.

就矽氧樹脂系界面活性劑而言，可列舉具有矽氧烷鍵的界面活性劑等。具體而言，可列舉TORAY SILICONE(商品名)DC3PA、TORAY SILICONE SH7PA、TORAY SILICONE DC11PA、TORAY SILICONE SH21PA、TORAY SILICONE SH28PA、TORAY SILICONE SH29PA、TORAY SILICONE SH30PA、TORAY SILICONE SH8400(東麗‧道康寧股份有限公司製)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452、TSF4460(MOMENTIVE PERFORMANCE JAPAN聯合公司製)等。 Examples of the siloxane resin-based surfactant include a surfactant having a siloxane bond. Specifically, TORAY SILICONE (brand name) DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (manufactured by Toray Dow Corning Corporation) ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by PERFORMANCE JAPAN) Wait.

就前述的氟系界面活性劑而言，可列舉具有氟碳鏈的界面活性劑等。具體而言，可列舉FLUORAD(登錄商標)FC430、FLUORAD FC431(住友3M股份有限公司製)、MEGAFAC(登錄商標)F142D、MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F177、MEGAFAC F183、MEGAFAC F554、MEGAFAC R30、MEGAFAC RS-718-K(DIC股份有限公司製)、EFTOP(登錄商標)EF301、EFTOP EF303、EFTOP EF351、EFTOP EF352(三菱材料電子化成股份有限公司製)、SURFRON(登錄商標)S381、SURFRON S382、SURFRON SC101、SURFRON SC105(旭玻璃股份有限公司 製)、E5844(DAIKIN FINE CHEMICAL研究所股份有限公司製)等。 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (made by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), SURFRON (registered trademark) S381, SURFRON S382, SURFRON SC101, SURFRON SC105 (Asahi Glass Co., Ltd. System), E5844 (made by Daikin Fine Chemical Research Co., Ltd.), etc.

就前述的聚有氟原子的矽氧樹脂系界面活性劑而言，可列舉具有矽氧烷鍵及氟碳鏈的界面活性劑等。具體而言，可列舉MEGAFAC(登錄商標)R08、MEGAFAC BL20、MEGAFAC F475、MEGAFAC F477、MEGAFAC F443(DIC股份有限公司製)等。 Examples of the polysiloxane-containing silicone-based surfactant include surfactants having a siloxane bond and a fluorocarbon chain. Specific examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC Corporation), and the like.

本發明的光敏性樹脂組成物包含界面活性劑(H)時，其含有量是相對於本發明的光敏性樹脂組成物的總量，係0.001質量%以上0.2質量%以下，較佳為0.002質量%以上0.1質量%以下，更佳為0.01質量%以上0.05質量%以下。界面活性劑(H)的含有量在前述的範圍內時，由於可提升組成物層的平坦性，因而有樹脂圖案中的高度不均勻變小，且硬化膜中的平坦性變高的傾向。 When the photosensitive resin composition of the present invention contains a surfactant (H), its content is 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass relative to the total amount of the photosensitive resin composition of the present invention. % To 0.1% by mass, more preferably 0.01 to 0.05% by mass. When the content of the surfactant (H) is within the aforementioned range, the flatness of the composition layer can be improved, and therefore, height unevenness in the resin pattern tends to be small, and flatness in the cured film tends to be high.

<溶劑(E)> <Solvent (E)>

溶劑(E)無特別的限定，可使用在該領域通常使用的溶劑。例如，可使用選自酯類溶劑(分子內包含-COO-，不含-O-的溶劑)、醚類溶劑(分子內包含-O-，不含-COO-的溶劑)、醚酯類溶劑(分子內包含-COO-與-O-的溶劑)、酮類溶劑(分子內包含-CO-，不含-COO-的溶劑)、醇類溶劑(分子內包含OH，不含-O-、-CO-及-COO-的溶劑)、芳香族烴類溶劑、醯胺類溶劑、二甲基亞碸等中之溶劑。 The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. For example, an ester solvent (a solvent containing -COO- and -O-free) in the molecule, an ether solvent (a solvent containing -O- and -COO-free in the molecule), and an ether ester solvent can be used. (Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and -COO-free in the molecule), alcohol solvents (containing OH in the molecule, -O- free, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amine-based solvents, dimethyl sulfene and the like.

就酯類溶劑而言，可列舉乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁烷酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯，丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙 酸甲酯、乙醯乙酸乙酯、乙酸環己醇酯、γ-丁內酯等。 Examples of the ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and acetic acid. Isoamyl, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethyl acetate Methyl ester, ethyl acetate, cyclohexanol acetate, γ-butyrolactone and the like.

就醚類溶劑而言，可列舉乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單丁基醚、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、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、苯基甲基醚(anisole)、乙基苯基醚(phenetole)、甲基苯基甲基醚(methyl anisole)等。 Examples of the ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butane Alcohol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-bis Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, phenyl Methyl ether (anisole), ethylphenyl ether (phenetole), methylphenylanisole (methyl anisole) and the like.

就醚酯類溶劑而言，可列舉甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、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-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、-乙氧基-2-甲基丙酸乙酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯等。 Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, -Ethyl ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate and the like.

就酮溶劑而言，可列舉4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛酮(isophorone)等。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl- 2-pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

就醇類溶劑而言，可列舉甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、甘油等。 Examples of the alcohol-based solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

就芳香旋烴溶劑而言，可列舉苯、甲苯、二甲苯、均三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

就醯胺溶劑而言，可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺，N-甲基吡咯酮等。 Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

上述的溶劑中，在塗佈性、乾燥性的點，較佳為在1 atm下的沸點在120℃以上180℃以下的有機溶劑。其中，就該有機溶劑而言，丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、二乙二醇甲基乙基醚、乙酸3-甲氧基丁酯及3-甲氧基-1-丁醇。溶劑(E)較佳為與包有這些溶劑的混合溶劑。 Among the solvents described above, in terms of coatability and drying properties, an organic solvent having a boiling point of 1 ° C. or higher and 180 ° C. or lower at 1 atm is preferred. Among these organic solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, and 3-methoxy-1 -Butanol. The solvent (E) is preferably a mixed solvent containing these solvents.

溶劑(E)的含有量是相對於本發明的光敏性樹脂組成物的總量較佳為60至95質量%，更佳為70至95質量%。換言之，本發明的光敏性樹脂組成物的固體成分較佳為5至40質量%，更佳為5至30質量%。溶劑(E)的含有量在前述的範圍內時，由於本發明的光敏性樹脂組成物所形成的組成物層的平坦性有高的傾向，因而樹脂圖案高度不均勻變小，且硬化膜有平坦性變高的傾向。 The content of the solvent (E) is preferably 60 to 95% by mass, and more preferably 70 to 95% by mass based on the total amount of the photosensitive resin composition of the present invention. In other words, the solid content of the photosensitive resin composition of the present invention is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. When the content of the solvent (E) is within the aforementioned range, the flatness of the composition layer formed of the photosensitive resin composition of the present invention tends to be high, so that the unevenness of the height of the resin pattern becomes small, and the cured film has The flatness tends to be high.

<其他的成分> <Other ingredients>

本發明的光敏性樹脂組成物中，有必要時，也可以含有填充劑、其他的高分子化合物、熱自由基產生劑、紫外線吸收劑、鏈轉移劑、黏著促進劑等的在該技術領域公知的添加劑。 The photosensitive resin composition of the present invention may contain fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, and the like, if necessary. Additives.

就填充劑而言，可列舉玻璃、氧化矽、氧化鋁等。 Examples of the filler include glass, silica, and alumina.

就其他的高分子化合物而言，可列舉馬來醯亞胺樹脂等的熱固性樹脂、聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、丙烯酸聚氟烷基酯、聚酯、聚胺基甲酸酯等的熱塑性樹脂等。 Examples of other polymer compounds include thermosetting resins such as maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyamine. Thermoplastic resins such as urethane.

就熱自由基產生劑具體而言，可列舉2,2'-偶氮雙(2-甲基戊腈)(valeronitrile)、2,2'-偶氮雙(2,4-二甲基戊腈)等。 Specific examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile) (valeronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). )Wait.

就紫外線吸收劑具體而言，可列舉2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并***、烷氧基二苯基酮等。 Specific examples of the ultraviolet absorber include 2- (3-thirdbutyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, and alkoxydiphenyl ketone.

就鏈轉移劑而言，可列舉十二烷硫醇、2,4-二苯基-4-甲基-1-戊烯等。 Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene, and the like.

就黏著促進劑而言，例如，可列舉乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯參(2-甲氧基乙氧基)矽烷、3-環氧丙基氧基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、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、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、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-胺基丙基甲基二乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷等。 Examples of the adhesion promoter include ethylene trimethoxysilane, ethylene triethoxysilane, ethylene ginseng (2-methoxyethoxy) silane, and 3-glycidyloxytrimethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropene Methoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- (aminoethylethyl ) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl ) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane Alkanes, etc.

本發明的光敏性樹脂組成物實質上不含顏料及染料等的著色劑。即，在本發明的光敏性樹脂組成物中，相對於組成物全體的著色劑的含量是，例如，未達1質量%，較佳為未達0.5質量%。 The photosensitive resin composition of the present invention contains substantially no coloring agents such as pigments and dyes. That is, the content of the coloring agent in the photosensitive resin composition of the present invention is, for example, less than 1% by mass, and preferably less than 0.5% by mass.

又，將本發明的光敏性樹脂組成物填充於光徑長 1cm的石英槽，並使用分光光度計，在測定波長400至700nm的條件下測定透光率時，平均透光率較佳為70%以上，更佳為80%以上。 Further, the photosensitive resin composition of the present invention is filled in a long optical path. When the light transmittance is measured at a measurement wavelength of 400 to 700 nm using a 1 cm quartz cell and a spectrophotometer, the average light transmittance is preferably 70% or more, and more preferably 80% or more.

本發明的光敏性樹脂組成物成為硬化膜時，硬化膜的平均透光率較佳為90%以上，更佳為95%以上。這個平均透光率是相對於加熱硬化(例如，100至250℃，5分鐘至3小時)後的厚度為2μm的硬化膜，使用分光光度計，在測定波長400至700nm的條件下測定時的平均值。藉此，可提供在可視光領域的透明性優異的樹脂圖案、硬化膜。 When the photosensitive resin composition of the present invention is a cured film, the average light transmittance of the cured film is preferably 90% or more, and more preferably 95% or more. This average light transmittance is measured relative to a cured film with a thickness of 2 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours) using a spectrophotometer at a measurement wavelength of 400 to 700 nm average value. This makes it possible to provide a resin pattern and a cured film excellent in transparency in the visible light field.

<光敏性樹脂組成物的製造方法> <Manufacturing method of photosensitive resin composition>

本發明的光敏性樹脂組成物可將樹脂、聚合性化合物(B)及聚合起始劑(C)，以及，有必要時使用的溶劑(E)、界面活性劑(H)及其他的成分，以公知的方法混合而製造。混合後，較佳為以孔徑0.05至1.0 μm左右的過濾器過濾。 The photosensitive resin composition of the present invention may include a resin, a polymerizable compound (B) and a polymerization initiator (C), and a solvent (E), a surfactant (H), and other components, if necessary, It is produced by mixing by a known method. After mixing, it is preferably filtered with a filter having a pore size of about 0.05 to 1.0 μm.

<樹脂圖案的製造方法> <Manufacturing method of resin pattern>

由本發明的光敏性樹脂組成物形成的樹脂圖案，例如，可進行下述的步驟(1)至(4)而製造。較佳為步驟(4)後再進行步驟(5)。 The resin pattern formed from the photosensitive resin composition of the present invention can be produced, for example, by performing the following steps (1) to (4). It is preferable to perform step (5) after step (4).

步驟(1)：將本發明的光敏性樹脂組成物塗佈在基板上的步驟；步驟(2)：使塗佈後的光敏性樹脂組成物乾燥，形成組成物層的步驟；步驟(3)：將組成物層透過光罩而曝光的步驟；步驟(4)：將曝光後的組成物層顯影的步驟； 步驟(5)：將顯影後的組成物層加熱的步驟。 Step (1): a step of coating the photosensitive resin composition of the present invention on a substrate; step (2): a step of drying the coated photosensitive resin composition to form a composition layer; step (3) : A step of exposing the composition layer through a photomask; step (4): a step of developing the exposed composition layer; Step (5): a step of heating the developed composition layer.

步驟(1)是將本發明的光敏性樹脂組成物塗佈在基板上的步驟。 Step (1) is a step of applying the photosensitive resin composition of the present invention on a substrate.

就基板而言，可列舉玻璃、金屬、塑膠等，在基板上亦可形成彩色濾片、絶緣膜、導電膜及/或驅動電路等。 The substrate includes glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a driving circuit may be formed on the substrate.

在基板上的塗佈較佳為使用旋轉塗佈機、狹縫及旋轉塗佈機、狹縫塗佈機、噴墨、輥塗佈機、浸塗機等的塗佈裝置。 The coating on the substrate is preferably a coating device using a spin coater, a slit and spin coater, a slit coater, an inkjet, a roll coater, a dip coater, or the like.

步驟(2)是使塗佈後的光敏性樹脂組成物乾燥而形成組成物層的步驟。藉由進行該步驟，可除去光敏性樹脂組成物中的溶劑等的揮發成分。就乾燥的方法而言，可列舉加熱乾燥(預焙，prebake)及減壓乾燥。 Step (2) is a step of drying the applied photosensitive resin composition to form a composition layer. By performing this step, a volatile component such as a solvent in the photosensitive resin composition can be removed. Examples of the drying method include heating drying (prebake) and drying under reduced pressure.

進行加熱乾燥時，乾燥溫度較佳為30至120℃，更佳為50至110℃的範圍，乾燥時間較佳為10秒鐘至60分鐘，更佳為30秒鐘至30分鐘。加熱乾燥通常是使用烤箱及熱板等的加熱裝置而進行。 When heating and drying, the drying temperature is preferably 30 to 120 ° C, more preferably 50 to 110 ° C, and the drying time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. Heating and drying are usually performed using a heating device such as an oven or a hot plate.

進行減壓乾燥時，較佳為在50至150Pa的壓力下，20至25℃的溫度範圍進行。 When drying under reduced pressure, it is preferably performed at a temperature in the range of 20 to 25 ° C under a pressure of 50 to 150 Pa.

步驟(3)是將在步驟(2)形成的組成物層，透過光罩而曝光的步驟。該光罩是使用與組成物層所想要除去的部分對應而形成遮光部分的光罩。遮光部分的形狀無特別的限定，可視目的之用途而選擇。亦可使用半色調罩或灰階罩。 Step (3) is a step of exposing the composition layer formed in step (2) through a photomask. This photomask is a photomask that forms a light-shielding portion corresponding to a portion to be removed from the composition layer. The shape of the light-shielding portion is not particularly limited, and can be selected depending on the intended use. You can also use halftone or grayscale hoods.

就用於曝光的光源而言，較佳為產生250至450nm波長的光的光源。例如，將未達350nm的光以將此波長區域遮斷的濾光片遮斷，亦可將436nm附近、408nm附近、365nm附近的 光的這些波長區域使用取出色帶透過性過濾片(band pass filter)而選擇性地取出具體而言，可列舉水銀燈、發光二極體、金屬鹵化物燈、鹵素燈等。 As the light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, if the light below 350 nm is cut off by a filter that cuts off this wavelength range, the light near 436 nm, 408 nm, and 365 nm can be cut off. These wavelength regions of light are selectively extracted using a band pass filter, and specific examples thereof include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

為了可進行在曝光面全面能均勻地照射平行光線，及能夠將光罩與組成物層的精確的對準位置，較佳為使用光罩對準器(mask aligner)及步進器等的曝光裝置。 In order to allow uniform light to be radiated uniformly on the entire exposure surface and to accurately position the mask and the composition layer, it is preferable to use a mask aligner, a stepper, etc. Device.

步驟(4)是將曝光後的組成物層顯影的步驟。藉由將曝光後的組成物層與顯影液接觸而顯影，組成物層的未曝光部分被顯影液溶解而除去，在基板上形成樹脂圖案。 Step (4) is a step of developing the exposed composition layer. When the exposed composition layer is brought into contact with a developing solution for development, the unexposed portion of the composition layer is dissolved and removed by the developing solution, and a resin pattern is formed on the substrate.

就顯影液而言，較佳為例如，氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等的鹼性化合物的水溶液。這些鹼性化合物的水溶液中的濃度較佳為0.01至10質量%，更佳為0.03至5質量%。再者，顯影液亦可含有界面活性劑。 The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, and the like. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

顯影方法可為槳板攪動(paddle)法、浸漬法及噴霧法等的任一種。再者，在顯影時亦可將基板以任意的角度傾斜。 The development method may be any of a paddle method, a dipping method, and a spray method. Furthermore, the substrate may be inclined at an arbitrary angle during development.

顯影後，較佳為以水清洗。 After development, washing with water is preferred.

步驟(5)是將顯影後的組成物層加熱(後焙，post-bake)的步驟。藉由進行加熱，樹脂圖案的耐久性，例如，耐熱性、耐藥品性及機械特性等會提高。加熱通常是使用烤箱及熱板等的加熱裝置進行。加熱溫度較佳為120至250℃，更佳為150至235℃。加熱時間較佳為1至180分鐘，更佳為10至60分鐘。 Step (5) is a step of heating (post-bake) the developed composition layer. By heating, the durability of the resin pattern, such as heat resistance, chemical resistance, and mechanical properties, is improved. Heating is usually performed using a heating device such as an oven or a hot plate. The heating temperature is preferably 120 to 250 ° C, and more preferably 150 to 235 ° C. The heating time is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

由本發明的光敏性樹脂組成物，亦可藉由下述的步驟而製造沒有圖案化的硬化膜。各步驟的較佳條件與樹脂圖案的製造方法相同。 From the photosensitive resin composition of the present invention, a cured film without patterning can also be produced by the following steps. The preferable conditions of each step are the same as those of the method for manufacturing a resin pattern.

步驟(1)：將本發明的光敏性樹脂組成物塗佈在基板上的步驟；步驟(2)：使塗佈後的光敏性樹脂組成物乾燥，形成組成物層的步驟；步驟(5)：將顯影後的組成物層加熱的步驟；必要時，在步驟(2)之後，進行步驟(3’)：將組成物層，不透過光罩而曝光的步驟。又，進行步驟(3')時，亦可進行步驟(4)：將曝光後的組成物層顯影的步驟。 Step (1): a step of coating the photosensitive resin composition of the present invention on a substrate; step (2): a step of drying the coated photosensitive resin composition to form a composition layer; step (5) : A step of heating the developed composition layer; if necessary, after step (2), performing step (3 ′): a step of exposing the composition layer without passing through a photomask. When step (3 ') is performed, step (4): a step of developing the exposed composition layer may be performed.

藉此而得的樹脂圖案由於特別有優異的機械性，因而在作為例如，構成彩色濾光片基板及/或排列板基板的一部分的光間隔物、可製圖案的外保護膜、層間絶緣膜、液晶配向控制用突起、微透鏡、膜厚調整用的被覆層等、觸控板用的構件、構成彩色濾光片基板及/或排列板基板的一部分的外保護膜而有用。再者，由本發明的光敏性樹脂組成物所得的樹脂圖案由於有優異的撥液性，即使在以噴墨法製作彩色濾光片、液晶顯示元件的ITO電極，有機EL顯示元件及電路配線基板等所用的分隔牆也有用。前述的彩色濾光片基板及排列板基板可合適使用於液晶顯示裝置、有機EL顯示裝置、電子報等。 Since the resin pattern thus obtained has particularly excellent mechanical properties, it is used as, for example, an optical spacer constituting a part of a color filter substrate and / or an alignment plate substrate, a patternable outer protective film, and an interlayer insulating film. , Protrusions for liquid crystal alignment control, microlenses, coating layers for film thickness adjustment, members for touch panels, and outer protective films constituting a part of a color filter substrate and / or an alignment plate substrate are useful. Furthermore, since the resin pattern obtained from the photosensitive resin composition of the present invention has excellent liquid repellency, even when an ITO electrode of a color filter, a liquid crystal display element, an organic EL display element, and a circuit wiring substrate are produced by an inkjet method. The partition walls used for this are also useful. The aforementioned color filter substrate and alignment plate substrate can be suitably used in a liquid crystal display device, an organic EL display device, a newsletter, and the like.

實施例 Examples

以下，以實施例更詳細說明本發明。例中的「%」及「份」無特別註明時，表示質量%及質量份。 Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, "%" and "part" indicate mass% and mass parts unless otherwise specified.

(合成例1) (Synthesis example 1)

在裝有迴流冷卻器、滴下漏斗及攪拌機的燒瓶內將 氮氣以0.02L/分流過，成為氮環境，裝入乙酸3-甲氧基丁酯140質量份，邊攪拌邊加熱至70℃。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer Nitrogen was flowed at 0.02 L / min to form a nitrogen environment. 140 parts by mass of 3-methoxybutyl acetate was charged, and heated to 70 ° C. while stirring.

接著，將甲基丙烯酸40質量份、式(x3-2-1)所示的單體(信越化學工業股份有限公司製，商品名X-22-174DX，Mw：4600)4質量份、丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯(式(I-1)所示的化合物及式(II-1)所示的化合物以莫耳比50：50的混合物)356質量份溶解於乙酸3-甲氧基丁酯190質量份而調配溶液，使用滴下幫浦費時4小時，將該溶液滴入保溫在70℃的燒瓶內。 Next, 4 parts by mass of 40 parts by mass of methacrylic acid and a monomer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-174DX, Mw: 4600) represented by the formula (x3-2-1), and 3 parts of acrylic acid were prepared. , 4-epoxytricyclo [5.2.1.0 2.6 ] decyl ester (compound of formula (I-1) and compound of formula (II-1) in a molar ratio of 50:50)) 356 mass Parts were dissolved in 190 parts by mass of 3-methoxybutyl acetate, and a solution was prepared. It took 4 hours to use a drop pump, and the solution was dropped into a flask kept at 70 ° C.

另一方面，將聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)30質量份溶解於乙酸3-甲氧基丁酯240質量份的溶液，以另外一個滴下幫浦費時4小時滴入於燒瓶內。聚合起始劑的溶液滴下完畢後，保持於70℃4小時，之後冷卻至室溫，得到固態成分42.5質量%的共聚物(樹脂Aa)的溶液。所得的樹脂Aa的重量平均分子量Mw是8000，分子量分佈是1.95。固態成分換算的酸價是60 mg-KOH/g。 On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in a solution of 240 parts by mass of 3-methoxybutyl acetate, and the other It took 4 hours to drip the pump into the flask. After the completion of the dropping of the solution of the polymerization initiator, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of the copolymer (resin Aa) with a solid content of 42.5% by mass. The weight average molecular weight Mw of the obtained resin Aa was 8000, and the molecular weight distribution was 1.95. The acid value in terms of solid content is 60 mg-KOH / g.

樹脂Aa具有下述的構造單元。 The resin Aa has the following structural units.

(合成例2) (Synthesis example 2)

在裝有迴流冷卻器，滴下漏斗及攪拌機的燒瓶內將氮氣以0.02L/分流過，成為氮環境，裝入乙酸3-甲氧基丁酯140質量份，邊攪拌下邊加熱至70℃。 In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen gas was flowed at 0.02 L / min to form a nitrogen atmosphere. 140 parts by mass of 3-methoxybutyl acetate was charged, and heated to 70 ° C. while stirring.

接著，將甲基丙烯酸40質量份、式(x3-1-1)所示的單體(信越化學工業股份有限公司製，商品名X-22-2475，Mw：420)4質量份、丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯(式(I-1)所示的化合物及式(II-1)所示的化合物，以莫耳比50：50的混合物)356質量份溶解於乙酸3-甲氧基丁酯190質量份而調配溶液。使用滴下幫浦費時4小時，將該溶液滴入保溫在70℃的燒瓶內。 Next, 40 parts by mass of methacrylic acid and a monomer (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name X-22-2475, Mw: 420) represented by the formula (x3-1-1) were 4 parts by mass and acrylic acid 3 , 4-epoxytricyclo [5.2.1.0 2.6 ] decyl ester (a compound represented by the formula (I-1) and a compound represented by the formula (II-1), a mixture with a molar ratio of 50:50) 356 Part by mass was dissolved in 190 parts by mass of 3-methoxybutyl acetate to prepare a solution. The dripping pump took 4 hours, and the solution was dropped into a flask held at 70 ° C.

另一方面，將聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)30質量份溶解於乙酸3-甲氧基丁酯240質量份的溶液，以另外一個滴下幫浦費時5小時滴入燒瓶內。聚合起始劑的溶液滴下完畢後，保持於70℃4小時，之後冷卻至室溫，得到固態成分42.3質量%的共聚物(樹脂Ab)的溶液。所得的樹脂Ab的重量平均分子量Mw是9300，分子量分佈是2.11。固態成分換算的酸價是 60 mg-KOH/g。 On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in a solution of 240 parts by mass of 3-methoxybutyl acetate, and the other It took 5 hours to drip the pump into the flask. After the completion of the dropping of the solution of the polymerization initiator, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) with a solid content of 42.3% by mass. The weight average molecular weight Mw of the obtained resin Ab was 9,300, and the molecular weight distribution was 2.11. The acid value in terms of solid content is 60 mg-KOH / g.

樹脂Ab具有下述的構造單元。 The resin Ab has the following structural units.

(合成例3) (Synthesis example 3)

在裝有迴流冷卻器、滴下漏斗及攪拌機的燒瓶內將氮氣以0.02L/分流過，成為氮環境，裝入3-甲氧基-1-丁醇200質量份及乙酸3-甲氧基丁酯105質量份，邊攪拌邊加熱至70℃。接著，將甲基丙烯酸60質量份、丙烯酸3,4-環氧基三環[5.2.1.02.6]癸酯(式(I-1)所示的化合物及式(II-1)所示的化合物，以莫耳比50：50的混合物。)240質量份溶解於乙酸3-甲氧基丁酯140質量份而調配溶液，使用滴下漏斗費時4小時，將該溶液滴入保溫在70℃的燒瓶內。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen gas was flowed at 0.02 L / minute to form a nitrogen environment, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl acetate were charged. 105 parts by mass of the ester was heated to 70 ° C while stirring. 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 compound represented by the formula (II-1) A mixture with a molar ratio of 50:50.) 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a flask held at 70 ° C using a dropping funnel for 4 hours. Inside.

另一方面，將聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)30質量份溶解於乙酸3-甲氧基丁酯225質量份的溶液，以 另外一個滴下漏斗費時4小時滴入燒瓶內。聚合起始劑的溶液滴下完畢後，保持於70℃4小時，之後冷卻至室溫，獲得固態成分32.6質量%的共聚物(樹脂Ac)的溶液。所得的樹脂Ac的重量平均分子量Mw是13,400，分子量分佈是2.50。固態成分換算的酸價是110 mg-KOH/g。 On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and The other dropping funnel took 4 hours to drip into the flask. After the completion of the dropping of the solution of the polymerization initiator, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin Ac) with a solid content of 32.6% by mass. The weight average molecular weight Mw of the obtained resin Ac was 13,400, and the molecular weight distribution was 2.50. The acid value in terms of solid content was 110 mg-KOH / g.

樹脂Ac具有下述的構造單元。 The resin Ac has the following structural units.

所得的樹脂的重量平均分子量(Mw)及數量平均分子量(Mn)的測定是使用GPC法，在以下的條件下進行。 The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using a GPC method under the following conditions.

裝置：K2479(島津製作所股份有限公司製) Device: K2479 (manufactured by Shimadzu Corporation)

管柱：SHIMADZU Shim-pack GPC-80M(商品名) Column: SHIMADZU Shim-pack GPC-80M (trade name)

管柱溫度：40℃ Column temperature: 40 ℃

溶媒：THF(四氫呋喃) Solvent: THF (tetrahydrofuran)

流速：1.0ml/min Flow rate: 1.0ml / min

檢測器：RI Detector: RI

校正用標準物質：TSK STANDARD POLYSTYRENE F-40，F-4，F-288，A-2500，A-500(商品名，東曹股份有限公司製) Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (trade name, manufactured by Tosoh Corporation)

以上述所得的聚苯乙烯換算的重量平均分子量及數量平均分子量的比(Mw/Mn)當作分子量分佈。 The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) in terms of the polystyrene conversion obtained above was taken as the molecular weight distribution.

實施例1至5及比較例1 Examples 1 to 5 and Comparative Example 1 <光敏性樹脂組成物的調配> <Preparation of photosensitive resin composition>

將表1所示的各成分以表1所示的比率混合而得到光敏性樹脂組成物。 Each component shown in Table 1 was mixed at the ratio shown in Table 1, and the photosensitive resin composition was obtained.

此外，表1中，樹脂(A)的含有量表示固態成分換算的質量份。 In addition, in Table 1, the content of the resin (A) represents mass parts in terms of solid content.

樹脂(A)：Aa；樹脂Aa Resin (A): Aa; Resin Aa

樹脂(A)：Ab；樹脂Ab Resin (A): Ab; Resin Ab

樹脂(A)：Ac；樹脂Ac Resin (A): Ac; Resin Ac

聚合性化合物(B)：六丙烯酸二季戊四醇酯(KAYARAD(登錄商標)DPHA；日本化藥股份有限公司製) Polymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

聚合起始劑(C)：2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑(B-CIM；保土谷化學股份有限公司製) Polymerization initiator (C): 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole (B-CIM; Hodogaya (Made by Chemical Co., Ltd.)

聚合起始助劑(C1)：9,10-二丁氧基蒽(ANTHRACURE(登錄商標)UVS-1331；川崎化成股份有限公司製) Polymerization initiation aid (C1): 9,10-dibutoxyanthracene (ANTHRACURE (registered trademark) UVS-1331; manufactured by Kawasaki Chemical Co., Ltd.)

硫醇化合物(T)：肆(3-巰基丙酸)季戊四醇酯(PEMP；SC有 機化學股份有限公司製) Thiol compound (T): (3-mercaptopropionic acid) pentaerythritol ester (PEMP; SC has (Made by Chemical Co., Ltd.)

界面活性劑(H)：聚醚改質矽油(TORAY SILICONE SH8400；東麗．道康寧股份有限公司製) Surfactant (H): Polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.)

抗氧化劑(F)：1,3,5-參(4-羥基-3,5-二第三丁基苄基)-1,3,5-三-2.4.6(1H,3H,5H)-三酮(IRGANOX(登錄商標)3114；BASF公司製) Antioxidant (F): 1,3,5-ginseng (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-tris -2.4.6 (1H, 3H, 5H) -trione (IRGANOX (registered trademark) 3114; manufactured by BASF)

溶劑(E)：Ea；丙二醇單甲基醚乙酸酯 Solvent (E): Ea; propylene glycol monomethyl ether acetate

溶劑(E)：Eb；3-乙氧基丙酸乙酯 Solvent (E): Eb; ethyl 3-ethoxypropionate

溶劑(E)：Ec；3-甲氧基-1-丁醇 Solvent (E): Ec; 3-methoxy-1-butanol

溶劑(E)：Ed；乙酸3-甲氧基丁酯 Solvent (E): Ed; 3-methoxybutyl acetate

溶劑(E)以光敏性樹脂組成物的固態成分量成為表1中的「固態成分量(%)」混合。溶劑(E)中的各成分Ea至Ed之值表示溶劑(E)中的質量比(%)。 The solvent (E) was mixed so that the solid content of the photosensitive resin composition would be the "solid content (%)" in Table 1. The values of the components Ea to Ed in the solvent (E) represent the mass ratio (%) in the solvent (E).

<組成物的透光率測定> <Measurement of light transmittance of composition>

就所得的光敏性性樹脂組成物方面，使用紫外線可視光近紅外光分光光度計(V-650；日本分光股份有限公司製)，(石英槽，光徑長：1 cm)，各別測定在400至700 nm的平均透光率(%)。結果顯示於表2。 With respect to the obtained photosensitive resin composition, an ultraviolet visible light near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) was used (quartz groove, optical path length: 1 cm), and each was measured at Average transmittance (%) from 400 to 700 nm. The results are shown in Table 2.

<硬化膜的形成> <Formation of hardened film>

將2英吋見方之玻璃基板(#1737；康寧公司製)，以中性洗劑、水及異丙醇依序清洗後乾燥。在此玻璃基板上，將光敏性樹脂組成物旋轉塗佈而使後焙後的膜厚成為3.0μm，以減壓乾燥機(MICROTECH股份有限公司減壓至減壓度達66kPa而乾燥後，以熱板在80℃下預焙2分鐘，乾燥而形成組成物層。放冷後，使用曝光機(TME-150 RSK；TOPCON股份有限公司製，光源：超 高壓水銀燈)，在大氣環境下，曝光量100mJ/cm2(以405nm為基準)，曝光此組成物層。此外，此時對組成物層的曝光是將來自超高壓水銀燈的放射光通過光學濾光片(LU0400；朝日分光股份有限公司製)而進行。曝光後，在包含非離子系界面活性劑0.12%與氫氧化鉀0.04%的水系顯影液中將曝光後的組成物層在25℃邊搖動邊浸漬100秒鐘而顯影，再以水清洗。之後，在烤箱中，進行235℃15分鐘後焙而獲得硬化膜。 A 2-inch square glass substrate (# 1737; manufactured by Corning Corporation) was sequentially washed with a neutral detergent, water, and isopropyl alcohol, and then dried. On this glass substrate, the photosensitive resin composition was spin-coated so that the film thickness after post-baking became 3.0 μm , and then dried in a vacuum dryer (MICROTECH Co., Ltd. to a reduced pressure of 66 kPa and dried, Pre-baked on a hot plate at 80 ° C for 2 minutes and dried to form a composition layer. After cooling, use an exposure machine (TME-150 RSK; manufactured by TOPCON Co., Ltd., light source: ultra-high pressure mercury lamp), in the atmospheric environment, The composition layer is exposed at an exposure of 100mJ / cm 2 (based on 405nm). In addition, at this time, the composition layer is exposed by passing the light emitted from the ultra-high pressure mercury lamp through an optical filter (LU0400; Asahi Spectrophoton Limited) After exposure, the exposed composition layer was immersed in an aqueous developing solution containing 0.12% of a non-ionic surfactant and 0.04% of potassium hydroxide for 100 seconds at 25 ° C with shaking, and developed. After washing with water, it was post-baked in an oven at 235 ° C for 15 minutes to obtain a cured film.

<硬化膜的透光率測定> <Measurement of transmittance of cured film>

將所得的硬化膜，使用顯微分光測光裝置(OSP-200；OLYMPUS公司製)，測定400至700nm的平均透光率(%)。結果顯示於表2。 The obtained cured film was measured for an average light transmittance (%) of 400 to 700 nm using a micro spectrophotometer (OSP-200; manufactured by OLYMPUS). The results are shown in Table 2.

<樹脂圖案的形成> <Formation of Resin Pattern>

除了在曝光時使用光罩以外，進行與硬化膜的製作同樣操作，獲得樹脂圖案。就光罩而言，使用在同一平面上形成圖案(具有1邊為20μm的正方形透光部，該正方形的間隔為100μm)(即透光部)者。 A resin pattern was obtained in the same manner as in the production of the cured film, except that a photomask was used during exposure. As for the photomask, a pattern formed on a same plane (having a square light-transmitting portion with 20 μm on one side and a space of 100 μm between the squares) (that is, a light-transmitting portion) is used.

<評估：樹脂圖案的寬度及高度的測定> <Evaluation: Measurement of width and height of resin pattern>

將所得的樹脂圖案的寬度及高度，以三維度非接觸表面形狀計算測量系統(MICROMAP MM 527N-PS-M100；菱化系統股份有限公司製)計算測量。樹脂圖案的寬度是自基板面，在樹脂圖案高度的5%的高度位置計算測量。 The width and height of the obtained resin pattern were calculated and measured with a three-dimensional non-contact surface shape calculation measurement system (MICROMAP MM 527N-PS-M100; manufactured by Rhombus System Co., Ltd.). The width of the resin pattern is measured from the substrate surface at a height position of 5% of the resin pattern height.

樹脂圖案的寬度愈大，表示敏感度愈高。結果顯示於表2。 The larger the width of the resin pattern, the higher the sensitivity. The results are shown in Table 2.

<機械特性(總變化量及恢復率)> <Mechanical characteristics (total change and recovery rate)>

對所得的樹脂圖案方面，使用動態超微小硬度計(DUH-W201；島津製作所股份有限公司製)，測定總變化量(μm)及彈性變化量(μm)，並算出恢復率(%)。由於圖案的恢復率愈高，柔軟性愈高，因此可說是作為有用的光間隔物。當這種樹脂圖案作為光間隔物而使用時，可製造有優異強度的液晶平板。結果顯示於表2。 For the obtained resin pattern, a dynamic ultra-micro hardness tester (DUH-W201; manufactured by Shimadzu Corporation) was used to measure the total change ( μm ) and elastic change ( μm ), and calculate the recovery rate (% ). The higher the recovery rate of the pattern, the higher the flexibility, and therefore it can be said to be a useful optical spacer. When such a resin pattern is used as a photo spacer, a liquid crystal panel having excellent strength can be manufactured. The results are shown in Table 2.

-測定條件- -Measurement conditions-

試驗模式：負荷-除荷試驗 Test mode: load-unload test

試驗力：50mN Test force: 50mN

負荷速度：4.41mN/sec Load speed: 4.41mN / sec

保持時間：5秒 Hold time: 5 seconds

穿透機：圓錐台穿透機(直徑50μm) Penetration machine: cone-shaped penetrating machine (50 μm diameter)

恢復率(%)：(彈性變化量(μm)/總變化量(μm)×100 Recovery rate (%): (elastic change (μm) / total change ( μm ) × 100

<接觸角> <Contact angle>

對所得的硬化膜，使用接觸角計(DGD Fast/60；GBX社製)，測定離子交換水、甲苯的接觸角。接觸角愈高，意指撥液性愈高。若硬化膜的接觸角高，則使用同一光敏性樹脂組成物所形成的樹脂圖案的接觸角亦高。較佳為將接觸角高的樹脂圖案用於作為噴墨用分隔牆時，藉由分隔牆撥開印墨，因而有抑制相鄰接的像素領域間混色的傾向。結果顯示於表2。 The contact angle of ion-exchanged water and toluene was measured on the obtained cured film using a contact angle meter (DGD Fast / 60; manufactured by GBX). The higher the contact angle, the higher the liquid repellency. When the contact angle of the cured film is high, the contact angle of a resin pattern formed using the same photosensitive resin composition is also high. When a resin pattern having a high contact angle is used as a partition wall for inkjet, it is preferable that the ink is removed by the partition wall, so that there is a tendency to suppress color mixing between adjacent pixel regions. The results are shown in Table 2.

由表2的結果可知，若為本發明的光敏性樹脂組成物，則恢復率高。據此，可確認由本發明的光敏性樹調組成物所形成的樹脂圖案有優異的機械特性。 As is clear from the results in Table 2, when the photosensitive resin composition of the present invention has a high recovery rate. From this, it was confirmed that the resin pattern formed from the photosensitive tree tone composition of the present invention has excellent mechanical characteristics.

若為本發明的光敏性樹脂組成物，則可獲得有優異的機械特性的圖案。 According to the photosensitive resin composition of the present invention, a pattern having excellent mechanical properties can be obtained.

Claims (5)

一種光敏性樹脂組成物，係包含(A)及(A’)之任一者、(B)及(C)：(A)一種共聚物，係由來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元所組成，其中，來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是，相對於該共聚物的所有構造單元的0.01質量%以上5質量%以下；(A’)一種共聚物，係由來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體的構造單元，與來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元，與至少1種選自由(甲基)丙烯酸酯、含有羥基的(甲基)丙烯酸酯、二羧酸二酯、雙環不飽和化合物、二羰基醯亞胺衍生物、苯乙烯、α-甲基苯乙烯、鄰-乙烯基甲苯、間-乙烯基甲苯、對-乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、氯亞乙烯、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-丁二烯所成群組的構造單元，所組成；其中，來源於具有矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是，相對於該共聚物的所有構造單元的0.01質量%以上5質量%以下，(B)不含矽原子的聚合性化合物(C)聚合起始劑。A photosensitive resin composition comprising any one of (A) and (A '), (B) and (C): (A) a copolymer derived from at least one selected from unsaturated carboxylic acids The structural unit formed by a group of unsaturated carboxylic anhydride and the structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and the structural unit derived from a siloxane structure and ethylene. It is composed of the structural unit of the monomer of the unsaturated unsaturated bond, and the content of the structural unit derived from the monomer having the siloxane structure and the ethylenically unsaturated bond is 0.01 with respect to all the structural units of the copolymer. (A ') A copolymer composed of at least one structural unit selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a copolymer having a carbon number of 2 to A cyclic ether structure and a structural unit of an ethylenically unsaturated monomer of 4 and a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond, and at least one selected from (methyl) Acrylate, hydroxyl-containing (meth) acrylate, dicarboxylic acid diester, bicyclic unsaturated Compounds, dicarbonylfluorenimine derivatives, styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-methoxystyrene, acrylonitrile, Methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 -Butadiene is composed of a group of structural units; wherein the content of the structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond is relative to all the structural units of the copolymer 0.01 mass% to 5 mass%, (B) a polymerizable compound containing no silicon atom (C) a polymerization initiator. 如申請專利範圍第1項所述的光敏性樹脂組成物，其中，具有矽氧烷構造及乙烯性不飽和鍵的單體的重量平均分子量為300至50000。The photosensitive resin composition according to item 1 of the scope of patent application, wherein the weight average molecular weight of the monomer having a siloxane structure and an ethylenically unsaturated bond is 300 to 50,000. 一種由申請專利範圍第1項或第2項所述的光敏性樹脂組成物所形成的樹脂圖案。A resin pattern formed from the photosensitive resin composition according to the first or second patent application scope. 一種顯示裝置，係包含申請專利範圍第3項所述的樹脂圖案。A display device includes the resin pattern described in item 3 of the scope of patent application. 一種共聚物，係由來源於至少1種選自由不飽和羧酸及不飽和羧酸酐所成群組的構造單元，與來源於具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體及來源於具有聚矽氧烷構造及乙烯性不飽和鍵的單體的構造單元所組成，其中，來源於具有聚矽氧烷構造及乙烯性不飽和鍵的單體的構造單元的含有量是，相對於該共聚物的所有構造單元的0.01質量%以上未達5質量%。A copolymer composed of at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a cyclic ether structure and ethylenic unsaturated bonds derived from a carbon number of 2 to 4. And a structural unit derived from a monomer having a polysiloxane structure and an ethylenically unsaturated bond, and the structural unit derived from a monomer having a polysiloxane structure and an ethylenically unsaturated bond The content is 0.01 mass% or more and less than 5 mass% with respect to all the structural units of the copolymer.
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