TW201944173A - Photosensitive resin composition, cured product, insulating material, resin material for solder resists and resist member - Google Patents

Photosensitive resin composition, cured product, insulating material, resin material for solder resists and resist member

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Publication number
TW201944173A
TW201944173A TW108111835A TW108111835A TW201944173A TW 201944173 A TW201944173 A TW 201944173A TW 108111835 A TW108111835 A TW 108111835A TW 108111835 A TW108111835 A TW 108111835A TW 201944173 A TW201944173 A TW 201944173A
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carbon atoms
meth
acid
acrylate
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TW108111835A
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Chinese (zh)
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宮本正紀
山田駿介
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日商迪愛生股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polymerisation Methods In General (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Provided are: a photosensitive resin composition comprising an acid group-containing (meth)acrylate resin (A) and a photopolymerization initiator (B), characterized in that the photopolymerization initiator (B) is a compound represented by general formula (1); a cured product that is a product of a curing reaction of the photosensitive resin composition; an insulating material; a resin material for solder resists; and a resist member. The photosensitive resin composition has a high photosensitivity and is capable of forming a cured product that has an excellent heat tolerance and generates little outgas.

Description

感光性樹脂組成物、硬化物、絕緣材料、阻焊劑用樹脂材料及阻焊構件    Photosensitive resin composition, hardened material, insulating material, resin material for solder resist, and solder resist member   

本發明係關於一種不易發生逸氣的感光性樹脂組成物、硬化物、包含前述感光性樹脂組成物的絕緣材料、阻焊劑用樹脂材料及阻焊構件。 The present invention relates to a photosensitive resin composition, hardened material, which is less prone to outgassing, an insulating material containing the photosensitive resin composition, a resin material for a solder resist, and a solder resist member.

近年來，作為適合印刷電路板的阻焊劑用樹脂材料，廣泛使用可藉由紫外線等的活性能量線硬化的感光性樹脂組成物。作為對於前述阻焊劑用樹脂材料要求的特性，可列舉：以少的曝光量進行硬化、鹼顯影性優異、硬化物之耐熱性或強度、介電特性等優異等各種特性。 In recent years, as a resin material for a solder resist suitable for a printed wiring board, a photosensitive resin composition that can be hardened by active energy rays such as ultraviolet rays has been widely used. As the characteristics required for the resin material for a solder resist, various characteristics such as hardening with a small exposure amount, excellent alkali developability, excellent heat resistance or strength of a cured product, and dielectric properties are mentioned.

作為以往的阻焊劑用樹脂材料，已知一種包含含酸基之環氧丙烯酸酯樹脂的感光性樹脂組成物，該含酸基之環氧丙烯酸酯樹脂係對於使甲酚酚醛清漆型環氧樹脂、丙烯酸、及酞酸酐反應而得到的中間體，進一步使四氫酞酐進行反應而得(例如，參照專利文獻1)，但光感度、硬化物之耐熱性不充分，而無法滿足如今益發提高的要求性能。 As a conventional resin material for a solder resist, there is known a photosensitive resin composition containing an acid group-containing epoxy acrylate resin. The acid group-containing epoxy acrylate resin is a cresol novolac type epoxy resin. The intermediate obtained by reacting acrylic acid, acrylic acid, and phthalic anhydride is further obtained by reacting tetrahydrophthalic anhydride (for example, refer to Patent Document 1). However, the photosensitivity and the heat resistance of the cured product are not sufficient, and it cannot meet the increasing improvement today. Required performance.

又，前述感光性樹脂組成物，在光硬化時、其後因應需求所進行的熱硬化時、或安裝時的焊接之 際，有光聚合起始劑等的含有成分揮發而氣化，汙染周圍的逸氣問題。 In addition, the photosensitive resin composition vaporizes and contaminates the surrounding components, such as a photopolymerization initiator, during photo-curing, subsequent heat-curing according to demand, or welding during installation. Yiqi issue.

於是，尋求一種光感度及硬化物之耐熱性優異、而且不易發生逸氣的感光性樹脂組成物。 Therefore, there is a need for a photosensitive resin composition which is excellent in light sensitivity and heat resistance of a cured product and is less prone to outgassing.

先前技術文獻Prior art literature 專利文獻Patent literature

專利文獻1 日本特開平8-259663号公報 Patent Document 1 Japanese Patent Laid-Open No. 8-259663

本發明所欲解決之課題在於提供一種具有高光感度及硬化物之優異耐熱性、且不易發生逸氣的感光性樹脂組成物、硬化物、包含前述感光性樹脂組成物的絕緣材料、阻焊劑用樹脂材料及阻焊構件。 The problem to be solved by the present invention is to provide a photosensitive resin composition having high light sensitivity and excellent heat resistance of a cured material, and less prone to outgassing, a cured product, an insulating material containing the photosensitive resin composition, and a solder resist. Resin material and solder mask.

本案發明人等為了解決上述課題而進行深入研究的結果，發現藉由使用包含含酸基之(甲基)丙烯酸酯樹脂及特定光聚合起始劑的感光性樹脂組成物，可解決上述課題，進而完成本發明。 As a result of intensive research in order to solve the above-mentioned problems, the inventors of the present case have found that the above-mentioned problems can be solved by using a photosensitive resin composition containing an acid group-containing (meth) acrylate resin and a specific photopolymerization initiator, The present invention has been completed.

亦即，本發明係關於一種感光性樹脂組成物、硬化物、包含前述感光性樹脂組成物的絕緣材料、阻焊劑用樹脂材料及阻焊構件，該感光性樹脂組成物係含有含酸基之(甲基)丙烯酸酯樹脂(A)及光聚合起始劑(B)的感光性樹脂組成物，其特徵為：前述光聚合起始劑(B)係以下述通式(1)表示之化合物。 That is, the present invention relates to a photosensitive resin composition, a cured product, an insulating material containing the photosensitive resin composition, a resin material for a solder resist, and a solder resist member. The photosensitive resin composition contains an acid group-containing The photosensitive resin composition of a (meth) acrylate resin (A) and a photopolymerization initiator (B), wherein the photopolymerization initiator (B) is a compound represented by the following general formula (1) .

Figure TW201944173A_D0001
Figure TW201944173A_D0001

[通式(1)中，R1表示碳原子數1~10之烷基，R2表示碳原子數1~12之烷基、碳原子數2~4之羥烷基、經碳原子數1或2之烷氧基所取代的碳原子數2~4之烷基的任一者，R3表示碳原子數1~12之烷基、碳原子數2~4之羥烷基、甲氧基乙基或乙氧基乙基，又，R2與R3亦可成為一體而為與氮原子一起形成環結構的伸烷基，R2與R3亦可成為一體而為與氮原子一起形成

Figure TW201944173A_D0002
啉骨架、N-甲基哌
Figure TW201944173A_D0003
骨架或2,6-二甲基
Figure TW201944173A_D0004
啉骨架的環結構形成部位，R4~R7分別獨立表示氫原子、碳原子數1~8之烷基或苯基，Y1表示不具有取代基或者具有鹵素原子或羥基作為取代基的碳原子數3~19之烷基(y1-1)、碳原子數7~19之芳烷基(y1-2)、或以下述結構式(y1-3)表示之結構部位(y1-3)、
Figure TW201944173A_D0005
 [In the general formula (1), R 1 represents an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and a carbon atom having 1 Or an alkoxy group substituted by 2 or 2 alkyl groups having 2 to 4 carbon atoms, R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, or a methoxy group Ethyl or ethoxyethyl, and R 2 and R 3 may be integrated to form an alkylene group that forms a ring structure with a nitrogen atom. R 2 and R 3 may also be integrated to form a group with a nitrogen atom.
Figure TW201944173A_D0002
Porphyrin skeleton, N-methyl piperazine
Figure TW201944173A_D0003
Backbone or 2,6-dimethyl
Figure TW201944173A_D0004
A ring structure forming site of a morpholine skeleton. R 4 to R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and Y 1 represents a carbon having no substituent or a halogen atom or a hydroxyl group as a substituent. Alkyl group (y1-1) having 3 to 19 atoms, aralkyl group (y1-2) having 7 to 19 carbon atoms, or a structural site (y1-3) represented by the following structural formula (y1-3),
Figure TW201944173A_D0005

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子或苯基或碳原子數1~4之烷基，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom or a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20.)

以下述結構式(y1-4)表示之結構部位(y1-4)、

Figure TW201944173A_D0006
Structural parts (y1-4) represented by the following structural formula (y1-4),
Figure TW201944173A_D0006

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子、苯基或碳數1~4之烷基，R10表示氫原子或甲基，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, and m represents 0 to 20 Integer.)

以下述結構式(y1-5)表示之結構部位(y1-5)、

Figure TW201944173A_D0007
Structural parts (y1-5) represented by the following structural formula (y1-5),
Figure TW201944173A_D0007

(式中，R10表示氫原子或甲基，R11表示碳原子數1~18之烷基或碳原子數6~18之芳基。) (In the formula, R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)

以下述結構式(y1-6)表示之結構部位(y1-6)、

Figure TW201944173A_D0008
The structural part (y1-6) represented by the following structural formula (y1-6),
Figure TW201944173A_D0008

(式中，R12表示碳原子數1~18之烷基。) (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)

以下述結構式(y1-7)表示之結構部位(y1-7)、

Figure TW201944173A_D0009
Structural parts (y1-7) represented by the following structural formula (y1-7),
Figure TW201944173A_D0009

(式中，R8表示碳原子數2~4之伸烷基，R13表示氫原子、碳原子數1~6之烷基或鹵素原子，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and m represents an integer of 0 to 20.)

以下述結構式(y1-8)表示之結構部位(y1-8)、

Figure TW201944173A_D0010
Structural parts (y1-8) represented by the following structural formula (y1-8),
Figure TW201944173A_D0010

(式中，R8分別獨立表示碳原子數2~4之伸烷基，R10表示氫原子或甲基，R14表示具有p+1個連接鍵(bonding hand)的碳原子數3~25之烴基，1表示0~20之整數，p表示1~3之整數。) (In the formula, R 8 each independently represents an alkylene group having 2 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, and R 14 represents 3 to 25 carbon atoms having p + 1 bonding hands. Hydrocarbon group, 1 represents an integer from 0 to 20, and p represents an integer from 1 to 3.)

下述結構式(y1-9)，

Figure TW201944173A_D0011
The following structural formula (y1-9),
Figure TW201944173A_D0011

(式中，R15表示碳原子數4~18之烷基、碳原子數6~10之脂肪族環狀烴基、芳香族基。) (In the formula, R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, and an aromatic group.)

X1表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，X2表示氫原子或甲基，X3表示氫原子、甲基或乙基，或者X2及X3在虛線部形成共價鍵並且一體地表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，或者X1、X2及X3一體地表示以下述結構式(X-1)所表示之與氮原子一起構成雙環的4價之脂肪族烴基，

Figure TW201944173A_D0012
X 1 represents ethyl, 1,3-propyl, 1,2-propyl, 2,3-propyl, X 2 represents a hydrogen atom or a methyl group, and X 3 represents a hydrogen atom, a methyl group, or an ethyl group Or X 2 and X 3 form a covalent bond in the dashed portion and collectively represent an ethyl group, a 1,3-propyl group, a 1,2-propyl group, a 2,3-propyl group, or X 1 , X 2 and X 3 integrally represent a tetravalent aliphatic hydrocarbon group represented by the following structural formula (X-1) and forming a bicyclic ring with a nitrogen atom,
Figure TW201944173A_D0012

Y2表示在其結構部位末端具有氮原子或氧原子的具有(n+1)個連接鍵之有機連結基，Y3表示單鍵、碳原子數1~3之伸烷基或碳原子數1~3之亞烷基，且n表示1~3之整數]。 Y 2 represents an organic linking group having (n + 1) connecting bonds having a nitrogen atom or an oxygen atom at the end of its structural portion, Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or 1 carbon atom An alkylene group of ~ 3, and n represents an integer of 1 to 3].

本發明之感光性樹脂組成物具有高光感度及硬化物之優異耐熱性，而且不易發生逸氣，因此可適合用於絕緣材料、阻焊劑用樹脂材料及包含前述阻焊劑用樹脂的阻焊構件。 The photosensitive resin composition of the present invention has high light sensitivity and excellent heat resistance of hardened materials, and is less prone to outgassing. Therefore, the photosensitive resin composition can be suitably used for insulating materials, resin materials for solder resists, and solder resist members including the resin for solder resists.

用以實施發明之形態Forms used to implement the invention

本發明之感光性樹脂組成物的特徵為含有含酸基之(甲基)丙烯酸酯樹脂(A)及以下述通式(1)表示之光聚合性起始劑(B)。 The photosensitive resin composition of the present invention is characterized by containing an acid group-containing (meth) acrylate resin (A) and a photopolymerizable initiator (B) represented by the following general formula (1).

Figure TW201944173A_D0013
Figure TW201944173A_D0013

[通式(1)中，R1表示碳原子數1~10之烷基， R2表示碳原子數1~12之烷基、碳原子數2~4之羥烷基、經碳原子數1或2之烷氧基所取代的碳原子數2~4之烷基的任一者，R3表示碳原子數1~12之烷基、碳原子數2~4之羥烷基、甲氧基乙基或乙氧基乙基，又，R2與R3亦可成為一體而為與氮原子一起形成環結構的伸烷基，R2與R3亦可成為一體而為與氮原子一起形成

Figure TW201944173A_D0014
啉骨架、N-甲基哌
Figure TW201944173A_D0015
骨架或2,6-二甲基
Figure TW201944173A_D0016
啉骨架的環結構形成部位，R4~R7分別獨立表示氫原子、碳原子數1~8之烷基或苯基，Y1表示不具有取代基或者具有鹵素原子或羥基作為取代基的碳原子數3~19之烷基(y1-1)、碳原子數7~19之芳烷基(y1-2)、或以下述結構式(y1-3)表示之結構部位(y1-3)、
Figure TW201944173A_D0017
 [In the general formula (1), R 1 represents an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and a carbon atom having 1 Or an alkoxy group substituted by 2 or 2 alkyl groups having 2 to 4 carbon atoms, R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, or a methoxy group Ethyl or ethoxyethyl, and R 2 and R 3 may be integrated to form an alkylene group that forms a ring structure with a nitrogen atom. R 2 and R 3 may also be integrated to form a group with a nitrogen atom.
Figure TW201944173A_D0014
Porphyrin skeleton, N-methyl piperazine
Figure TW201944173A_D0015
Backbone or 2,6-dimethyl
Figure TW201944173A_D0016
A ring structure forming site of a morpholine skeleton. R 4 to R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and Y 1 represents a carbon having no substituent or a halogen atom or a hydroxyl group as a substituent. Alkyl group (y1-1) having 3 to 19 atoms, aralkyl group (y1-2) having 7 to 19 carbon atoms, or a structural site (y1-3) represented by the following structural formula (y1-3),
Figure TW201944173A_D0017

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子或苯基或碳原子數1~4之烷基，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom or a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20.)

以下述結構式(y1-4)表示之結構部位(y1-4)、

Figure TW201944173A_D0018
Structural parts (y1-4) represented by the following structural formula (y1-4),
Figure TW201944173A_D0018

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子、苯基或碳數1~4之烷基，R10表示氫原子或甲基，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, and m represents 0 to 20 Integer.)

以下述結構式(y1-5)表示之結構部位(y1-5)、

Figure TW201944173A_D0019
Structural parts (y1-5) represented by the following structural formula (y1-5),
Figure TW201944173A_D0019

(式中，R10表示氫原子或甲基，R11表示碳原子數1~18之烷基或碳原子數6~18之芳基。) (In the formula, R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)

以下述結構式(y1-6)表示之結構部位(y1-6)、

Figure TW201944173A_D0020
The structural part (y1-6) represented by the following structural formula (y1-6),
Figure TW201944173A_D0020

(式中，R12表示碳原子數1~18之烷基。) (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)

以下述結構式(y1-7)表示之結構部位(y1-7)、

Figure TW201944173A_D0021
Structural parts (y1-7) represented by the following structural formula (y1-7),
Figure TW201944173A_D0021

(式中，R8表示碳原子數2~4之伸烷基，R13表示氫原子、碳原子數1~6之烷基或鹵素原子，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and m represents an integer of 0 to 20.)

以下述結構式(y1-8)表示之結構部位(y1-8)、

Figure TW201944173A_D0022
Structural parts (y1-8) represented by the following structural formula (y1-8),
Figure TW201944173A_D0022

(式中，R8分別獨立表示碳原子數2~4之伸烷基，R10表示氫原子或甲基，R14表示具有p+1個連接鍵的碳原子數3~25之烴基，1表示0~20之整數，p表示1~3之整數。) (In the formula, R 8 independently represents an alkylene group having 2 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, R 14 represents a hydrocarbon group having 3 to 25 carbon atoms having p + 1 connection bonds, 1 Represents an integer from 0 to 20, and p represents an integer from 1 to 3.)

下述結構式(y1-9)，

Figure TW201944173A_D0023
The following structural formula (y1-9),
Figure TW201944173A_D0023

(式中，R15表示碳原子數4~18之烷基、碳原子數6~10之脂肪族環狀烴基、芳香族基。) (In the formula, R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, and an aromatic group.)

X1表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，X2表示氫原子或甲基，X3表示氫原子、甲基或乙基，或者X2及X3在虛線部形成共價鍵並且一體地表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，或者X1、X2及X3一體地表示以下述結構式(X-1)所表示之與氮原子一起構成雙環的4價之脂肪族烴基，

Figure TW201944173A_D0024
X 1 represents ethyl, 1,3-propyl, 1,2-propyl, 2,3-propyl, X 2 represents a hydrogen atom or a methyl group, and X 3 represents a hydrogen atom, a methyl group, or an ethyl group Or X 2 and X 3 form a covalent bond in the dashed portion and collectively represent an ethyl group, a 1,3-propyl group, a 1,2-propyl group, a 2,3-propyl group, or X 1 , X 2 and X 3 integrally represent a tetravalent aliphatic hydrocarbon group represented by the following structural formula (X-1) and forming a bicyclic ring with a nitrogen atom,
Figure TW201944173A_D0024

Y2表示在其結構部位末端具有氮原子或氧原子的具有(n+1)個連接鍵之有機連結基，Y3表示單鍵、碳原子數1~3之伸烷基或碳原子數1~3之亞烷基，且n表示1~3之整數]。 Y 2 represents an organic linking group having (n + 1) connecting bonds having a nitrogen atom or an oxygen atom at the end of its structural portion, Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or 1 carbon atom An alkylene group of ~ 3, and n represents an integer of 1 to 3].

此外，在本發明中，「(甲基)丙烯酸酯樹脂」係指分子中具有丙烯醯基及甲基丙烯醯基之一者或兩者的樹脂。又，「(甲基)丙烯醯基」係指丙烯醯基及甲基丙烯醯基之一者或兩者，「(甲基)丙烯酸酯」係指丙烯酸酯及甲基丙烯酸酯之一者或兩者。 In addition, in the present invention, the "(meth) acrylate resin" means a resin having one or both of an acrylic fluorenyl group and a methacrylic fluorene group in the molecule. In addition, "(meth) acrylfluorenyl" means one or both of acrylyl and methacrylmethyl, and "(meth) acrylate" refers to one or both of acrylate and methacrylate. Both.

針對前述含酸基之(甲基)丙烯酸酯樹脂(A)進行說明。 The acid group-containing (meth) acrylate resin (A) will be described.

作為前述含酸基之(甲基)丙烯酸酯樹脂(A)，只要具有酸基及(甲基)丙烯醯基即可，其他之具體結構或分子量等無特別限制，可使用各式各樣的樹脂。 As the acid group-containing (meth) acrylate resin (A), it is only necessary to have an acid group and a (meth) acrylfluorenyl group, and other specific structures and molecular weights are not particularly limited, and various types can be used. Resin.

作為前述含酸基之(甲基)丙烯酸酯樹脂(A)所含有的酸基，可列舉例如：羧基、磺酸基、磷酸基等。此等之中，從表現優異鹼顯影性來看，較佳為羧基。 Examples of the acid group contained in the acid group-containing (meth) acrylate resin (A) include a carboxyl group, a sulfonic acid group, and a phosphate group. Among these, from the viewpoint of exhibiting excellent alkali developability, a carboxyl group is preferred.

作為前述含酸基之(甲基)丙烯酸酯樹脂(A)，可列舉例如：[1]以環氧樹脂(a1-1)、不飽和單羧酸(a1-2)及多羧酸酐(a1-3)作為必要反應原料的含酸基之(甲基)丙烯酸酯樹脂(A-1)；[2]以含酚性羥基之樹脂(a2-1)、環狀碳酸酯化合物(a2-2a)或環狀醚化合物(a2-2b)、不飽和單羧酸(a2-3a)及/或N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)、以及多羧酸酐(a2-4)作為必要反應原料的含酸基之(甲基)丙烯酸酯樹脂(A-2)；[3]以具有酸基或酸酐基之醯胺醯亞胺樹脂(a3-1)、含羥基之(甲基)丙烯酸酯化合物(a3-2)、含(甲基)丙烯醯基之環氧化合物(a3-3)及多羧酸酐(a3-4)作為必要反應原料的含酸基之(甲基)丙烯酸酯樹脂(A-3)等。 Examples of the acid group-containing (meth) acrylate resin (A) include [1] epoxy resin (a1-1), unsaturated monocarboxylic acid (a1-2), and polycarboxylic anhydride (a1). -3) An acid group-containing (meth) acrylate resin (A-1) as a necessary reaction raw material; [2] A phenolic hydroxyl group-containing resin (a2-1), and a cyclic carbonate compound (a2-2a ) Or cyclic ether compound (a2-2b), unsaturated monocarboxylic acid (a2-3a) and / or N-alkoxyalkyl (meth) acrylamidonium compound (a2-3b), and polycarboxylic anhydride (a2-4) an acid group-containing (meth) acrylate resin (A-2) as an essential reaction raw material; [3] a fluorene and imine resin (a3-1) having an acid group or an acid anhydride group, (Meth) acrylic acid compound (a3-2) containing hydroxyl group, epoxy compound (a3-3) containing (meth) acrylfluorenyl group, and acid group containing polycarboxylic anhydride (a3-4) as essential raw materials for reaction (Meth) acrylate resin (A-3) and the like.

針對[1]含酸基之(甲基)丙烯酸酯樹脂(A-1)進行說明。 [1] The (meth) acrylate resin (A-1) containing an acid group will be described.

前述含酸基之(甲基)丙烯酸酯樹脂(A-1)係將環氧樹脂(a1-1)、不飽和單羧酸(a1-2)及多羧酸酐(a1-3)作為必要反應原料所得者。 The aforementioned (meth) acrylic acid resin (A-1) containing an acid group requires an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2), and a polycarboxylic anhydride (a1-3) as essential reactions. The winner of raw materials.

作為前述環氧樹脂(a1-1)，只要是樹脂中具有複數環氧基者，則其具體結構並無特別限定。 The specific structure of the epoxy resin (a1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin.

作為前述環氧樹脂(a1-1)，可列舉例如：雙酚型環氧樹脂、氫化雙酚型環氧樹脂、聯苯酚型環氧樹脂、氫化聯苯酚型環氧樹脂、伸苯醚型環氧樹脂、伸萘醚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、雙環戊二烯-酚加成反應型環氧樹脂等。 Examples of the epoxy resin (a1-1) include a bisphenol epoxy resin, a hydrogenated bisphenol epoxy resin, a biphenol epoxy resin, a hydrogenated biphenol epoxy resin, and a phenylene ether ring. Epoxy resin, naphthyl ether epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, phenol aralkyl Epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, etc.

前述不飽和單羧酸(a1-2)係指一分子中具有(甲基)丙烯醯基與羧基的化合物，可列舉例如丙烯酸、甲基丙烯酸等。又，亦可使用前述不飽和單羧酸(a1-2)的酯化物、酸鹵化物、酸酐等。此等不飽和單羧酸(a1-2)可單獨使用亦可併用2種以上。 The unsaturated monocarboxylic acid (a1-2) refers to a compound having a (meth) acryl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, an esterified product, an acid halide, an acid anhydride, or the like of the unsaturated monocarboxylic acid (a1-2) may be used. These unsaturated monocarboxylic acids (a1-2) may be used alone or in combination of two or more.

作為前述不飽和單羧酸(a1-2)的酯化物，可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸2-乙基己酯等的(甲基)丙烯酸烷酯化合物；(甲基)丙烯酸羥乙酯、(甲基) 丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯等的含羥基之(甲基)丙烯酸酯化合物；(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯等的含氮之(甲基)丙烯酸酯化合物；(甲基)丙烯酸環氧丙酯(glycidyl(meth)acrylate)、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸

Figure TW201944173A_D0025
啉酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯等的其他(甲基)丙烯酸酯化合物等。 Examples of the esterified product of the unsaturated monocarboxylic acid (a1-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethyl (meth) acrylate (Meth) acrylic acid alkyl ester compounds such as methylhexyl ester; hydroxyl-containing (meth) acrylic acid such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate Ester compounds; nitrogen-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; glycidyl (meth) acrylate (meth) acrylate), tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid
Figure TW201944173A_D0025
Other (meth) acrylate compounds, such as phosphonoester, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

作為前述不飽和單羧酸(a1-2)的酸鹵化物，可列舉例如(甲基)丙烯醯氯等。 Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid chloride and the like.

作為前述不飽和單羧酸(b1-3)的酸酐，可列舉例如(甲基)丙烯酸酐等。 Examples of the acid anhydride of the unsaturated monocarboxylic acid (b1-3) include (meth) acrylic anhydride.

前述多羧酸酐(a1-3)，只要是一分子中具有2個以上羧基之化合物的酸酐，可使用任一者。作為前述多羧酸酐，可列舉例如：乙二酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、馬來酸、富馬酸、酞酸、異酞酸、對酞酸、四氫酞酸、六氫酞酸、甲基六氫酞酸等二羧酸化合物的酸酐等。 The polycarboxylic acid anhydride (a1-3) may be any acid anhydride as long as it is an acid anhydride of a compound having two or more carboxyl groups in one molecule. Examples of the polycarboxylic anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, rich Acid anhydrides of dicarboxylic acid compounds such as maleic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid.

前述含酸基之(甲基)丙烯酸酯樹脂(A-1)的製造方法，只要是以前述環氧樹脂(a1-1)、前述不飽和單羧酸(a1-2)及前述多羧酸酐(a1-3)作為必要反應原料者，則並無特別限定，可藉由任意方法製造。例如，可藉由使全部反應原料一次性反應的方法製造，亦可藉由使反應原料依序反應的方法製造。其中，從容易控制反應來看，較佳為先使環氧樹脂(a1-1)與不飽和單羧酸(a1-2)反應，接著使多羧酸酐(a1-3)反應的方法。該反應 例如可藉由下述方法進行：在酯化反應觸媒的存在下、100~150℃的溫度範圍內使環氧樹脂(a1-1)與不飽和單羧酸(a1-2)反應後，於反應系中加入多羧酸酐(a1-3)，並於90~120℃的溫度範圍內使其反應的方法等。 The method for producing the acid group-containing (meth) acrylate resin (A-1) includes the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic anhydride. (a1-3) There are no particular limitations on the material required as a reaction raw material, and it can be produced by any method. For example, it can manufacture by the method which makes all the reaction raw materials react at one time, and can also manufacture by the method which makes the reaction raw materials react sequentially. Among these, from the viewpoint of easy control of the reaction, a method of first reacting the epoxy resin (a1-1) with an unsaturated monocarboxylic acid (a1-2) and then reacting the polycarboxylic anhydride (a1-3) is preferred. This reaction can be performed, for example, by reacting an epoxy resin (a1-1) with an unsaturated monocarboxylic acid (a1-2) in the temperature range of 100 to 150 ° C. in the presence of an esterification reaction catalyst. Then, a method such as adding a polycarboxylic anhydride (a1-3) to the reaction system and reacting it at a temperature range of 90 to 120 ° C.

前述環氧樹脂(a1-1)與不飽和單羧酸(a1-2)的反應比例，較佳為相對於環氧樹脂(a1-1)中的環氧基1莫耳，以0.9~1.1莫耳的範圍使用不飽和單羧酸(a1-2)。又，前述多羧酸酐(a1-3)的反應比例，較佳為相對於環氧樹脂(a1-1)中的環氧基1莫耳，以0.2~1.0莫耳的範圍使用。 The reaction ratio of the epoxy resin (a1-1) to the unsaturated monocarboxylic acid (a1-2) is preferably 0.9 to 1.1 relative to 1 mole of the epoxy group in the epoxy resin (a1-1). The Mohr range uses an unsaturated monocarboxylic acid (a1-2). The reaction ratio of the polycarboxylic anhydride (a1-3) is preferably used in the range of 0.2 to 1.0 mol relative to 1 mol of the epoxy group in the epoxy resin (a1-1).

作為前述酯化反應觸媒，可列舉例如：三甲膦、三丁膦、三苯膦等的磷化合物、三乙胺、三丁胺、二甲基芐胺等的胺化合物、2-甲基咪唑、2-十七基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-異丁基-2-甲基咪唑等的咪唑化合物等。此等反應觸媒可單獨使用亦可併用2種以上。 Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine; and 2-methylimidazole. , Imidazole compounds such as 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, and the like. These reaction catalysts may be used alone or in combination of two or more.

相對於反應原料的合計100質量份，前述反應觸媒的添加量較佳為0.001~5質量份的範圍。 The addition amount of the reaction catalyst is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total of the reaction raw materials.

前述環氧樹脂(a1-1)、前述不飽和單羧酸(a1-2)及前述多羧酸酐(a1-3)的反應，亦可因應需求在有機溶媒中進行。使用之有機溶媒的選擇，可根據反應原料及生成物的含酸基之(甲基)丙烯酸酯樹脂的溶解性、反應溫度條件而適當選擇，可列舉例如：甲乙酮、丙酮、二甲基甲醯胺、甲基異丁酮、甲氧基丙醇、環己酮、甲基賽路蘇、二烷二醇單烷基醚乙酸酯、二烷二醇乙酸酯 等。此等有機溶媒可單獨使用，亦可併用2種以上而作為混合溶媒使用。 The reaction of the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic anhydride (a1-3) may also be performed in an organic solvent as required. The choice of the organic solvent to be used can be appropriately selected according to the solubility of the acid group-containing (meth) acrylate resin of the reaction raw material and the product, and the reaction temperature conditions. Examples include methyl ethyl ketone, acetone, and dimethyl formamidine. Amines, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celex, dioxane monoalkyl ether acetate, dioxane glycol acetate, and the like. These organic solvents may be used alone or as a mixed solvent in combination of two or more.

前述有機溶媒的使用量，從反應效率變得良好來看，相對於反應原料的合計100質量份，較佳為10~500質量份的範圍。 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials, from the viewpoint of improving the reaction efficiency.

用於本發明的含酸基之(甲基)丙烯酸酯樹脂(A-1)的酸價，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為30~150mgKOH/g的範圍，更佳為40~100mgKOH/g的範圍。此外，在本案發明中，含酸基之(甲基)丙烯酸酯樹脂的酸價係以JIS K 0070(1992)的中和滴定法所測量的值。 The acid value of the acid group-containing (meth) acrylate resin (A-1) used in the present invention can be obtained from the acid group-containing (meth) acrylic acid which has a high light sensitivity and can form a cured product excellent in heat resistance. From the viewpoint of the ester resin composition, a range of 30 to 150 mgKOH / g is preferable, and a range of 40 to 100 mgKOH / g is more preferable. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method of JIS K 0070 (1992).

接著，針對[2]含酸基之(甲基)丙烯酸酯樹脂(A-2)進行說明。 Next, [2] the acid group-containing (meth) acrylate resin (A-2) will be described.

前述含酸基之(甲基)丙烯酸酯樹脂(A-2)係將含酚性羥基之樹脂(a2-1)、環狀碳酸酯化合物(a2-2a)或環狀醚化合物(a2-2b)、不飽和單羧酸(a2-3a)及/或N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)、以及多羧酸酐(a2-4)作為必要反應原料所得者。 The acid group-containing (meth) acrylate resin (A-2) is a resin (a2-1) containing a phenolic hydroxyl group, a cyclic carbonate compound (a2-2a), or a cyclic ether compound (a2-2b). ), Unsaturated monocarboxylic acid (a2-3a) and / or N-alkoxyalkyl (meth) acrylamidonium compound (a2-3b), and polycarboxylic anhydride (a2-4) as necessary raw materials for reaction By.

前述含酚性羥基之樹脂(a2-1)係指分子內具有2個以上酚性羥基的樹脂，可列舉例如：芳香族多羥基化合物、以1種或2種以上的分子內具有1個酚性羥基之化合物作為反應原料的酚醛清漆型酚樹脂、或者以前述具有1個酚性羥基之化合物與下述結構式(x-1)~(x-5)的任一者所表示之化合物(x)作為必要反應原料的反應生成物等。 The phenolic hydroxyl group-containing resin (a2-1) means a resin having two or more phenolic hydroxyl groups in a molecule, and examples thereof include an aromatic polyhydroxy compound, and one or two or more kinds of phenolic molecules in a molecule. A novolak phenol resin used as a reaction raw material of a compound of a hydroxyl group or a compound represented by the aforementioned compound having one phenolic hydroxyl group and any one of the following structural formulae (x-1) to (x-5) ( x) A reaction product or the like as an essential reaction raw material.

Figure TW201944173A_D0026
Figure TW201944173A_D0026

(式中，h為0或1；R1分別獨立為脂肪族烴基、烷氧基、鹵素原子、芳基、芳氧基、芳烷基的任一者，i為0或1~4之整數；Z為乙烯基、鹵甲基、羥甲基、烷氧基甲基的任一者；Y為碳原子數1~4之伸烷基、氧原子、硫原子、羰基的任一者。j為1~4之整數)。 (Wherein h is 0 or 1; R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, and i is an integer of 0 or 1 to 4 ; Z is any of vinyl, halomethyl, methylol, and alkoxymethyl; Y is any of alkylene, oxygen, sulfur, and carbonyl groups having 1 to 4 carbon atoms; j Is an integer from 1 to 4).

作為前述芳香族多羥基化合物，例如，除了二羥苯、三羥苯、四羥苯、二羥萘、三羥萘、四羥萘、二羥蒽、三羥蒽、四羥蒽、聯苯酚、四羥基聯苯、雙酚等以外，亦可列舉於此等的芳香核上具有1個或複數的取代基的化合物等。又，作為芳香核上的取代基，可列舉例如：甲基、乙基、乙烯基、丙基、丁基、戊基、己基、環己基、庚基、辛基、壬基等的脂肪族烴基；甲氧基、乙氧基、丙氧基、丁氧基等的烷氧基；氟原子、氯原子、溴原子等的鹵素原子；苯基、萘基、蒽基、及此等的芳香核上取代有前述脂肪族烴基、前述烷氧基、前 述鹵素原子等的芳基；苯氧基、萘氧基、及此等的芳香核上取代有前述脂肪族烴基、前述烷氧基、前述鹵素原子等的芳氧基；苯基甲基、苯基乙基、萘基甲基、萘基乙基、及此等的芳香核上取代有前述脂肪族烴基、前述烷氧基、前述鹵素原子等的芳烷基等。此等芳香族多羥基化合物可單獨使用亦可併用2種以上。此等之中，從可得到具有高絕緣可靠度的含酸基之(甲基)丙烯酸酯樹脂來看，較佳為不含鹵素的化合物。 Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, In addition to tetrahydroxybiphenyl, bisphenol, and the like, compounds having one or more substituents on the aromatic nucleus can also be mentioned. Examples of the substituent on the aromatic nucleus include aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl. ; Alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, naphthyl, anthracenyl, and the aromatic nuclei Aryl groups substituted with the aforementioned aliphatic hydrocarbon group, the alkoxy group, the aforementioned halogen atom, etc .; phenoxy, naphthyloxy, and the aromatic nuclei are substituted with the aforementioned aliphatic hydrocarbon group, the alkoxy group, the aforementioned halogen Aryloxy groups such as atoms; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl, and these aromatic nuclei are substituted with the aforementioned aliphatic hydrocarbon group, the aforementioned alkoxy group, the aforementioned halogen atom, etc. Aralkyl and so on. These aromatic polyhydroxy compounds may be used alone or in combination of two or more. Among these, in view of obtaining an acid group-containing (meth) acrylate resin having high insulation reliability, a halogen-free compound is preferred.

作為前述酚醛清漆型酚樹脂，可列舉例如：在酸性觸媒下使1種或2種以上的分子內具有1個酚性羥基之化合物與醛化合物進行反應而得者。 Examples of the novolac-type phenol resin include those obtained by reacting a compound having one phenolic hydroxyl group in one molecule or two or more molecules with an aldehyde compound under an acidic catalyst.

作為前述分子內具有1個酚性羥基之化合物，只要是芳香核上具有1個羥基的芳香族化合物，可為任意化合物，可列舉例如：苯酚或於苯酚的芳香核上具有1個或複數的取代基的苯酚化合物、萘酚或於萘酚的芳香核上具有1個或複數的取代基的萘酚化合物、蒽酚(anthracenol)或於蒽酚的芳香核上具有1個或複數的取代基的蒽酚化合物等。又，作為芳香核上的取代基，可列舉例如脂肪族烴基、烷氧基、鹵素原子、芳基、芳氧基、芳烷基等，分別的具體例係如上所述。此等具有1個酚性羥基之化合物，可單獨使用，亦可併用2種以上。 The compound having one phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having one hydroxyl group on an aromatic nucleus, and examples thereof include phenol or one having a plurality of aromatic nucleus on phenol. Substituted phenol compound, naphthol, or naphthol compound having one or more substituents on the aromatic core of naphthol, anthracenol, or one or more substituents on the aromatic core of anthracene Anthracene compounds, etc. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples thereof are as described above. These compounds having one phenolic hydroxyl group may be used alone or in combination of two or more kinds.

作為前述醛化合物，可列舉例如：甲醛；乙醛、丙醛、丁醛、異丁醛、戊醛、己醛等的烷基醛；柳醛、3-羥基苯甲醛、4-羥基苯甲醛、2-羥基-4-甲基苯 甲醛、2,4-二羥基苯甲醛、3,4-二羥基苯甲醛等的羥基苯甲醛；2-羥基-3-甲氧基苯甲醛、3-羥基-4-甲氧基苯甲醛、4-羥基-3-甲氧基苯甲醛、3-乙氧基-4-羥基苯甲醛、4-羥基-3,5-二甲氧基苯甲醛等具有羥基與烷氧基兩者的苯甲醛；甲氧基苯甲醛、乙氧基苯甲醛等的烷氧基苯甲醛；1-羥基-2-萘甲醛、2-羥基-1-萘甲醛、6-羥基-2-萘甲醛等的羥基萘甲醛；溴苯甲醛等的鹵化苯甲醛等。 Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and hexanal; and salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, and other hydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy- 4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, etc. Benzaldehyde of both alkoxy groups; alkoxybenzaldehyde of methoxybenzaldehyde, ethoxybenzaldehyde, etc .; 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy- 2-naphthaldehyde and other hydroxynaphthaldehydes; bromobenzaldehyde and other halogenated benzaldehydes.

作為前述酸性觸媒，可列舉例如：鹽酸、硫酸、磷酸等的無機酸、甲磺酸、對甲苯磺酸、乙二酸等的有機酸、三氟化硼、無水氯化鋁、氯化鋅等的路易士酸等。此等酸性觸媒可單獨使用亦可併用2種以上。 Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. Louis acid etc. These acid catalysts can be used alone or in combination of two or more.

作為以前述具有1個酚性羥基的化合物與前述化合物(x)作為必要反應原料的反應生成物，例如，可藉由在酸性觸媒下、80~200℃左右的溫度條件下將前述分子內具有1個酚性羥基的化合物與前述化合物(x)進行加熱攪拌的方法而得。前述分子內具有1個酚性羥基的化合物與前述化合物(x)的反應比例，較佳係相對於前述化合物(x)1莫耳，前述分子內具有1個酚性羥基的化合物為0.5~5莫耳的比例。 As a reaction product using the aforementioned compound having one phenolic hydroxyl group and the aforementioned compound (x) as an essential reaction raw material, the aforementioned molecule can be intramolecularly, for example, under an acid catalyst at a temperature of about 80 to 200 ° C. It is obtained by heating and stirring the compound which has one phenolic hydroxyl group and the said compound (x). The reaction ratio between the compound having one phenolic hydroxyl group in the molecule and the compound (x) is preferably 0.5 to 5 moles relative to the compound (x). Mohr's ratio.

作為前述酸性觸媒，係與上述相同。 The acidic catalyst is the same as described above.

作為前述環狀碳酸酯化合物(a2-2a)，可列舉例如：碳酸伸乙酯、碳酸伸丙酯、碳酸伸丁酯、碳酸伸戊酯等。此等環狀碳酸酯化合物可單獨使用亦可併用2種以上。又，此等之中，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為碳酸伸乙酯或碳酸伸丙酯。 Examples of the cyclic carbonate compound (a2-2a) include ethyl carbonate, propylene carbonate, butyl carbonate, and pentyl carbonate. These cyclic carbonate compounds may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having a high light sensitivity and a cured product having excellent heat resistance, ethyl carbonate or propylene carbonate is preferred. ester.

作為前述環狀醚化合物(a2-2b)，可列舉例如：環氧乙烷(ethylene oxide)、環氧丙烷(propylene oxide)、四氫呋喃等。此等環狀醚化合物可單獨使用亦可併用2種以上。又，此等之中，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為環氧乙烷或環氧丙烷。 Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having a high light sensitivity and a cured product having excellent heat resistance, ethylene oxide or propylene oxide is preferred. .

作為前述不飽和單羧酸(a2-3a)，可使用與上述不飽和單羧酸(a1-2)相同者。 As said unsaturated monocarboxylic acid (a2-3a), the same thing as the said unsaturated monocarboxylic acid (a1-2) can be used.

作為前述N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)，可列舉例如：N-甲氧基甲基(甲基)丙烯醯胺、N-乙氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-甲氧基乙基(甲基)丙烯醯胺、N-乙氧基乙基(甲基)丙烯醯胺、N-丁氧基乙基(甲基)丙烯醯胺等。此等之中，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為N-甲氧基甲基(甲基)丙烯醯胺。又，此等N-烷氧基烷基(甲基)丙烯醯胺化合物可單獨使用亦可併用2種以上。 Examples of the N-alkoxyalkyl (meth) acrylamidonium compound (a2-3b) include N-methoxymethyl (meth) acrylamidonium and N-ethoxymethyl ( Methacrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamine Amine, N-butoxyethyl (meth) acrylamide and the like. Among these, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having a high light sensitivity and a cured product having excellent heat resistance, N-methoxymethyl (methyl ) Acrylamide. These N-alkoxyalkyl (meth) acrylamido compounds may be used alone or in combination of two or more.

作為前述多羧酸酐(a2-4)，可使用與上述多羧酸酐(a1-3)相同者。 As said polycarboxylic anhydride (a2-4), the same thing as the said polycarboxylic anhydride (a1-3) can be used.

使用前述N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)的情況下，其與前述多羧酸酐(a2-4))的當量比[(a2-3b)/(a2-4))]，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為0.2~7的範圍，更佳為0.25~6.7的範圍。 When using the aforementioned N-alkoxyalkyl (meth) acrylamide compound (a2-3b), its equivalent ratio to the aforementioned polycarboxylic anhydride (a2-4)) [(a2-3b) / (a2 -4))], from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having a high light sensitivity and a hardened material having excellent heat resistance, a range of 0.2 to 7 is more preferred, and more preferably The range is 0.25 ~ 6.7.

前述含酸基之(甲基)丙烯酸酯樹脂(A-2)的製造方法並無特別限定，可藉由任意方法製造。例如，可藉由使全部反應原料一次性反應的方法製造，亦可藉由使反應原料依序反應的方法製造。其中，從容易控制反應來看，較佳為下述方法：先使含酚性羥基之樹脂(a2-1)與環狀碳酸酯化合物(a2-2a)或環狀醚化合物(a2-2b)反應，接著使不飽和單羧酸(a2-3a)及/或N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)反應後，使多羧酸酐(a2-4)進行反應。該反應例如可藉由下述方法進行：在鹼性觸媒的存在下、100~200℃的溫度範圍內，使前述含酚性羥基之樹脂(a2-1)與前述環狀碳酸酯化合物(a2-2a)或前述環狀醚化合物(a2-2b)反應後，在酸性觸媒的存在下，使不飽和多羧酸(b2-3a)及/或N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)於80~140℃的溫度範圍內進行反應，接著，加入多羧酸酐(a2-4)，並於80~140℃的溫度範圍內使其反應的方法等。 The method for producing the acid group-containing (meth) acrylate resin (A-2) is not particularly limited, and it can be produced by any method. For example, it can manufacture by the method which makes all the reaction raw materials react at one time, and can also manufacture by the method which makes the reaction raw materials react sequentially. Among them, from the viewpoint of easy control of the reaction, the following method is preferred: first, a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b) After the reaction, the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamidonium compound (a2-3b) are reacted, and then the polycarboxylic anhydride (a2-4) is allowed to proceed. reaction. This reaction can be performed, for example, by a method in which the phenolic hydroxyl group-containing resin (a2-1) and the cyclic carbonate compound ( a2-2a) or the aforementioned cyclic ether compound (a2-2b), the unsaturated polycarboxylic acid (b2-3a) and / or N-alkoxyalkyl (methyl ) A method in which the acrylamide compound (a2-3b) is reacted in a temperature range of 80 to 140 ° C, and then a polycarboxylic anhydride (a2-4) is added and reacted in a temperature range of 80 to 140 ° C. .

作為前述鹼性觸媒，可列舉例如：氫氧化鈣、氫氧化鋇等的鹼土金屬氫氧化物；碳酸鈉、碳酸鉀等的鹼金屬碳酸鹽；氫氧化鈉、氫氧化鉀等的鹼金屬氫氧化物、三甲膦、三丁膦、三苯膦等的磷化合物、三乙胺、三丁胺、二甲基芐胺等的胺化合物、2-甲基咪唑、2-十七基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-異丁基-2-甲基咪唑等的咪唑化合物等。此等鹼性觸媒可單獨使用亦可併用2種以上。 Examples of the alkaline catalyst include alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and alkali metal hydrogens such as sodium hydroxide and potassium hydroxide. Oxides, phosphorus compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine, amine compounds such as triethylamine, tributylamine, dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2 -Imidazole compounds such as ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, and the like. These alkaline catalysts can be used alone or in combination of two or more.

作為前述酸性觸媒，可列舉例如：鹽酸、硫酸、磷酸等的無機酸、甲磺酸、對甲苯磺酸、乙二酸等的有機酸、三氟化硼、無水氯化鋁、氯化鋅等的路易士酸等。此等酸觸媒可單獨使用亦可併用2種以上。 Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. Louis acid etc. These acid catalysts may be used alone or in combination of two or more.

前述含酚性羥基之樹脂(a2-1)、前述環狀碳酸酯化合物(a2-2a)或前述環狀醚化合物(a2-2b)、前述不飽和單羧酸(a2-3a)及/或前述N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)、以及前述多羧酸酐(a2-4)的反應，亦可因應需求在有機溶媒中進行。使用之有機溶媒的選擇，可根據反應原料及生成物的含酸基之(甲基)丙烯酸酯樹脂的溶解性、反應溫度條件而適當選擇，可列舉例如：甲乙酮、丙酮、二甲基甲醯胺、甲基異丁酮、甲氧基丙醇、環己酮、甲基賽路蘇、二烷二醇單烷基醚乙酸酯、二烷二醇乙酸酯等。此等有機溶媒可單獨使用，亦可併用2種以上而作為混合溶媒使用。 The phenolic hydroxyl-containing resin (a2-1), the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), the unsaturated monocarboxylic acid (a2-3a), and / or The reaction of the N-alkoxyalkyl (meth) acrylamidonium compound (a2-3b) and the polycarboxylic anhydride (a2-4) may be performed in an organic solvent as required. The choice of the organic solvent to be used can be appropriately selected according to the solubility of the acid group-containing (meth) acrylate resin of the reaction raw material and the product, and the reaction temperature conditions. Examples include methyl ethyl ketone, acetone, and dimethyl formamidine. Amines, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celex, dioxane monoalkyl ether acetate, dioxane glycol acetate, and the like. These organic solvents may be used alone or as a mixed solvent in combination of two or more.

前述有機溶媒的使用量，從反應效率變得良好來看，相對於反應原料的合計100質量份，較佳為10~500質量份的範圍。 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials, from the viewpoint of improving the reaction efficiency.

前述含酸基之(甲基)丙烯酸酯樹脂(A-2)的具體結構並無特別限定，只要是以含酚性羥基之樹脂(a2-1)、環狀碳酸酯化合物(a2-2a)或環狀醚化合物(a2-2b)、不飽和單羧酸(a2-3a)及/或N-烷氧基烷基(甲基)丙烯醯胺化合物(a2-3b)、以及多羧酸酐(a2-4)作為必要反應原料而樹脂中具有酸基及(甲基)丙烯醯基者即可，作為所得到的前述含酸基之(甲基)丙烯酸酯樹脂(A-2)， 可列舉例如：具有以下述結構式(a-1)所表示之結構部位(I)與下述結構式(a-2)所表示之結構部位(II)作為重複結構單元的樹脂結構者；或具有以下述結構式(a-3)所表示之結構部位(III)與下述結構式(a-4)所表示之結構部位(IV)作為重複結構單元的樹脂結構者。 The specific structure of the acid group-containing (meth) acrylate resin (A-2) is not particularly limited as long as it is a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) Or cyclic ether compound (a2-2b), unsaturated monocarboxylic acid (a2-3a) and / or N-alkoxyalkyl (meth) acrylamidonium compound (a2-3b), and polycarboxylic anhydride ( a2-4) It is only necessary that the resin has an acid group and a (meth) acryl group in the resin as an essential reaction raw material. Examples of the obtained acid group-containing (meth) acrylate resin (A-2) include: For example: a resin structure having a structural portion (I) represented by the following structural formula (a-1) and a structural portion (II) represented by the following structural formula (a-2) as repeating structural units; or having the following A resin structure in which the structural part (III) represented by the structural formula (a-3) and the structural part (IV) represented by the following structural formula (a-4) are used as repeating structural units.

Figure TW201944173A_D0027
Figure TW201944173A_D0027

[式中，R2分別獨立為氫原子或碳原子數1~4之烴基；R3分別獨立為氫原子、碳原子數1~4之烴基、碳原子數1~4之烷氧基、鹵素原子的任一者，n分別獨立為1或2；R4分別獨立為亞甲基或以下述結構式(x’-1)~(x’-5)的任一者所表示之結構部位；R5、R6分別獨立為氫原子或碳原子數1~20之烴基；又，R5與R6可連結而形成飽和或不飽和的環；R7為碳原子數1~12之烴基；R8為氫原子或甲基；x為前述R3所表示之結構部位、或者透過標註*號之R4與結構式(a-1)所表示之結構部位(I)或結構式(a-2)所表示之結構部位(II)連結的鍵結點]。 [Wherein R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R 3 is independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen For any atom, n is independently 1 or 2; R 4 is independently methylene or a structural site represented by any one of the following structural formulae (x'-1) to (x'-5); R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 5 and R 6 may be connected to form a saturated or unsaturated ring; R 7 is a hydrocarbon group having 1 to 12 carbon atoms; R 8 is a hydrogen atom or a methyl group; x is the structural moiety represented by the R 3, or through the structural site marked with * number of R 4 of formula (a-1) represented by the (I) or formula (A- 2) Bonding point of the structural part (II) shown].

Figure TW201944173A_D0028
Figure TW201944173A_D0028

[式中，R2分別獨立為氫原子或碳原子數1~4之烴基；R3分別獨立為氫原子、碳原子數1~4之烴基、碳原子數1~4之烷氧基、鹵素原子的任一者，n分別獨立為1或2；R4分別獨立為亞甲基或以下述結構式(x’-1)~(x’-5)的任一者所表示之結構部位；R5、R6分別獨立為氫原子或碳原子數1~20之烴基；又，R5與R6可連結而形成飽和或不飽和的環；R7為碳原子數1~12之烴基；R8為氫原子或甲基；x為前述R3所表示之結構部位、或者透過標註*號之R4與結構式(a-3)所表示之結構部位(III)或結構式(a-4)所表示之結構部位(IV)連結的鍵結點]。 [Wherein R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R 3 is independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen For any atom, n is independently 1 or 2; R 4 is independently methylene or a structural site represented by any one of the following structural formulae (x'-1) to (x'-5); R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 5 and R 6 may be connected to form a saturated or unsaturated ring; R 7 is a hydrocarbon group having 1 to 12 carbon atoms; R 8 is a hydrogen atom or a methyl group; x is the structural moiety represented by the R 3, or through the structural site marked with * number of R 4 of formula (a-3) represented by the (III) or formula (A- 4) Bonding point of the structural part (IV) shown].

Figure TW201944173A_D0029
Figure TW201944173A_D0029

Figure TW201944173A_D0030
Figure TW201944173A_D0030

Figure TW201944173A_D0031
Figure TW201944173A_D0031

Figure TW201944173A_D0032
Figure TW201944173A_D0032

Figure TW201944173A_D0033
Figure TW201944173A_D0033

[式中，h為0或1；R9分別獨立為脂肪族烴基、烷氧基、鹵素原子、芳基、芳烷基的任一者，i為0或1~4之整數；R10為氫原子或甲基；W為下述結構式(w-1)或(w-2)；Y為碳原子數1~4之伸烷基、氧原子、硫原子、羰基的任一者。j為1~4之整數]。 [Wherein h is 0 or 1; R 9 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is an integer of 0 or 1 to 4; R 10 is A hydrogen atom or a methyl group; W is the following structural formula (w-1) or (w-2); Y is any of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer from 1 to 4].

Figure TW201944173A_D0034
Figure TW201944173A_D0034

(式中，R11分別獨立為氫原子或碳原子數1~4之烴基；R12、R13分別獨立為氫原子或碳原子數1~20之烴基；又，R12與R13可連結而形成飽和或不飽和的環；R14為碳原子數1~12之烴基；R15為氫原子或甲基)。 (In the formula, R 11 is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R 12 and R 13 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and R 12 and R 13 may be linked A saturated or unsaturated ring is formed; R 14 is a hydrocarbon group having 1 to 12 carbon atoms; R 15 is a hydrogen atom or a methyl group).

前述含酸基之(甲基)丙烯酸酯樹脂(A-2)的酸價，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為30~150mgKOH/g的範圍，更佳為40~100mgKOH/g的範圍。此外，在本發明中，前述含酸基之(甲基)丙烯酸酯樹脂的酸價係基於JIS K 0070(1992)的中和滴定法所測量的值。 The acid value of the acid group-containing (meth) acrylate resin (A-2) can be obtained from the acid group-containing (meth) acrylate resin composition which has a high light sensitivity and can form a cured product having excellent heat resistance. In view of this, a range of 30 to 150 mgKOH / g is preferable, and a range of 40 to 100 mgKOH / g is more preferable. In the present invention, the acid value of the acid group-containing (meth) acrylate resin is a value measured based on the neutralization titration method of JIS K 0070 (1992).

接著，針對[3]含酸基之(甲基)丙烯酸酯樹脂(A-3)進行說明。 Next, [3] an acid group-containing (meth) acrylate resin (A-3) will be described.

前述含酸基之(甲基)丙烯酸酯樹脂(A-3)係將具有酸基或酸酐基之醯胺醯亞胺樹脂(a3-1)、含羥基之(甲基)丙烯酸酯化合物(a3-2)、含(甲基)丙烯醯基之環氧化合物(a3-3)及多羧酸酐(a3-4)作為必要反應原料所得者。 The aforementioned (meth) acrylate resin (A-3) containing an acid group is a fluorene amine imine resin (a3-1) having an acid group or an acid anhydride group, and a (meth) acrylate compound (a3) containing a hydroxyl group -2) An epoxy compound (a3-3) containing a (meth) acrylfluorenyl group and a polycarboxylic anhydride (a3-4) are obtained as necessary reaction raw materials.

作為前述醯胺醯亞胺樹脂(a3-1)，可僅具有酸基或酸酐基的任一者，亦可具有兩者。從與前述含羥基之(甲基)丙烯酸酯化合物(a3-2)或前述含(甲基)丙烯醯基之環氧化合物(a3-3)的反應性、反應控制的觀點來看，較佳為具有酸酐基，更佳為具有酸基與酸酐基兩者。前述醯胺醯亞胺樹脂(a3-1)的酸價，較佳係中性條件下、亦即未使酸酐基開環的條件下的測量值為 60~350mgKOH/g的範圍。另一方面，較佳係在水的存在下等、使酸酐基開環的條件下的測量值為61~360mgKOH/g的範圍。 The amidamine-imine resin (a3-1) may have only either an acid group or an acid anhydride group, or both. It is preferable from the viewpoint of reactivity and reaction control with the hydroxyl-containing (meth) acrylate compound (a3-2) or the (meth) acrylfluorenyl-containing epoxy compound (a3-3). To have an acid anhydride group, it is more preferable to have both an acid group and an acid anhydride group. The acid value of the amidamine and imine resin (a3-1) is preferably in a range of 60 to 350 mgKOH / g under a neutral condition, that is, a condition in which the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measurement value is in the range of 61 to 360 mgKOH / g in the presence of water and under conditions where the acid anhydride group is ring-opened.

前述醯胺醯亞胺樹脂(a3-1)的具體結構、製造方法並無特別限定，可廣泛使用一般的醯胺醯亞胺樹脂等。可列舉例如以聚異氰酸酯化合物與多羧酸或其酸酐作為反應原料而得者。 The specific structure and production method of the amidamide imine resin (a3-1) are not particularly limited, and general amidamide imine resin and the like can be widely used. Examples thereof include those obtained by using a polyisocyanate compound and a polycarboxylic acid or an anhydride thereof as a reaction raw material.

作為前述聚異氰酸酯化合物，可列舉例如：丁烷二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等的脂肪族二異氰酸酯化合物；降莰烷二異氰酸酯、異佛爾酮二異氰酸酯、氫化伸茬基二異氰酸酯、氫化二苯甲烷二異氰酸酯等的脂環式二異氰酸酯化合物；甲苯二異氰酸酯、伸茬基二異氰酸酯、四甲基伸茬基二異氰酸酯、二苯甲烷二異氰酸酯、1,5-萘二異氰酸酯、4,4’-二異氰酸基-3,3’-二甲基聯苯、聯鄰甲苯胺二異氰酸酯(o-tolidine diisocyanate)等的芳香族二異氰酸酯化合物；具有以下述結構式(i-1)表示之重複結構的聚亞甲基聚苯基聚異氰酸酯；此等的異三聚氰酸酯(isocyanurate)改質物、雙脲(biuret)改質物、脲甲酸酯(allophanate)改質物等。又，此等聚異氰酸酯化合物可單獨使用亦可併用2種以上。 Examples of the polyisocyanate compound include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene. Aliphatic diisocyanate compounds such as diisocyanates; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated diisocyanate, hydrogenated diphenylmethane diisocyanate; toluene diisocyanate, Stubble diisocyanate, tetramethyl stubble diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl Aromatic diisocyanate compounds such as o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); Isocyanurate modifier, biuret modifier, allophanate modifier, and the like. These polyisocyanate compounds may be used alone or in combination of two or more.

Figure TW201944173A_D0035
Figure TW201944173A_D0035

[式中，R1分別獨立為氫原子、碳原子數1~6之烴基的任一者；R2分別獨立為碳原子數1~4之烷基、或者透過標註*號之亞甲基與結構式(i-1)所表示之結構部位連結的鍵結點之任一者；1為0或1~3之整數，m為1以上之整數]。 [Wherein R 1 is each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; R 2 is independently an alkyl group having 1 to 4 carbon atoms, or through a methylene group marked with an * Any one of the bond nodes connected to the structural part represented by the structural formula (i-1); 1 is an integer of 0 or 1 to 3, and m is an integer of 1 or more].

又，作為前述聚異氰酸酯化合物，從可得到具有高溶劑溶解性的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為脂環式二異氰酸酯化合物或其改質物、脂肪族二異氰酸酯化合物或其改質物，更佳為脂環式二異氰酸酯或其異三聚氰酸酯改質物、脂肪族二異氰酸酯或其異三聚氰酸酯改質物。 In addition, as the polyisocyanate compound, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having high solvent solubility, an alicyclic diisocyanate compound or a modified product thereof, or an aliphatic diisocyanate compound is preferred. The isocyanate compound or the modified product thereof is more preferably an alicyclic diisocyanate or an isotricyanate modified product thereof, an aliphatic diisocyanate or an isotricyanate modified product thereof.

又，前述聚異氰酸酯化合物的總質量中，脂環式二異氰酸酯化合物或其改質物與脂肪族二異氰酸酯化合物或其改質物之合計質量的比例，較佳為70質量%以上，更佳為90質量%以上。 Moreover, in the total mass of the said polyisocyanate compound, the ratio of the total mass of an alicyclic diisocyanate compound or its modification and the aliphatic diisocyanate compound or its modification is 70 mass% or more, 90 mass is more preferable %the above.

又，在併用脂環式二異氰酸酯化合物或其改質物與脂肪族二異氰酸酯化合物或其改質物的情況下，兩者的質量比較佳為30/70~70/30的範圍。 When an alicyclic diisocyanate compound or a modified product thereof is used in combination with an aliphatic diisocyanate compound or a modified product thereof, the mass of the two is preferably in the range of 30/70 to 70/30.

作為前述多羧酸或其酸酐，只要是分子結構中具有複數羧基的化合物或其酸酐，則其具體結構並無特別限制，可使用各式各樣的化合物。此外，為了使 前述醯胺醯亞胺樹脂(a3-1)具有醯胺基與醯亞胺基兩者，系統中必須存在羧基及酸酐基兩者，但在本發明中，可使用分子中具有羧基與酸酐基兩者的化合物，亦可併用具有羧基的化合物與具有酸酐基的化合物。 As the polycarboxylic acid or its anhydride, as long as it is a compound having a plurality of carboxyl groups in the molecular structure or its anhydride, the specific structure is not particularly limited, and various compounds can be used. In addition, in order for the amidamine and imine resin (a3-1) to have both amidino group and amidino group, it is necessary to have both a carboxyl group and an acid anhydride group in the system. As the compound having both a carboxyl group and an acid anhydride group, a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.

作為前述多羧酸或其酸酐，可列舉例如：脂肪族多羧酸化合物或其酸酐、脂環式多羧酸化合物或其酸酐、芳香族多羧酸化合物或其酸酐等。 Examples of the polycarboxylic acid or its anhydride include an aliphatic polycarboxylic acid compound or its anhydride, an alicyclic polycarboxylic acid compound or its anhydride, an aromatic polycarboxylic acid compound or its anhydride, and the like.

作為前述脂肪族多羧酸化合物或其酸酐，脂肪族烴基可為直鏈型及分支型的任一者，亦可於結構中具有不飽和鍵。 As said aliphatic polycarboxylic acid compound or its anhydride, an aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in a structure.

作為前述脂肪族多羧酸化合物或其酸酐，可列舉例如：乙二酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、馬來酸、富馬酸、檸康酸、衣康酸、戊烯二酸、1,2,3,4-丁烷四甲酸及此等的酸酐等。 Examples of the aliphatic polycarboxylic acid compound or its anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. , Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaric acid, 1,2,3,4-butanetetracarboxylic acid and their anhydrides.

作為前述脂環式多羧酸化合物或其酸酐，本發明中，將羧基或酸酐基鍵結於脂環結構者當作脂環式多羧酸化合物或其酸酐，而不限制其以外的結構部位中有無芳香環。作為前述脂環式多羧酸化合物或其酸酐，可列舉例如：四氫酞酸、六氫酞酸、甲基六氫酞酸、環己烷三甲酸、環己烷四甲酸、雙環[2.2.1]庚烷-2,3-二甲酸、甲基雙環[2.2.1]庚烷-2,3-二甲酸、4-(2,5-二側氧四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二甲酸及此等的酸酐等。 As the aforementioned alicyclic polycarboxylic acid compound or its anhydride, in the present invention, those having a carboxyl group or an acid anhydride group bonded to an alicyclic structure are regarded as an alicyclic polycarboxylic acid compound or its anhydride, without restricting other structural sites. With or without aromatic rings. Examples of the alicyclic polycarboxylic acid compound or its anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclic [2.2. 1] Heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2 , 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid and anhydrides thereof.

作為前述芳香族多羧酸化合物或其酸酐，可列舉例如：酞酸、苯偏三酸(trimellitic acid)、苯均四酸(pyromellitic acid)、萘二甲酸、萘三甲酸、萘四甲酸、聯苯二甲酸、聯苯三甲酸、聯苯四甲酸、二苯甲酮四甲酸等。 Examples of the aromatic polycarboxylic acid compound or its anhydride include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyl Phthalic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc.

此等之中，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為前述脂環式多羧酸化合物或其酸酐、或者前述芳香族多羧酸化合物或其酸酐。又，從可有效率地製造前述醯胺醯亞胺樹脂(a3-1)來看，較佳為使用分子結構中具有羧基與酸酐基兩者的三羧酸酐，特佳為使用環己烷三甲酸酐或苯偏三酸酐。再者，相對於前述多羧酸或其酸酐的總質量，脂環式三羧酸酐與芳香族三羧酸酐之合計量的比例較佳為70質量%以上，更佳為90質量%以上。 Among these, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having a high light sensitivity and capable of forming a cured product having excellent heat resistance, the aforementioned alicyclic polycarboxylic acid compound or its An acid anhydride, or the aforementioned aromatic polycarboxylic acid compound or an anhydride thereof. Moreover, from the viewpoint of efficient production of the amidamine and imine resin (a3-1), it is preferable to use a tricarboxylic anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and particularly preferred is to use cyclohexanetrimethyl ether. Acid anhydride or trimellitic anhydride. In addition, the ratio of the total amount of the alicyclic tricarboxylic anhydride and the aromatic tricarboxylic anhydride to the total mass of the polycarboxylic acid or the anhydride thereof is preferably 70% by mass or more, and more preferably 90% by mass or more.

前述醯胺醯亞胺樹脂(a3-1)係以前述聚異氰酸酯化合物與前述多羧酸或其酸酐作為反應原料的情況下，亦可因應期望的樹脂性能等而併用此等以外的反應原料。此情況下，從充分發揮本發明所發揮之效果來看，相對於醯胺醯亞胺樹脂(a3-1)的反應原料總質量，前述聚異氰酸酯化合物與前述多羧酸或其酸酐之合計質量的比例較佳為90質量%以上，更佳為95質量%以上。 When the said fluorene amine and imine resin (a3-1) uses the said polyisocyanate compound and the said polycarboxylic acid or its anhydride as a reaction raw material, you may use together other reaction raw materials according to a desired resin performance etc. In this case, from the viewpoint of giving full play to the effects exerted by the present invention, the total mass of the polyisocyanate compound and the polycarboxylic acid or the anhydride thereof relative to the total mass of the reaction raw materials of the amidamine and imine resin (a3-1). The ratio is preferably 90% by mass or more, and more preferably 95% by mass or more.

前述醯胺醯亞胺樹脂(a3-1)係以聚異氰酸酯化合物與多羧酸或其酸酐作為反應原料的情況下，無特別限定，可藉由任意方法製造。例如，能夠以與一般的 醯胺醯亞胺樹脂相同的方法製造。具體而言，可列舉：相對於聚異氰酸酯化合物所具有之異氰酸酯基1莫耳，使用0.8~1.2莫耳的多羧酸或其酸酐，於120~180℃左右的溫度條件下進行攪拌混合而使其反應的方法。 When the said fluorene amine and imine resin (a3-1) uses a polyisocyanate compound and a polycarboxylic acid or its anhydride as a reaction raw material, it does not specifically limit, It can manufacture by arbitrary methods. For example, it can be produced by the same method as that of general amidinimide resin. Specifically, the polyisocyanate compound may be stirred and mixed at a temperature of about 120 to 180 ° C. using a polycarboxylic acid or an anhydride of 0.8 to 1.2 mol with respect to 1 mol of the isocyanate group of the polyisocyanate compound. Its reaction method.

前述聚異氰酸酯化合物與多羧酸或其酸酐的反應，亦可因應需求在有機溶媒中進行。作為前述有機溶媒，可列舉例如：甲乙酮、丙酮、二甲基甲醯胺、甲基異丁酮、甲氧基丙醇、環己酮、甲基賽路蘇、二烷二醇單烷基醚乙酸酯、二烷二醇乙酸酯等。此等有機溶媒可單獨使用，亦可併用2種以上而作為混合溶媒使用。 The reaction between the aforementioned polyisocyanate compound and the polycarboxylic acid or its anhydride can also be carried out in an organic solvent as required. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cyrusux, and dioxane monoalkyl ether. Acetate, dioxane glycol acetate, and the like. These organic solvents may be used alone or as a mixed solvent in combination of two or more.

前述有機溶媒的使用量，從反應效率變得良好來看，相對於反應原料的合計100質量份，較佳為10~500質量份的範圍。 The amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw materials, from the viewpoint of improving the reaction efficiency.

作為前述含羥基之(甲基)丙烯酸酯化合物(a3-2)，只要是分子結構中具有羥基與(甲基)丙烯醯基的化合物，則其他具體結構並無特別限定，可使用各式各樣的化合物。可列舉例如：(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等的羥基(甲基)丙烯酸酯化合物；於前述各種羥基(甲基)丙烯酸酯化合物的分子結構中導入有(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等的(聚)氧伸烷基鏈的(聚)氧伸烷基改質物；於前述各種的羥基(甲基)丙烯酸酯化合物的分子結構中導入有(聚)內酯結構的內酯改質物等。此等之中， 從可得到可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為分子量1,000以下者。又，前述含羥基之(甲基)丙烯酸酯化合物(a3-2)為前述氧伸烷基改質物或內酯改質物的情況下，其重量平均分子量(Mw)較佳為1,000以下。此等含羥基之(甲基)丙烯酸酯化合物可單獨使用亦可併用2種以上。 As the hydroxyl-containing (meth) acrylate compound (a3-2), as long as it is a compound having a hydroxyl group and a (meth) acrylfluorenyl group in its molecular structure, other specific structures are not particularly limited, and various formulae can be used. Like compound. Examples include: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentaerythritol tri (meth) acrylate, di-tris Hydroxy (meth) acrylate compounds such as methylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc .; in the molecular structure of the aforementioned various hydroxy (meth) acrylate compounds (Poly) oxyalkylene modified products having (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, etc .; Modified lactones having a (poly) lactone structure and the like are introduced into the molecular structures of the various hydroxy (meth) acrylate compounds described above. Among these, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance, a molecular weight of 1,000 or less is preferred. When the hydroxy-containing (meth) acrylate compound (a3-2) is the oxyalkylene modified product or lactone modified product, its weight average molecular weight (Mw) is preferably 1,000 or less. These hydroxyl-containing (meth) acrylate compounds may be used alone or in combination of two or more.

前述含(甲基)丙烯醯基之環氧化合物(a3-3)，只要是分子結構中具有(甲基)丙烯醯基與環氧基者，則其他具體結構並無特別限定，可使用各式各樣的化合物。可列舉例如：(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸4-羥丁酯環氧丙基醚(4-hydroxybutyl (meth)acrylate glycidyl ether)、(甲基)丙烯酸環氧環己基甲酯等含環氧丙基之(甲基)丙烯酸酯單體；二羥苯二環氧丙基醚、二羥萘二環氧丙基醚、聯苯酚二環氧丙基醚、雙酚二環氧丙基醚等的二環氧丙基醚化合物的單(甲基)丙烯酸酯化物等。此等之中，從可得到可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為含環氧丙基之(甲基)丙烯酸酯單體。又，其分子量較佳為500以下。再者，前述含(甲基)丙烯醯基之環氧化合物(a3-3)的總質量中的前述含環氧丙基之(甲基)丙烯酸酯單體的比例較佳為70質量%以上，更佳為90質量%以上。 The aforementioned (meth) acrylfluorene-containing epoxy compound (a3-3) is not particularly limited as long as it has a (meth) acrylfluorenyl group and an epoxy group in its molecular structure, and each of them may be used. Various compounds. Examples include: glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, epoxy cyclohexyl (meth) acrylate (Meth) acrylic acid ester-containing monomers such as methyl ester; dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, bisphenol di Mono (meth) acrylates of diglycidyl ether compounds such as glycidyl ether and the like. Among these, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition capable of forming a cured product having excellent heat resistance, an epoxypropyl group-containing (meth) acrylate monomer is preferred. . The molecular weight is preferably 500 or less. The proportion of the (meth) acrylic acid-containing (meth) acrylate monomer in the total mass of the (meth) acrylfluorene-containing epoxy compound (a3-3) is preferably 70% by mass or more. , More preferably 90% by mass or more.

作為前述多羧酸酐(a3-4)，係與上述多羧酸酐(a1-3)及多羧酸酐(a2-4)相同。 The polycarboxylic anhydride (a3-4) is the same as the polycarboxylic anhydride (a1-3) and the polycarboxylic anhydride (a2-4).

前述含酸基之(甲基)丙烯酸酯樹脂(A-3)，除了前述具有酸基或酸酐基之醯胺醯亞胺樹脂(a3-1)、前述含羥基之(甲基)丙烯酸酯化合物(a3-2)、含(甲基)丙烯醯基之環氧化合物(a3-3)及多羧酸酐(a3-4)以外，亦可因應期望的樹脂性能等併用其他反應原料。此情況下，含酸基之(甲基)丙烯酸酯樹脂(A-3)的反應原料總質量中的前述(a3-1)~(a3-4)成分之合計質量的比例較佳為80質量%以上，更佳為90質量%以上。 The aforementioned (meth) acrylic resin (A-3) containing an acid group, in addition to the aforementioned amido-imine resin (a3-1) having an acid group or an anhydride group, and the aforementioned (meth) acrylate compound containing a hydroxyl group In addition to (a3-2), the (meth) acrylfluorene-containing epoxy compound (a3-3) and polycarboxylic anhydride (a3-4), other reaction materials may be used in combination with the desired resin properties and the like. In this case, the ratio of the total mass of the components (a3-1) to (a3-4) in the total mass of the reaction raw materials of the acid group-containing (meth) acrylate resin (A-3) is preferably 80 mass. % Or more, more preferably 90% by mass or more.

前述含酸基之(甲基)丙烯酸酯樹脂(A-3)的製造方法並無特別限定，可藉由任意方法製造。例如，可藉由使全部反應原料一次性反應的方法製造，亦可藉由使反應原料依序反應的方法製造。其中，較佳係以下述方法製造：使醯胺醯亞胺樹脂(a3-1)與含羥基之(甲基)丙烯酸酯化合物(a3-2)反應(步驟1)，使步驟1的生成物與含(甲基)丙烯醯基之環氧化合物(a3-3)反應(步驟2)，並使步驟2之生成物與前述多羧酸酐(a3-4)反應。 The manufacturing method of the said acid group containing (meth) acrylate resin (A-3) is not specifically limited, It can manufacture by any method. For example, it can manufacture by the method which makes all the reaction raw materials react at one time, and can also manufacture by the method which makes the reaction raw materials react sequentially. Among these, it is preferable to produce it by the method of reacting the amidine and imine resin (a3-1) with the hydroxyl-containing (meth) acrylate compound (a3-2) (step 1), and making the product of step 1 It is reacted with the (meth) acrylfluorene-containing epoxy compound (a3-3) (step 2), and the product of step 2 is reacted with the aforementioned polycarboxylic anhydride (a3-4).

前述步驟1係使醯胺醯亞胺樹脂(a3-1)與含羥基之(甲基)丙烯酸酯化合物(a3-2)反應的步驟。作為前述反應，主要是前述醯胺醯亞胺樹脂(a3-1)中的酸基或酸酐基與前述含羥基之(甲基)丙烯酸酯化合物(a3-2)中的羥基進行反應。由於前述含羥基之(甲基)丙烯酸酯化合物(a3-2)與酸酐基的反應性優異，因此如上所述，前述醯胺醯亞胺樹脂(a3-1)較佳為具有酸酐基。前述醯胺醯亞胺樹脂(a3-1)與前述含羥基之(甲基)丙烯酸酯化合物(a3-2)的反應比例，較佳係相對於前述醯胺醯亞胺樹脂(a3-1) 中的酸基及酸酐基之合計，以0.9~1.1莫耳的範圍使用前述含羥基之(甲基)丙烯酸酯化合物(a3-2)，特佳係相對於前述醯胺醯亞胺樹脂(a3-1)中的酸酐基之合計，以0.9~1.1莫耳的範圍使用前述含羥基之(甲基)丙烯酸酯化合物(a3-2)。前述醯胺醯亞胺樹脂(a3-1)中的酸酐基含量，可從前述兩種方式的酸價測量值的差分、亦即使酸酐基開環的條件下的酸價與未使酸酐基開環的條件下的酸價的差分而算出。 The aforementioned step 1 is a step of reacting the amidoamine imine resin (a3-1) with a hydroxyl group-containing (meth) acrylate compound (a3-2). As the aforementioned reaction, an acid group or an acid anhydride group in the amidoamine imine resin (a3-1) and a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a3-2) are mainly reacted. Since the hydroxyl group-containing (meth) acrylate compound (a3-2) is excellent in reactivity with an acid anhydride group, as described above, it is preferable that the amidinimide resin (a3-1) has an acid anhydride group. The reaction ratio of the amidamide ammine resin (a3-1) and the hydroxyl-containing (meth) acrylate compound (a3-2) is preferably relative to the amidamide ammine resin (a3-1) The total of the acid group and the acid anhydride group in the above is used in the range of 0.9 to 1.1 mol. The above-mentioned hydroxyl group-containing (meth) acrylate compound (a3-2) is particularly preferably used in comparison to the aforementioned amidoamine imine resin (a3 The total of the acid anhydride groups in -1) is in the range of 0.9 to 1.1 mol, and the aforementioned hydroxyl-containing (meth) acrylate compound (a3-2) is used. The content of the acid anhydride group in the amidamine and imine resin (a3-1) can be obtained from the difference between the measured values of the acid values of the two methods, and the acid value even when the acid anhydride group is ring-opened is not opened. It is calculated by the difference of the acid value under the condition of the ring.

前述醯胺醯亞胺樹脂(a3-1)與前述含羥基之(甲基)丙烯酸酯化合物(a3-2)的反應，例如，可在酯化反應觸媒的存在下、90~140℃左右的溫度條件下加熱攪拌而進行。作為前述酯化反應觸媒，可列舉例如：三甲膦、三丁膦、三苯膦等的磷化合物、三乙胺、三丁胺、二甲基芐胺等的胺化合物、2-甲基咪唑、2-十七基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-異丁基-2-甲基咪唑等的咪唑化合物等。此等反應觸媒可單獨使用亦可併用2種以上。 The reaction between the amidamine and imine resin (a3-1) and the hydroxyl-containing (meth) acrylate compound (a3-2) can be performed at, for example, about 90 to 140 ° C. in the presence of an esterification catalyst. It is carried out by heating and stirring under the temperature conditions. Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine; and 2-methylimidazole. , Imidazole compounds such as 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, and the like. These reaction catalysts may be used alone or in combination of two or more.

相對於反應原料的合計100質量份，前述反應觸媒的添加量較佳為0.001~5質量份的範圍。 The addition amount of the reaction catalyst is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total of the reaction raw materials.

前述步驟1的反應，亦可因應需求在有機溶媒中進行。使用之有機溶媒的選擇，可根據反應原料及生成物的含酸基之(甲基)丙烯酸酯樹脂的溶解性、反應溫度條件而適當選擇，可列舉例如：甲乙酮、丙酮、二甲基甲醯胺、甲基異丁酮、甲氧基丙醇、環己酮、甲基賽路蘇、二烷二醇單烷基醚乙酸酯、二烷二醇乙酸酯 等。此等有機溶媒可單獨使用，亦可併用2種以上而作為混合溶媒使用。連續進行前述醯胺醯亞胺樹脂(a3-1)的製造與步驟1的情況下，亦可在製造前述醯胺醯亞胺樹脂(a3-1)所使用的有機溶媒中直接繼續反應。 The reaction in step 1 can also be carried out in an organic solvent according to requirements. The choice of the organic solvent to be used can be appropriately selected according to the solubility of the acid group-containing (meth) acrylate resin of the reaction raw material and the product, and the reaction temperature conditions. Examples include methyl ethyl ketone, acetone, and dimethyl formamidine. Amines, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celex, dioxane monoalkyl ether acetate, dioxane glycol acetate, and the like. These organic solvents may be used alone or as a mixed solvent in combination of two or more. In the case where the production of the amidinofluorene imine resin (a3-1) and step 1 are continuously performed, the reaction may be continued directly in the organic solvent used for producing the amidinofluorine imine resin (a3-1).

前述步驟2係使前述步驟1所得到之生成物與含(甲基)丙烯醯基之環氧化合物(a3-3)反應的步驟。作為前述反應，主要是含(甲基)丙烯醯基之環氧化合物(a3-3)與前述步驟1之生成物中的羧基進行反應。其反應比例，相對於步驟1之生成物中的羧基，較佳係以0.5~1.2莫耳的範圍使用前述含(甲基)丙烯醯基之環氧化合物(a3-3)，更佳係以0.9~1.1莫耳的範圍使用。步驟2的反應，例如，可在酯化反應觸媒的存在下、90~140℃左右的溫度條件下加熱攪拌而進行。連續進行步驟1與步驟2的情況下，可不追加酯化反應觸媒，亦可適當追加。又，亦可因應需求在有機溶媒中進行反應。 The aforementioned step 2 is a step of reacting the product obtained in the aforementioned step 1 with the (meth) acrylfluorenyl-containing epoxy compound (a3-3). As the aforementioned reaction, the (meth) acrylfluorenyl-containing epoxy compound (a3-3) is mainly reacted with the carboxyl group in the product of the aforementioned step 1. The reaction ratio is preferably 0.5 to 1.2 moles relative to the carboxyl group in the product of Step 1. The aforementioned (meth) acrylfluorenyl-containing epoxy compound (a3-3) is more preferably used. Use in the range of 0.9 ~ 1.1 mol. The reaction in step 2 can be carried out, for example, by heating and stirring in the presence of an esterification catalyst at a temperature of about 90 to 140 ° C. When step 1 and step 2 are performed continuously, the esterification reaction catalyst may not be added, and may be added appropriately. In addition, the reaction may be performed in an organic solvent as required.

前述步驟3係使前述步驟2所得到之生成物與多羧酸酐(a3-4)反應的步驟。作為前述反應，主要是前述多羧酸酐(a3-4)與前述步驟2之生成物中的羥基進行反應。其反應比例，較佳係以最終生成物的含酸基之(甲基)丙烯酸酯樹脂(A-3)的酸價成為50~100mgKOH/g左右的方式進行調整。前述步驟3的反應，例如，可在酯化反應觸媒的存在下、90~140℃左右的溫度條件下加熱攪拌而進行。連續進行步驟2與步驟3的情況下，可不追加酯化反應觸媒，亦可適當追加。又，亦可因應需求在有機溶媒中進行反應。 The step 3 is a step of reacting the product obtained in the step 2 with a polycarboxylic anhydride (a3-4). As said reaction, the said polycarboxylic anhydride (a3-4) mainly reacts with the hydroxyl group in the product of the said 2nd step. The reaction ratio is preferably adjusted so that the acid value of the acid group-containing (meth) acrylate resin (A-3) in the final product becomes about 50 to 100 mgKOH / g. The reaction in the step 3 can be carried out, for example, by heating and stirring in the presence of an esterification catalyst at a temperature of about 90 to 140 ° C. When step 2 and step 3 are performed continuously, the esterification reaction catalyst may not be added, and may be added appropriately. In addition, the reaction may be performed in an organic solvent as required.

前述含酸基之(甲基)丙烯酸酯樹脂(A-3)的酸價，從可得到具有高光感度且可形成耐熱性優異之硬化物的含酸基之(甲基)丙烯酸酯樹脂組成物來看，較佳為30~150mgKOH/g的範圍，更佳為40~100mgKOH/g的範圍。此外，在本案發明中，含酸基之(甲基)丙烯酸酯樹脂(A-3)的酸價係以JIS K 0070(1992)的中和滴定法所測量的值。 The acid value of the acid group-containing (meth) acrylate resin (A-3) can be obtained from the acid group-containing (meth) acrylate resin composition which has a high light sensitivity and can form a cured product having excellent heat resistance. In view of this, a range of 30 to 150 mgKOH / g is preferable, and a range of 40 to 100 mgKOH / g is more preferable. In the present invention, the acid value of the acid group-containing (meth) acrylate resin (A-3) is a value measured by a neutralization titration method of JIS K 0070 (1992).

針對前述光聚合起始劑(B)進行說明。 The photopolymerization initiator (B) will be described.

作為前述光聚合起始劑(B)，係使用以下述通式(1)表示之化合物。 As the photopolymerization initiator (B), a compound represented by the following general formula (1) is used.

Figure TW201944173A_D0036
Figure TW201944173A_D0036

於本發明，上述通式(1)中，以下述結構式

Figure TW201944173A_D0037
In the present invention, the general formula (1) has the following structural formula
Figure TW201944173A_D0037

表示之結構部位因光照射而產生自由基，藉此發揮作為聚合起始劑的功能。本發明中，儘管分子量較大而其自由基產生部位的量相對變少，仍可表現優異的硬化性，此點特別值得一提。 The indicated structural sites generate radicals by light irradiation, thereby functioning as a polymerization initiator. In the present invention, although the molecular weight is large and the amount of the radical generating site is relatively small, it can still exhibit excellent hardenability, which is particularly worth mentioning.

此處，前述通式(1)中，R1表示甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、 戊基、己基、庚基、辛基、壬基、癸基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、異癸基等的碳原子數1~10之烷基。此等之中，從因光照射所產生之自由基的反應性之點來看，較佳為乙基。 Here, in the general formula (1), R 1 represents methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, 1, Alkyl groups having 1 to 10 carbon atoms such as 1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, and isodecyl. Among these, in view of the reactivity of radicals generated by light irradiation, ethyl is preferred.

接著，前述通式(1)中，R2及R3分別獨立表示甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基等的碳原子數1~12之直鏈狀或分支狀烷基；羥乙基、羥丙基、羥丁基等的碳原子數2~4之羥烷基；甲氧基乙基；乙氧基乙基；R2及R3成為一體而表示與氮原子一起形成環結構的伸烷基，亦即就相當於

Figure TW201944173A_D0038
Next, in the general formula (1), R 2 and R 3 each independently represent methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, or pentyl. Alkyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. linear or branched alkyl groups having 1 to 12 carbon atoms; hydroxyethyl, hydroxypropyl, hydroxy A hydroxyalkyl group having 2 to 4 carbon atoms such as butyl; methoxyethyl group; ethoxyethyl group; R 2 and R 3 are integrated and represent an alkylene group that forms a ring structure with a nitrogen atom, that is, Is equivalent to
Figure TW201944173A_D0038

的結構而言，表示形成以下述結構式

Figure TW201944173A_D0039
The structure of
Figure TW201944173A_D0039

表示之吡咯啶結構或哌啶結構的伸丁基、戊烯基；R2及R3成為一體而表示與氮原子一起形成

Figure TW201944173A_D0040
啉骨架、N-甲基哌
Figure TW201944173A_D0041
骨架、2,6-二甲基
Figure TW201944173A_D0042
啉骨架的環結構形成部位，亦即就相當於
Figure TW201944173A_D0043
 A pyrrolidine structure or a piperidine structure of butylene and pentenyl; R 2 and R 3 are integrated and are formed together with a nitrogen atom
Figure TW201944173A_D0040
Porphyrin skeleton, N-methyl piperazine
Figure TW201944173A_D0041
Backbone, 2,6-dimethyl
Figure TW201944173A_D0042
The ring structure forming site of the morpholine skeleton is equivalent to
Figure TW201944173A_D0043

的結構而言，表示形成下述結構式

Figure TW201944173A_D0044
In terms of the structure, it shows the following structural formula
Figure TW201944173A_D0044

的結構部位。此等之中，特別是從合成上之高產率之點來看，較佳為碳原子數1~12之直鏈狀或分支狀烷基。 Structural parts. Among these, a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferred from the viewpoint of high synthetic yield.

前述通式(1)中，R4~R7分別獨立，表示氫原子；甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基等的碳原子數1~8之烷基；或苯基。此等之中，從原料的取得簡易度之點來看，較佳係R4~R7皆為氫原子。 In the aforementioned general formula (1), R 4 to R 7 are each independently a hydrogen atom; methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, or secondary butyl , Pentyl, hexyl, heptyl, octyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, etc. An alkyl group having 1 to 8 atoms; or a phenyl group. Among these, it is preferable that all of R 4 to R 7 are hydrogen atoms in view of the ease of obtaining the raw materials.

又，前述通式(1)中，X1表示伸乙基、1,3-伸丙基、1,2-伸丙基或2,3-伸丙基，X2表示氫原子或甲基，X3表示氫原子、甲基或乙基，或者X2及X3在虛線部形成共價鍵並且一體地表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，或者X1、X2及X3一體地表示以下述結構式(X-1)所表示之與氮原子一起構成雙環的4價之脂肪族烴基。 Furthermore, in the general formula (1), X 1 represents an ethylidene group, 1,3-propylidene group, 1,2-propylidene group, or 2,3-propylidene group, X 2 represents a hydrogen atom or a methyl group, X 3 represents a hydrogen atom, a methyl group, or an ethyl group, or X 2 and X 3 form a covalent bond in a dotted line portion and integrally represent an ethylidene group, a 1,3-propylidene group, a 1,2-propylidene group, and 2 , 3-propenyl, or X 1 , X 2, and X 3 collectively represent a tetravalent aliphatic hydrocarbon group represented by the following structural formula (X-1) and forming a bicyclic ring with a nitrogen atom.

Figure TW201944173A_D0045
Figure TW201944173A_D0045

此等之中，作為藉由上述X1、X2及X3與氮原子所構成的以下述部分結構式

Figure TW201944173A_D0046
Among these, the following partial structural formulas constituted by the above-mentioned X 1 , X 2, and X 3 and a nitrogen atom are
Figure TW201944173A_D0046

(式中，*表示與其他結構部位的連接鍵。) (In the formula, * represents a connection key with other structural parts.)

表示之結構部位，可列舉

Figure TW201944173A_D0047
Structure parts indicated, can be listed
Figure TW201944173A_D0047

(式中，*表示與其他結構部位的連接鍵。) (In the formula, * represents a connection key with other structural parts.)

等，但從前述通式(1)表示之化合物的製造方法的[步驟V]中的產率變高之點來看，較佳為以下述結構式表示者。 Etc. However, from the viewpoint that the yield in [Step V] of the method for producing a compound represented by the aforementioned general formula (1) is high, it is preferably represented by the following structural formula.

Figure TW201944173A_D0048
Figure TW201944173A_D0048

接著，通式(1)中，Y1可列舉：丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、異癸基、1-甲基十一基或1,1,3,3,5,5-六甲基己基等的直鏈狀或分支狀的烷基、環庚基、環己基、環戊基；1-氟丙基、1,1,1-三氟丙基、1,1,1-三氟丁基、2-三氟甲基丙基、1,1,1,2,2-五氟丙基、1,1,1,2,2-五氟戊基、1,1,1,2,2,3,3-七氟丙基、1,1,1,2,2,3,3-七氟丁基、2-(全氟丁基)乙基、1-氯丙基、1,1,1-三氯丙基、1-氯丁基、1,1,1-三氯丁基、1-氯己基、1,1,1-三氯己基、1-氯十二基、1,1,1-三氯十二基、1-氯十八基、1,1,1-三氯十八基；1-羥丙基、2-羥丙基、1-羥丁基、1-羥己基、1-羥基十二基、1-羥基十八基等不具有取代基或者具有鹵素原子或羥基作為取代基的碳原子數3~18之烷基(y1-1)；苄基、甲氧基苄基、氯苄基、羥基苄基、苯乙基、苯基苄基、甲氧基苯基苄基、萘基甲基、甲氧基萘基甲基、苯基丙基、苯基丙烯基、苯氧基苄基、甲硫基苄基、聯三苯基甲基等的碳原子數7~19之芳烷基(y1-2)； 以下述結構式(y1-3)表示之結構部位(y1-3)、

Figure TW201944173A_D0049
Next, in the general formula (1), Y 1 includes propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptyl, octadecyl, 2-ethylbutyl, isopentyl, 1 -Methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 2,2,4,4-tetramethyl Butylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, isopropyl Linear or branched alkyl, cycloheptyl, cyclohexyl, cyclopentyl, such as decyl, 1-methylundecyl, or 1,1,3,3,5,5-hexamethylhexyl; 1-fluoropropyl, 1,1,1-trifluoropropyl, 1,1,1-trifluorobutyl, 2-trifluoromethylpropyl, 1,1,1,2,2-pentafluoropropyl Base, 1,1,1,2,2-pentafluoropentyl, 1,1,1,2,2,3,3-heptafluoropropyl, 1,1,1,2,2,3,3- Heptafluorobutyl, 2- (perfluorobutyl) ethyl, 1-chloropropyl, 1,1,1-trichloropropyl, 1-chlorobutyl, 1,1,1-trichlorobutyl, 1-chlorohexyl, 1,1,1-trichlorohexyl, 1-chlorododecyl, 1,1,1-trichlorododecyl , 1-chlorooctadecyl, 1,1,1-trichlorooctadecyl; 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 1-hydroxyhexyl, 1-hydroxydodecyl Alkyl groups (y1-1) having 3 to 18 carbon atoms which do not have a substituent or a halogen atom or a hydroxyl group as substituents, such as 1-hydroxyoctadecyl; benzyl, methoxybenzyl, chlorobenzyl, Hydroxybenzyl, phenethyl, phenylbenzyl, methoxyphenylbenzyl, naphthylmethyl, methoxynaphthylmethyl, phenylpropyl, phenylpropenyl, phenoxybenzyl, Arylalkyl (y1-2) having 7 to 19 carbon atoms, such as methylthiobenzyl, bitriphenylmethyl, etc .; a structural site (y1-3) represented by the following structural formula (y1-3),
Figure TW201944173A_D0049

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子或苯基或碳原子數1~4之烷基，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom or a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20.)

以下述結構式(y1-4)表示之結構部位(y1-4)、

Figure TW201944173A_D0050
Structural parts (y1-4) represented by the following structural formula (y1-4),
Figure TW201944173A_D0050

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子、苯基或碳數1~4之烷基，R10表示氫原子或甲基，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, and m represents 0 to 20 Integer.)

以下述結構式(y1-5)表示之結構部位(y1-5)、

Figure TW201944173A_D0051
Structural parts (y1-5) represented by the following structural formula (y1-5),
Figure TW201944173A_D0051

(式中，R10表示氫原子或甲基，R11表示碳原子數1~18之烷基或碳原子數6~18之芳基。) (In the formula, R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)

以下述結構式(y1-6)表示之結構部位(y1-6)、

Figure TW201944173A_D0052
The structural part (y1-6) represented by the following structural formula (y1-6),
Figure TW201944173A_D0052

(式中，R12表示碳原子數1~18之烷基。) (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)

以下述結構式(y1-7)表示之結構部位(y1-7)、

Figure TW201944173A_D0053
Structural parts (y1-7) represented by the following structural formula (y1-7),
Figure TW201944173A_D0053

(式中，R8表示碳原子數2~4之伸烷基，R13表示氫原子、碳原子數1~6之烷基或鹵素原子，m表示0~20之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and m represents an integer of 0 to 20.)

以下述結構式(y1-8)表示之結構部位(y1-8)、

Figure TW201944173A_D0054
Structural parts (y1-8) represented by the following structural formula (y1-8),
Figure TW201944173A_D0054

(式中，R8表示碳原子數2~4之伸烷基，R10表示氫原子或甲基，R14表示具有p+1個連接鍵的碳原子數5~18之烴基，1表示0~20之整數，p表示1~3之整數。) (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, R 14 represents a hydrocarbon group having 5 to 18 carbon atoms having p + 1 connection bonds, and 1 represents 0. An integer of ~ 20, p represents an integer of 1 to 3.)

以下述結構式(y1-9)表示之結構部位(y1-9)。 The structural part (y1-9) represented by the following structural formula (y1-9).

Figure TW201944173A_D0055
Figure TW201944173A_D0055

(式中，R15表示碳原子數4~18之烷基、碳原子數6~10之脂肪族環狀烴基、芳香族基。) (In the formula, R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, and an aromatic group.)

此處，前述結構式(y1-3)中，作為R8的碳原子數2~4之伸烷基，可列舉：正伸丙基、1,2-伸丙基、 正伸丁基、2-甲基-丙-1,2-二基等；又，作為R9中的碳原子數1~4之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基或二級丁基等。 Here, as the alkylene group having 2 to 4 carbon atoms in R 8 in the structural formula (y1-3), n-propyl, 1,2-propyl, n-butyl, and 2-methyl are listed. -Propyl-1,2-diyl and the like; Examples of the alkyl group having 1 to 4 carbon atoms in R 9 include methyl, ethyl, propyl, isopropyl, n-butyl, and iso Butyl, tertiary butyl or secondary butyl, etc.

前述結構部位(y1-4)中的R8及R9係與前述結構式(y1-3)同義。 R 8 and R 9 in the structural portion (y1-4) are synonymous with the structural formula (y1-3).

前述結構式(y1-5)中，作為R11的碳原子數1~18之烷基或碳原子數1~18之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、異癸基、1-甲基十一基或1,1,3,3,5,5-六甲基己基等的直鏈狀或分支狀烷基、環庚基、環己基、環戊基等的環烷基等；另一方面，作為碳原子數6~18之芳基，可列舉：苯基、苄基、苯乙基、聯苯基、萘基、甲苯基、二甲苯基、

Figure TW201944173A_D0056
基、
Figure TW201944173A_D0057
基、氯苯基、溴苯基、氯甲基苯基、羥苯基、甲氧基苯基、乙氧基苯基、苯氧基苯基、乙醯氧基苯基、苯甲醯氧基苯基、甲硫基苯基、苯硫基苯基、甲胺基苯基、二甲胺基苯基、乙醯基胺基苯基、羧苯基、甲氧基羰基苯基、苯氧基羰基苯基、N-苯基胺甲醯基苯基、氰基苯基、磺苯基、磺酸根基苯基、膦醯基苯基及膦酸根基苯基等。 Examples of the alkyl group having 1 to 18 carbon atoms or the alkyl group having 1 to 18 carbon atoms in R 11 in the structural formula (y1-5) include methyl, ethyl, propyl, isopropyl, N-butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl , Pentadecyl, hexadecyl, heptyl, octadecyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl , Isoheptyl, 1,1,3,3-tetramethylbutyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethyl Hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, isodecyl, 1-methylundecyl, or 1,1,3,3,5, Linear or branched alkyl groups such as 5-hexamethylhexyl, cycloalkyl groups such as cycloheptyl, cyclohexyl, cyclopentyl, etc. On the other hand, as aryl groups having 6 to 18 carbon atoms, Examples: phenyl, benzyl, phenethyl, biphenyl, naphthyl, tolyl, xylyl,
Figure TW201944173A_D0056
base,
Figure TW201944173A_D0057
Methyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxyphenyl, benzophenoxy Phenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, phenoxy Carbonylphenyl, N-phenylaminomethylmethylphenyl, cyanophenyl, sulfophenyl, sulfonylphenyl, phosphinophenyl, and phosphonophenyl.

前述結構式(y1-6)中，作為R12的碳原子數1~18之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、異癸基、1-甲基十一基或1,1,3,3,5,5-六甲基己基等的直鏈狀或分支狀烷基、環庚基、環己基、環戊基等的環烷基等。 Examples of the alkyl group having 1 to 18 carbon atoms in R 12 in the structural formula (y1-6) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tertiary Butyl, secondary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, ten Heptyl, octadecyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3 , 3-tetramethylbutyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, 1,1,3-tri Linear chains of methylhexyl, 1,1,3,3-tetramethylpentyl, isodecyl, 1-methylundecyl or 1,1,3,3,5,5-hexamethylhexyl, etc. Cycloalkyl groups such as shaped or branched alkyl, cycloheptyl, cyclohexyl, cyclopentyl and the like.

前述結構式(y1-7)中的R8與結構部位(y1-3)中的R8同義；作為R13的碳原子數1~6之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基等；作為鹵素原子，可列舉：溴原子、氯原子、氟原子。 In the foregoing structural formula and the structural moiety R 8 (y1-3) (y1-7) is synonymous R 8; R 13 carbon atoms in the alkyl group of 1 to 6, include: methyl, ethyl, propyl Base, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3 -Dimethylbutyl and the like; examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom.

前述結構式(y1-8)中的R8與結構部位(y1-3)中的R8同義；R14中所謂具有p+1個連接鍵的碳原子數3~25之烴基，可列舉：甘油殘基、三羥甲基丙烷殘基、新戊四醇殘基等的脂肪族多元醇殘基；正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基、1,7-庚烷二基、1,8-辛烷二基、1,9-壬烷二基、1,10-癸烷二基、3,8-癸烷二基、1,11-十一烷二基、1,12-十二烷二基、1,13-十三烷二基、1,14-十四烷二基、 1,15-十五烷二基、1,16-十六烷二基、1,17-十七烷二基、1,18-十八烷二基、1,19-十九烷二基、1,20-二十烷二基、1,21-二十一烷二基、1,22-二十二烷二基、1,23-二十三烷二基、1,24-二十四烷二基、1,25-二十五烷二基。 R 8 and structural formula structural site (y1-8) of (y1 - 3) in same meaning as R 8; R & lt called 14 having a number p + 1 linkages hydrocarbon group having 3 to 25 carbon atoms of, include: Glycerol residues, trimethylolpropane residues, neopentyl alcohol residues, and other aliphatic polyol residues; n-propyl, 1,2-propyl, n-butyl, 2-methyl-propane- 1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl Base, 1,10-decanediyl, 3,8-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl, 1,13-tridecanediyl, 1,14-tetradecanediyl, 1,15-pentadecanediyl, 1,16-hexadecanediyl, 1,17-heptadecanediyl, 1,18-octadecanediyl, 1,19-Undecanediyl, 1,20-Eicosanediyl, 1,21-Eicosanediyl, 1,22-Eicosanediyl, 1,23-Eicosanediyl Diyl, 1,24-tetracosanediyl, 1,25-pentadecanediyl.

此處，所謂殘基表示除了多元醇的羥基以外的烴結構部位。 Here, the term "residue" means a hydrocarbon structure site other than the hydroxyl group of the polyhydric alcohol.

以上詳述的通式(1)中的Y1所示之結構部位中，特別是前述碳原子數3~18之烷基(y1-1)、以前述結構式(y1-4)表示之結構部位(y1-4)、以前述結構式(y1-5)表示之結構部位(y1-5)、以前述結構式(y1-8)表示之結構部位(y1-8)，在合成以前述通式(1)表示之化合物時容易導入Y1，而且可得到具有高光感度及硬化物之優異耐熱性、且不易發生逸氣的感光性樹脂組成物，因而較佳，更佳為前述結構部位(y1-8)。 Among the structural sites represented by Y 1 in the general formula (1) described above, in particular, the aforementioned alkyl group (y1-1) having 3 to 18 carbon atoms and the structure represented by the aforementioned structural formula (y1-4) The part (y1-4), the structural part (y1-5) represented by the aforementioned structural formula (y1-5), and the structural part (y1-8) represented by the aforementioned structural formula (y1-8) are synthesized by the aforementioned general formula The compound represented by the formula (1) is easy to introduce Y 1 , and a photosensitive resin composition having high light sensitivity and excellent heat resistance of hardened materials and less outgassing can be obtained. Therefore, it is more preferable, and more preferably, it is the aforementioned structural portion ( y1-8).

接著，前述通式(1)中的下述結構式1a所表示之結構部位可從上述各種結構任意選擇，但從可得到具有高光感度及硬化物之優異耐熱性、且不易發生逸氣之感光性樹脂組成物來看，較佳為該結構式1a所示部分的總質量數為300~2000。 Next, the structural site represented by the following structural formula 1a in the aforementioned general formula (1) can be arbitrarily selected from the various structures described above, but a light-sensitive photoreceptor having high light sensitivity and excellent heat resistance of hardened materials and less prone to outgassing can be obtained From the viewpoint of the resin composition, the total mass of the portion shown in the structural formula 1a is preferably 300 to 2000.

Figure TW201944173A_D0058
Figure TW201944173A_D0058

(結構式1a中，X1、X2、X3、R4~R7及Y1係與通式(1)同義)。 (In the structural formula 1a, X 1 , X 2 , X 3 , R 4 to R 7, and Y 1 are synonymous with the general formula (1)).

接著，前述通式(1)中，如上所述，Y2係該結構部位末端具有氮原子或氧原子的具有(n+1)個連接鍵之有機連結基，具體而言，從原料容易取得、且容易控制反應之點來看，較佳為選自包含下述所示之結構部位(y2-1)~(y2-6)之群組的醯胺鍵形成型結構部位、或以下述所示結構部位(y2-7)~(y2-9)表示之酯鍵形成型結構部位。 Next, in the aforementioned general formula (1), as described above, Y 2 is an organic linking group having (n + 1) connecting bonds having a nitrogen atom or an oxygen atom at the end of the structural site. Specifically, it can be easily obtained from raw materials. In view of the ease of controlling the reaction, it is preferred that the amine bond-forming structural site selected from the group consisting of the structural sites (y2-1) to (y2-6) shown below, or The structural sites shown in (y2-7) to (y2-9) are ester bond-forming structure sites.

此處，前述結構部位(y2-1)係前述通式(1)中的n為1且以下述結構式(y2-1)表示的結構部位。 Here, the structural site (y2-1) is a structural site where n in the general formula (1) is 1 and is represented by the following structural formula (y2-1).

-NH-R16-NH- (y2-1) -NH-R 16 -NH- (y2-1)

(式中，R16表示碳原子數2~18之直鏈或環狀伸烷基、伸苯基、伸茬基、具有碳原子數1~3之烷基作為核取代基的伸苯基、具有碳原子數1~3之烷基作為核取代基的伸茬基)。 (Wherein R 16 represents a linear or cyclic alkylene group having 2 to 18 carbon atoms, a phenylene group, a stubyl group, a phenylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent, (Stubby group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent).

作為構成前述結構式(y2-1)中之R16的碳原子數2~18之直鏈或環狀伸烷基，可列舉：伸乙基、正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基、1,7-庚烷二基、1,8-辛烷二基、1,9-壬烷二基、1,10-癸烷二基、3,8-癸烷二基、1,11-十一烷二基、1,12-十二烷二基、1,13-十三烷二基、1,14-十四烷二基、1,15-十五烷二基、1,16-十六烷二基、1,17-十七烷二基、1,18-十八烷二基、1,4-環己烷二基。 Examples of the straight-chain or cyclic alkylene group having 2 to 18 carbon atoms constituting R 16 in the aforementioned structural formula (y2-1) include ethylidene, n-propylidene, 1,2-propylidene, N-butylene, 2-methyl-propane-1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octyl Alkanediyl, 1,9-nonanediyl, 1,10-decanediyl, 3,8-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl , 1,13-tridecanediyl, 1,14-tetradecanediyl, 1,15-pentadecanediyl, 1,16-hexadecanediyl, 1,17-heptadecanediyl , 1,18-octadecanediyl, 1,4-cyclohexanediyl.

又，前述結構式(y2-1)中，就具有碳原子數1~3之烷基作為核取代基的伸苯基而言，可列舉：甲基 伸苯基、乙基伸苯基、正丙基伸苯基、異丙基伸苯基；又，就具有碳原子數1~3之烷基作為核取代基的伸茬基而言，可列舉：甲基伸茬基、乙基伸茬基、正丙基伸茬基、異丙基伸茬基。 Further, in the structural formula (y2-1), as the phenylene group having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent, methyl phenylene, ethyl phenylene, and n-propyl are listed. Phenylphenyl, isopropylphenyl; and stubyl groups having an alkyl group having 1 to 3 carbon atoms as a nuclear substituent, methyl stubyl, ethyl stubyl, and n-propyl Base extension base, isopropyl extension base.

此等之中，作為該結構部位(y2-1)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二胺化合物之點來看，較佳為以下述結構式表示者。 Among these, as the structural portion (y2-1), specifically, it is easy to obtain a constituent material of the aforementioned structure in the manufacturing method [Step IV] of the compound represented by the general formula (1) described later, which is easy to obtain. From the viewpoint of the diamine compound, it is preferably represented by the following structural formula.

Figure TW201944173A_D0059
Figure TW201944173A_D0059

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

前述結構部位(y2-2)係前述通式(1)中的n為1且以下述結構式表示者。 The structural site (y2-2) is a structure in which n in the general formula (1) is 1 and is represented by the following structural formula.

Figure TW201944173A_D0060
Figure TW201944173A_D0060

(式中，R17表示碳原子數2~6之直鏈狀、分支狀伸烷基或伸苯基，R18表示碳原子數2~6之直鏈狀、分支狀伸烷基或伸苯基，q表示0~12之整數)。 (In the formula, R 17 represents a linear, branched alkylene or phenylene group having 2 to 6 carbon atoms, and R 18 represents a linear, branched alkylene or phenylene group having 2 to 6 carbon atoms. Base, q represents an integer from 0 to 12).

此處，作為構成通式(y2-2)中之R17及R18的碳原子數2~6之直鏈狀、分支狀伸烷基，可列舉例如：伸乙基、正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基。 Here, as the linear and branched alkylene group having 2 to 6 carbon atoms constituting R 17 and R 18 in the general formula (y2-2), for example, ethylene, n-propyl, 1 2,2-propylidene, n-butylene, 2-methyl-propane-1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl.

作為該結構部位(y2-2)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二胺化合物之點來看，較佳為以下述結構式表示者。 As this structural part (y2-2), specifically, it is easy to obtain the diamine compound which becomes the structural raw material of the said structure in the manufacturing method [step IV] of the compound represented by the said general formula (1) mentioned later. From a viewpoint, it is preferable to express it by the following structural formula.

Figure TW201944173A_D0061
Figure TW201944173A_D0061

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

前述結構部位(y2-3)係前述通式(1)中的n為1且以下述結構式(y2-3)表示者。 The structural site (y2-3) is a structure in which n in the general formula (1) is 1 and is represented by the following structural formula (y2-3).

Figure TW201944173A_D0062
Figure TW201944173A_D0062

(式中，R19~R22分別獨立，表示氫或碳原子數1~3之直鏈狀、分支狀烷基)。 (In the formula, R 19 to R 22 are each independently and represent hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms.)

此處，所謂構成R19~R22的碳原子數1~3之直鏈狀、分支狀烷基，可列舉：甲基、乙基、丙基及異丙基。 Here, the linear or branched alkyl group having 1 to 3 carbon atoms constituting R 19 to R 22 includes methyl, ethyl, propyl, and isopropyl.

作為該結構部位(y2-3)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二胺化合物之點來看，較佳為以下述結構式表示者。 As this structural site (y2-3), specifically, it is easy to obtain a diamine compound which becomes a constituent raw material of the above-mentioned structure in the production method [Step IV] of the compound represented by the general formula (1) described later, which is easy to obtain. From a viewpoint, it is preferable to express it by the following structural formula.

Figure TW201944173A_D0063
Figure TW201944173A_D0063

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

前述結構部位(y2-4)係前述通式(1)中的n為1且以下述結構式(y2-4)表示者。 The structural site (y2-4) is a structure in which n in the general formula (1) is 1 and is represented by the following structural formula (y2-4).

Figure TW201944173A_D0064
Figure TW201944173A_D0064

(式中，R23表示氧原子、亞甲基、伸乙基、亞乙基、2,2-伸丙基或1,3-伸丙基)。 (In the formula, R 23 represents an oxygen atom, a methylene group, an ethylene group, an ethylene group, 2,2-propylene group, or 1,3-propylene group).

作為該結構部位(y2-4)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二胺化合物之點來看，較佳為以下述結構式表示者。 As this structural part (y2-4), specifically, it is easy to obtain the diamine compound which becomes the structural raw material of the said structure in the manufacturing method [step IV] of the compound represented by the said general formula (1) mentioned later. From a viewpoint, it is preferable to express it by the following structural formula.

Figure TW201944173A_D0065
Figure TW201944173A_D0065

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

前述結構部位(y2-5)係前述通式(1)中的n為1且以下述結構式(y2-5)表示者。 The structural portion (y2-5) is one in which n in the general formula (1) is 1 and is represented by the following structural formula (y2-5).

Figure TW201944173A_D0066
Figure TW201944173A_D0066

(式中，R24分別獨立表示氫原子或碳原子數1~3之直鏈狀、分支狀烷基，R25分別獨立表示氫原子或碳原子 數1~3之直鏈狀、分支狀烷基，R26表示氧原子、亞甲基、2,2-伸丙基、磺醯基或羰基)。 (In the formula, R 24 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and R 25 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms. And R 26 represents an oxygen atom, a methylene group, a 2,2-propylidene group, a sulfofluorenyl group or a carbonyl group).

此處，所謂構成R24或R25的碳原子數1~3之直鏈狀、分支狀烷基，可列舉：甲基、乙基、丙基及異丙基。 Here, the linear or branched alkyl group having 1 to 3 carbon atoms constituting R 24 or R 25 includes a methyl group, an ethyl group, a propyl group, and an isopropyl group.

作為該結構部位(y2-5)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二胺化合物之點來看，較佳為以下述結構式表示者。 As this structural part (y2-5), specifically, it is easy to obtain the diamine compound which becomes the structural raw material of the said structure in the manufacturing method [step IV] of the compound represented by the said general formula (1) mentioned later. From a viewpoint, it is preferable to express it by the following structural formula.

Figure TW201944173A_D0067
Figure TW201944173A_D0067

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

前述結構部位(y2-6)係前述通式(1)中的n為2或3且以下述結構式(y2-6)表示者。 The structural portion (y2-6) is one in which n in the general formula (1) is 2 or 3 and is represented by the following structural formula (y2-6).

Figure TW201944173A_D0068
Figure TW201944173A_D0068

(式中，R27為碳原子數2~6之伸烷基，R28係碳原子數4~12之連接鍵數為(n+1)價的烴基，r為0~3之整數)。 (In the formula, R 27 is an alkylene group having 2 to 6 carbon atoms, and R 28 is a hydrocarbon group having a linking number of 4 to 12 carbon atoms (n + 1), and r is an integer of 0 to 3).

此處，作為構成R27的碳原子數2~6之伸烷基，可列舉：伸乙基、正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基；作為構成R28的碳原子數4~12之連接鍵數為(n+1)價的烴基，可列舉多元醇的殘基，可列舉例如：三羥甲基丙烷殘基、新戊四醇殘基、甘油殘基、二-三羥甲基丙烷殘基。此處，所謂「殘基」係從該多元醇除去羥基的烴結構部位。 Here, examples of the alkylene group having 2 to 6 carbon atoms constituting R 27 include ethylidene, n-propylidene, 1,2-propylidene, n-butylidene, and 2-methyl-propane-1. 2,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl; as a hydrocarbon group having 4 to 12 carbon atoms constituting R 28 and having a (n + 1) valent hydrocarbon group, Examples of the polyhydric alcohol residue include a trimethylolpropane residue, a neopentyl alcohol residue, a glycerol residue, and a di-trimethylolpropane residue. Here, the "residue" is a hydrocarbon structure site where a hydroxyl group is removed from the polyol.

作為該結構部位(y2-6)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二胺化合物之點來看，較佳為以下述結構式表示者。 As this structural part (y2-6), specifically, it is easy to obtain the diamine compound which becomes the structural raw material of the said structure in the manufacturing method [step IV] of the compound represented by the said general formula (1) mentioned later. From a viewpoint, it is preferable to express it by the following structural formula.

Figure TW201944173A_D0069
Figure TW201944173A_D0069

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

接著，酯鍵形成型結構部位的結構部位(y2-7)係前述通式(1)中的n為1且以下述結構式(y2-7)表示者。 Next, the structural site (y2-7) of the ester-bond-forming structural site is one in which n in the general formula (1) is 1 and is represented by the following structural formula (y2-7).

-O-R29-O- (y2-7) -OR 29 -O- (y2-7)

(式中，R29表示碳原子數2~18之直鏈、分支狀或環狀伸烷基、伸苯基、伸茬基)。 (In the formula, R 29 represents a linear, branched or cyclic alkylene group, a phenylene group, or a stubyl group having 2 to 18 carbon atoms.)

此處，構成R29的碳原子數2~18之直鏈、分支狀或環狀伸烷基，可列舉：伸乙基、正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基、1,7-庚烷二基、1,8-辛烷二基、1,9-壬烷二基、1,10-癸烷二基、3,8-癸烷二基、1,11-十一烷二基、1,12-十二烷二基、1,13-十三烷二基、1,14-十四烷二基、1,15-十五烷二基、1,16-十六烷二基、1,17-十七烷二基、1,18-十八烷二基、1,4-環己烷二基。 Here, the straight-chain, branched, or cyclic alkylene group having 2 to 18 carbon atoms constituting R 29 can be exemplified by ethylene, n-propyl, 1,2-propyl, n-butyl, 2 -Methyl-propane-1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1 , 9-nonanediyl, 1,10-decanediyl, 3,8-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl, 1,13- Tridecanediyl, 1,14-tetradecanediyl, 1,15-pentadecanediyl, 1,16-hexadecanediyl, 1,17-heptadecanediyl, 1,18- Octadecanediyl, 1,4-cyclohexanediyl.

作為該結構部位(y2-7)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二元醇化合物之點來看，較佳為以下述結構式表示者。 As this structural site (y2-7), specifically, the diol compound which becomes a constituent raw material of the said structure in the manufacturing method [step IV] which is easy to obtain the compound represented by the said general formula (1) mentioned later is easily obtained. From the point of view, it is preferably expressed by the following structural formula.

Figure TW201944173A_D0070
Figure TW201944173A_D0070

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

接著，酯鍵形成型結構部位的結構部位(y2-8)係前述通式(1)中的n為1且以下述結構式(y2-8)表示者。 Next, the structural site (y2-8) of the ester-bond-forming structural site is one in which n in the general formula (1) is 1 and represented by the following structural formula (y2-8).

Figure TW201944173A_D0071
Figure TW201944173A_D0071

(式中，R30分別獨立表示碳原子數2~6之伸烷基，q表示1~20之整數)。 (In the formula, R 30 each independently represents an alkylene group having 2 to 6 carbon atoms, and q represents an integer of 1 to 20).

此處，作為構成R30的碳原子數2~6之伸烷基，可列舉：伸乙基、正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基。 Here, examples of the alkylene group having 2 to 6 carbon atoms constituting R 30 include ethylidene, n-propylidene, 1,2-propylidene, n-butylidene, and 2-methyl-propane-1. 2,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl.

作為該結構部位(y2-8)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二元醇化合物之點來看，較佳為以下述結構式表示者。 As this structural site (y2-8), specifically, the diol compound which becomes a constituent raw material of the said structure in the manufacturing method [step IV] which is easy to obtain the compound represented by the said general formula (1) mentioned later is easily obtained. From the point of view, it is preferably expressed by the following structural formula.

Figure TW201944173A_D0072
Figure TW201944173A_D0072

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

酯鍵形成型結構部位的結構部位(y2-9)係前述通式(1)中的n為2或3且以下述結構式(y2-9)表示者。 The structural part (y2-9) of the ester bond formation type structural part is one in which n in the aforementioned general formula (1) is 2 or 3 and is represented by the following structural formula (y2-9).

Figure TW201944173A_D0073
Figure TW201944173A_D0073

(式中，R31係碳原子數4~12之連接鍵數為(n+1)價的烴基，R32為碳原子數2~6之伸烷基，s為0~3之整數)。 (In the formula, R 31 is a hydrocarbon group having 4 to 12 carbon atoms and a (n + 1) -valent hydrocarbon group, R 32 is an alkylene group having 2 to 6 carbon atoms, and s is an integer of 0 to 3).

此處，作為構成R31的碳原子數4~12之連接鍵數為(n+1)價的烴基，可列舉多元醇的殘基，可列舉 例如：三羥甲基丙烷殘基、新戊四醇殘基、甘油殘基、二-三羥甲基丙烷殘基。此處，所謂「殘基」係從該多元醇除去羥基的烴結構部位。 Here, as the hydrocarbon group having 4 to 12 carbon atoms constituting R 31 and having a (n + 1) valence hydrocarbon group, polyhydric alcohol residues may be mentioned, and examples thereof include trimethylolpropane residues and neopentyl. Tetraol residue, glycerol residue, di-trimethylolpropane residue. Here, the "residue" is a hydrocarbon structure site where a hydroxyl group is removed from the polyol.

又，作為構成R32的碳原子數2~6之伸烷基，可列舉：伸乙基、正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基、1,5-戊烷二基、1,6-己烷二基。 Examples of the alkylene group having 2 to 6 carbon atoms constituting R 32 include ethylene, n-propyl, 1,2-propyl, n-butyl, and 2-methyl-propyl-1, 2-diyl, 1,5-pentanediyl, 1,6-hexanediyl.

作為該結構部位(y2-9)，具體而言，從容易取得在後述之以前述通式(1)表示之化合物的製造方法[步驟IV]中成為前述結構之構成原料的二元醇化合物之點來看，較佳為以下述結構式表示者。 As this structural site (y2-9), specifically, the diol compound which becomes the constituent raw material of the said structure in the manufacturing method [step IV] which is easy to obtain the compound represented by the said general formula (1) mentioned later is easily obtained From the point of view, it is preferably expressed by the following structural formula.

Figure TW201944173A_D0074
Figure TW201944173A_D0074

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

以上詳述的通式(1)中，Y2之中，特別是選自包含結構部位(y2-1)~(y2-6)之群組的醯胺鍵形成型結構部位，從生成物的化學穩定性優異之點來看為較佳，特別是結構部位(y2-1)、結構部位(y2-2)、結構部位(y2-3)，從原料的取得簡易度與光硬化性優異之點來看為較佳。尤其是選自下述結構的結構部位(y2-3)，從中間體容易結晶化而在製造上可容易精製之點來看為較佳。 In the general formula (1) detailed above, among Y 2 , particularly the amido bond-forming structural site selected from the group consisting of structural sites (y2-1) to (y2-6), from the product's It is preferable from the viewpoint of excellent chemical stability. In particular, the structural portion (y2-1), the structural portion (y2-2), and the structural portion (y2-3) are excellent in ease of obtaining raw materials and excellent light-hardening properties. From a point of view, it is better. In particular, the structural site (y2-3) selected from the following structures is preferable in that the intermediate is easily crystallized and can be easily purified in manufacturing.

Figure TW201944173A_D0075
Figure TW201944173A_D0075

(各結構式中*表示與其他結構部位的連接鍵)。 (In each structural formula, * indicates a connection key with another structural part).

接著，通式(1)中的Y3表示單鍵、碳原子數1~3之伸烷基或者碳原子數2或3之亞烷基；作為碳原子數1~3之伸烷基，可列舉：亞甲基、伸乙基、正伸丙基、1,2-伸丙基；作為碳原子數2或3之亞烷基，可列舉亞乙基、亞丙基。 Next, Y 3 in the general formula (1) represents a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylene group having 2 or 3 carbon atoms; as an alkylene group having 1 to 3 carbon atoms, Examples include methylene, ethylidene, n-propylidene, and 1,2-propylidene. Examples of the alkylene group having 2 or 3 carbon atoms include ethylene and propylene.

此等之中，從構成該結構部位之原料成分的溴甲苯衍生物其取得簡易度之點來看，較佳為單鍵或者碳原子數2或3之亞烷基，特別是從光照射後之分解物的安全性之點來看，較佳為碳原子數2或3之亞烷基。 Among these, from the viewpoint of simplicity of the bromotoluene derivative constituting the raw material component constituting the structural portion, a single bond or an alkylene group having 2 or 3 carbon atoms is preferred, especially after light irradiation From the viewpoint of safety of the decomposed product, an alkylene group having 2 or 3 carbon atoms is preferred.

以上詳述的通式(1)表示之化合物，更具體而言，可列舉例如：以下表1~表12所示的化合物M1~M86。 The compound represented by the general formula (1) described above in more detail includes, for example, compounds M1 to M86 shown in the following Tables 1 to 12.

上述M1~M86的化合物之中，特別是從可得到具有高光感度及硬化物之優異耐熱性且不易發生逸氣之感光性樹脂組成物、而且亦容易取得原料之點來 看，較佳為M1、M4、M7、M14、M23、M28、M31、M32、M41、M43、M45、M50、M55、M64及M78的化合物。 Among the above-mentioned compounds M1 to M86, M1 is particularly preferred from the viewpoint that a photosensitive resin composition having high photosensitivity and excellent heat resistance of the cured material and less outgassing can be obtained, and raw materials are also easily obtained. , M4, M7, M14, M23, M28, M31, M32, M41, M43, M45, M50, M55, M64 and M78.

以上述通式(1)表示之化合物，可經由下述[步驟I]~[步驟VI]進行工業上的生產。 The compound represented by the general formula (1) can be industrially produced through the following [Step I] to [Step VI].

[步驟I]     [Step I]    

使鹵化苯與α位具有鹵化物原子之酸鹵化物化合物進行反應，合成在羰基的α碳原子上具有鹵素原子的烷基苯乙酮衍生物。[步驟I]的反應可在無水氯化鋁的存在下，藉由夫里德耳-夸夫特(Friedel-Crafts)醯化反應而進行。此處，作為前述鹵化苯，可列舉：氟化苯、氯苯、溴苯等。又，作為前述α位具有鹵化物原子的酸鹵化物化合物，可列舉：2-溴丙醯溴(2-bromopropionic acid bromide)、2-溴丙醯氯(2-bromopropionic acid chloride)、2-溴戊醯溴、2-溴戊醯氯、2-溴己醯溴、2-溴辛醯溴等。 A halogenated benzene is reacted with an acid halide compound having a halide atom at the α position to synthesize an alkylacetophenone derivative having a halogen atom at the α carbon atom of the carbonyl group. The reaction of [Step I] can be performed by a Friedel-Crafts dehydration reaction in the presence of anhydrous aluminum chloride. Here, examples of the halogenated benzene include fluorinated benzene, chlorobenzene, and bromobenzene. Examples of the acid halide compound having a halide atom at the α-position include 2-bromopropionic acid bromide, 2-bromopropionic acid chloride, and 2-bromopropionic acid chloride. Pentamidine bromide, 2-bromopentamidine chloride, 2-bromohexamidine bromide, 2-bromooctamidine bromide and the like.

[步驟II]     [Step II]    

接著，使二級單胺化合物(HN(R2)(R3))進行反應，將α位轉化成胺基。作為此處使用的二級單胺化合物(HN(R2)(R3))，可列舉：二甲胺、二乙胺、甲基丁胺、甲基辛胺、甲基十二胺、乙基己胺、二乙醇胺、二異丙醇胺、二異丁醇胺、2,2’-二乙氧基二乙胺、2,2’-二甲氧基二乙胺、

Figure TW201944173A_D0088
啉、吡咯啶、哌啶、N-甲基哌
Figure TW201944173A_D0089
、2,6-二甲基
Figure TW201944173A_D0090
啉等。反應條件例如可在碳酸鈣、碳酸鉀、碳酸鈉等的碳酸鹽、或三乙胺、二異丙基乙胺等之三級胺等的 鹼存在下，於0℃~80℃的溫度條件下進行。又，使二級胺作為鹼發揮作用的情況下，可過量地使用來製造。 Next, a secondary monoamine compound (HN (R 2 ) (R 3 )) is reacted to convert the α-position into an amine group. Examples of the secondary monoamine compound (HN (R 2 ) (R 3 )) used here include dimethylamine, diethylamine, methylbutylamine, methyloctylamine, methyldodecylamine, and ethyl Hexylamine, diethanolamine, diisopropanolamine, diisobutanolamine, 2,2'-diethoxydiethylamine, 2,2'-dimethoxydiethylamine,
Figure TW201944173A_D0088
Porphyrin, pyrrolidine, piperidine, N-methylpiperidine
Figure TW201944173A_D0089
2,6-dimethyl
Figure TW201944173A_D0090
Porphyrin, etc. The reaction conditions can be, for example, in the presence of a carbonate such as calcium carbonate, potassium carbonate, sodium carbonate, or a tertiary amine such as triethylamine, diisopropylethylamine, or the like at a temperature of 0 ° C to 80 ° C. get on. Moreover, when a secondary amine is made to act as a base, it can be manufactured by using it excessively.

[步驟III]     [Step III]    

接著，使具有取代基(-Y3-C(=O)-OR)作為芳香核上之取代基的溴甲苯(此處，R為烷基或氫原子)對於苯乙酮衍生物的三級胺進行反應而導向四級銨鹽，之後，藉由鹼處理，進行1,2-重排反應(史蒂文斯重排(Stevens rearrangement))，合成以通式3表示之α-胺基苯乙酮中間體化合物A(通式3)。以此方式所得到之α-胺基苯乙酮中間化合物(通式3)係在苯乙酮部的芳香環上具有鹵素原子、且在α位上取代之苄基的芳香環上具有羧基者。 Next, the tertiary order of bromotoluene (here, R is an alkyl group or a hydrogen atom) having a substituent (-Y 3 -C (= O) -OR) as a substituent on the aromatic nucleus for the acetophenone derivative The amine is reacted to lead to a quaternary ammonium salt, and then, by a base treatment, a 1,2-rearrangement reaction (Stevens rearrangement) is performed to synthesize an α-aminobenzene represented by Formula 3 Ethyl ketone intermediate compound A (general formula 3). The α-aminoacetophenone intermediate compound (general formula 3) obtained in this way is one having a halogen atom on the aromatic ring of the acetophenone moiety and a carboxyl group on the aromatic ring of the benzyl group substituted at the α position. .

Figure TW201944173A_D0091
Figure TW201944173A_D0091

(上述反應式中，「Hal」表示鹵素原子)。 (In the above reaction formula, "Hal" represents a halogen atom).

此處，具有取代基(-Y3-C(=O)-OR)作為芳香核上之取代基的溴甲苯中的Y3，如上所述，其為單鍵、碳原子數1~3之伸烷基、或者碳原子數2或3之亞烷基， 特別是單鍵、亞甲基或亞乙基，從原料之取得簡易度之點來看為較佳；R較佳為氫原子、或甲基、乙基等的烷基；因此，作為具有取代基(-Y3-C(=O)-OR)作為芳香核上之取代基的溴甲苯化合物(此處，R為甲基、乙基或氫原子)，可列舉例如：溴甲基苯甲酸甲酯、2-[4-(溴甲基)苯基]]丙酸甲酯、2-[4-(溴甲基)苯基]]乙酸乙酯等。 Here, having a substituent group (-Y 3 -C (= O) -OR) benzyl bromide as a substituent on the aromatic nucleus in the Y 3, as described above, which is a single bond, a carbon number of 1 to 3 An alkylene group or an alkylene group having 2 or 3 carbon atoms, especially a single bond, a methylene group, or an ethylene group, is preferred from the viewpoint of simplicity of the raw material; R is preferably a hydrogen atom, Or an alkyl group such as methyl or ethyl; therefore, a bromotoluene compound having a substituent (-Y 3 -C (= O) -OR) as a substituent on the aromatic core (here, R is methyl, Ethyl or hydrogen atom), for example, methyl bromomethylbenzoate, 2- [4- (bromomethyl) phenyl]] propanoic acid methyl ester, 2- [4- (bromomethyl) phenyl ]] Ethyl acetate and the like.

又，[步驟III]中的四級銨化係於20~100℃下進行，接著1,2-重排反應(史蒂文斯重排)可於鹼使用氫氧化鈉水溶液，於20~80℃下進行。 In addition, the quaternary ammonium system in [Step III] is performed at 20 to 100 ° C, followed by a 1,2-rearrangement reaction (Stevens rearrangement). A sodium hydroxide aqueous solution can be used for the alkali at 20 to 80 ℃.

[步驟IV]     [Step IV]    

接著，使前述α-胺基苯乙酮中間化合物(通式3)的羧基與二官能以上之一級或二級胺或者二官能以上之醇(通式4)進行縮合反應，分別誘導至聚醯胺化合物及聚酯化合物的中間體化合物B。 Next, the carboxyl group of the aforementioned α-aminoacetophenone intermediate compound (general formula 3) is subjected to a condensation reaction with a di- or higher-functional primary or secondary amine or a di-functional or higher alcohol (general formula 4) to induce a polyfluorene Intermediate compound B of an amine compound and a polyester compound.

例如，使用二官能之二胺作為以通式4表示之化合物的情況下，相對於2莫耳的α-胺基苯乙酮中間化合物(通式3)，使1莫耳的二官能之二胺進行反應，可合成2個醯胺基成為對稱之分子結構的中間體化合物B。具體而言，可列舉：使用亞硫醯氯等，將以通式3表示之α-胺基苯乙酮中間化合物的芳香環上所配置的羧基轉化成醯氯後，使其與二官能以上之胺進行反應的方法；使用二環己碳二亞胺(dicyclohexylcarbodiimide)(DCC)等的活性酯化試劑，使以通式3表示之α-胺基苯乙酮中間化合物與二官能以上之醇進行反應的方法；使 用乙酸酐等的酸酐，將以通式3表示之α-胺基苯乙酮中間化合物轉化成混合酸酐後，使其與二官能以上之醇進行反應的方法等。 For example, when a difunctional diamine is used as the compound represented by Formula 4, a mole of 1-mole difunctional bis is used relative to 2 moles of the α-aminoacetophenone intermediate compound (General Formula 3). The amine reacts to synthesize two intermediate compounds B, each of which has a symmetric molecular structure. Specifically, the carboxyl group arrange | positioned on the aromatic ring of the α-aminoacetophenone intermediate compound represented by General formula 3 using thionyl chloride, etc. can be mentioned, and it can be made bifunctional or more. A method for reacting an amine; using an active esterification reagent such as dicyclohexylcarbodiimide (DCC), an α-aminoacetophenone intermediate compound represented by the general formula 3 and a bifunctional or higher alcohol A method of performing a reaction; a method of converting an α-aminoacetophenone intermediate compound represented by Formula 3 to a mixed acid anhydride using an acid anhydride such as acetic anhydride, and then reacting the compound with a difunctional or higher alcohol.

另一方面，使用二官能以上之醇作為以通式4表示之化合物時的中間體化合物B的合成法，可列舉：使用亞硫醯氯等，將通式3之中間化合物的芳香環上所配置的羧基轉化成醯氯後，使其與二官能以上之醇進行反應的方法；使用對甲苯磺酸等的酸觸媒，藉由脫水縮合使其與二官能以上之醇進行反應的方法；使用二環己碳二亞胺(DCC)等的活性酯化試劑，使其與二官能以上之醇進行反應的方法；使用乙酸酐等的酸酐，將其轉化成混合酸酐後，使其與二官能以上之醇進行反應的方法等。 On the other hand, a method for synthesizing the intermediate compound B when using a difunctional or higher alcohol as the compound represented by the general formula 4 includes the use of thionyl chloride or the like to place the aromatic ring of the intermediate compound of the general formula 3 on the aromatic ring. A method for converting a configured carboxyl group into arsine chloride and reacting it with a difunctional or higher alcohol; a method of using an acid catalyst such as p-toluenesulfonic acid to react with a difunctional or higher alcohol through dehydration condensation; Method for using dicyclohexylcarbodiimide (DCC) and other active esterification reagents to react with di- or higher-functional alcohols; using acid anhydrides such as acetic anhydride to convert them into mixed acid anhydrides A method for reacting a functional alcohol or the like.

Figure TW201944173A_D0092
Figure TW201944173A_D0092

(上述反應式中，「Hal」表示鹵素原子)。 (In the above reaction formula, "Hal" represents a halogen atom).

此處，以通式4表示之化合物之中，作為一級或二級胺，可列舉例如：乙二胺、1,3-二胺丙烷、 1,2-二胺丙烷、1,4-二胺丁烷、1,2-二胺基-2-甲基丙烷、2-甲基-1,3-丙二胺、1,5-二胺戊烷、2,2-二甲基-1,3-丙二胺、1,6-二胺己烷、1,2-二胺基環己烷、1,3-二胺基環己烷、1,4-二胺基環己烷、2,2'-二胺基-N-甲基二乙胺、1,7-二胺庚烷、1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、1,8-二胺辛烷、N-(3-胺基丙基)-N-甲基-1,3-丙二胺、1,10-二胺十二烷、1,11-二胺十一烷、1,12-二胺十二烷、1,18-二胺基十八烷、雙(4-胺基環己基)甲烷、哌

Figure TW201944173A_D0093
、2-甲基哌
Figure TW201944173A_D0094
、2,5-二甲基哌
Figure TW201944173A_D0095
、2,3-二甲基哌
Figure TW201944173A_D0096
、2,5-二吖雙環[2.2.1]庚烷、高哌
Figure TW201944173A_D0097
(homopiperazine)、N,N'-二甲基乙二胺、N,N'-伸乙基二乙基二胺、N,N'-雙[2-(甲胺基)乙基]甲胺、1,1-參(胺基甲基)乙烷、次乙基參(甲胺)等的烷胺；2,2’-氧雙(乙胺)、1,8-二胺基-3,6-二氧辛烷、3,6,9-三
Figure TW201944173A_D0098
十一烷-1,11-二胺、4,9-二
Figure TW201944173A_D0099
-1,12-十二烷二胺、4,7,10-三
Figure TW201944173A_D0100
-1,13-十三烷二胺、3,6,9,12-四
Figure TW201944173A_D0101
十四烷-1,14-二胺等的聚伸烷基醚胺；間苯二甲胺、對苯二甲胺、1,3-苯二胺、1,4-苯二胺、1,5-二胺基萘、3,3'-二甲基聯苯胺、3,3'-二乙基聯苯胺、3,3'-二甲氧基聯苯胺、3,3'，5,5'-四甲基聯苯胺、2,2'-二甲基聯苯胺、1,3,5-參(4-胺基苯基)苯、2,7-二胺基茀、4,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、3,3'-二胺二苯甲烷、4,4'-伸乙基二苯胺、1,1-雙(4-胺基苯基)環己烷、9,9-雙(4-胺基苯基)茀、1,4-雙[2-(4-胺基苯基)-2-丙基]苯、2,2-雙(4-胺基苯基)六氟丙烷、4,4'-二胺二苯碸、3,3'-二胺二苯碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙 烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-雙(4-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]碸、1,4-雙(4-胺基-2-三氟甲基苯氧基)苯等的芳香族二胺。 Here, among the compounds represented by the general formula 4, examples of the primary or secondary amine include ethylenediamine, 1,3-diaminepropane, 1,2-diaminepropane, and 1,4-diamine. Butane, 1,2-diamino-2-methylpropane, 2-methyl-1,3-propanediamine, 1,5-diaminepentane, 2,2-dimethyl-1,3 -Propanediamine, 1,6-diaminehexane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 2,2 ' -Diamino-N-methyldiethylamine, 1,7-diamine heptane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) ring Hexane, 1,8-diamineoctane, N- (3-aminopropyl) -N-methyl-1,3-propanediamine, 1,10-diaminedodecane, 1,11- Diamine undecane, 1,12-diamine dodecane, 1,18-diaminooctadecane, bis (4-aminocyclohexyl) methane, piperazine
Figure TW201944173A_D0093
2-methylpiperazine
Figure TW201944173A_D0094
2,5-dimethylpiperazine
Figure TW201944173A_D0095
2,3-dimethylpiperazine
Figure TW201944173A_D0096
, 2,5-Diazylbicyclo [2.2.1] heptane, homopiperazine
Figure TW201944173A_D0097
(homopiperazine), N, N ' - dimethylethylenediamine, N, N' - diethyl extending triethylenediamine, N, N '- bis [2- (methylamino) ethyl] methylamine, Alkylamines such as 1,1-gins (aminomethyl) ethane, ethylidene (methylamine); 2,2'-oxybis (ethylamine), 1,8-diamino-3,6 -Dioxane, 3,6,9-tri
Figure TW201944173A_D0098
Undecane-1,11-diamine, 4,9-diamine
Figure TW201944173A_D0099
-1,12-dodecanediamine, 4,7,10-tri
Figure TW201944173A_D0100
-1,13-tridecanediamine, 3,6,9,12-tetra
Figure TW201944173A_D0101
Polyalkylene etheramines such as tetradecane-1,14-diamine; m-xylylenediamine, p-xylylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 1,5 - naphthalene diamine, 3,3 '- dimethyl benzidine, 3,3' - diethyl benzidine, 3,3 '- dimethoxy benzidine, 3,3', 5,5 '- tetramethyl benzidine, 2,2 '- dimethyl benzidine, 3,5 ginseng (4-aminophenyl) benzene, 2,7-diamino-fluorene, 4,4' - diamine benzophenone, 3,3 '- diamino benzophenone, 3,3' - diphenylmethane diamine, 4,4 '- diethyl aniline extending, 1,1-bis (4-amine Phenyl) cyclohexane, 9,9-bis (4-aminophenyl) fluorene, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2 - bis (4-aminophenyl) hexafluoropropane, 4,4 '- diamine diphenyl sulfone, 3,3' - diamine diphenyl sulfone, 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) ) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 '- bis (4-aminophenoxy) biphenyl, bis [ Aromatic diamines such as 4- (4-aminophenoxy) phenyl] fluorene and 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene.

另一方面，以通式4表示之化合物之中，作為二官能以上之醇，可列舉例如：乙二醇、二乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、1,14-十四烷二醇、1,16-十六烷二醇、1,18-十八烷二醇、1,20-二十烷二醇等的直鏈之烷二醇及此等的環氧乙烷改質物或環氧丙烷改質物；聚氧乙二醇、聚氧丙二醇等的醚二醇；藉由前述直鏈之烷二醇與環氧乙烷、環氧丙烷、四氫呋喃、乙基環氧丙基醚、丙基環氧丙基醚、丁基環氧丙基醚、苯基環氧丙基醚、烯丙基環氧丙基醚等各種含環狀醚鍵之化合物的開環聚合而得的改質聚醚多元醇；藉由前述直鏈之烷二醇與ε-己內酯等各種內酯的聚縮合反應而得的內酯系聚酯多元醇等的二官能型含羥基之化合物；三羥甲基乙烷、三羥甲基丙烷、2,2,4-三甲基-1,3-戊二醇、甘油、己三醇、新戊四醇及此等的環氧乙烷改質物或環氧丙烷改質物等的3官能以上之多元醇。 On the other hand, among the compounds represented by the general formula 4, examples of the difunctional or higher alcohols include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12- Dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, etc. Alkanediols and such ethylene oxide or propylene oxide modifications; ether glycols such as polyoxyethylene glycol, polyoxypropylene glycol; and the aforementioned linear alkylene glycol and ethylene oxide, Various ring-containing materials such as propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc. Modified polyether polyols obtained by ring-opening polymerization of compounds in the form of ether bonds; lactone polyesters obtained by the polycondensation reaction of the aforementioned linear alkanediols and various lactones such as ε-caprolactone Difunctional hydroxyl-containing compounds such as polyols; trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3- Trifunctional or higher polyhydric alcohols such as pentanediol, glycerol, hexanetriol, neopentyl tetraol, and ethylene oxide modifiers or propylene oxide modifiers.

[步驟V]     [Step V]    

之後，以通式5所表示之二官能性環狀胺取代中間體化合物B之分子末端部分的芳基鹵素部，合成分子末端為二級胺的中間生成物C。 Then, the bifunctional cyclic amine represented by Formula 5 is substituted for the aryl halogen part of the molecular terminal part of the intermediate compound B, and the intermediate product C whose molecular terminal is a secondary amine is synthesized.

Figure TW201944173A_D0102
Figure TW201944173A_D0102

該反應可在60℃~160℃的溫度條件下進行。此時，作為系統內產生之酸的捕捉劑，除了過剩地使用以通式5表示之二官能性環狀胺以外，亦可使用碳酸鉀等的無機碳酸鹽。此處，作為以通式5表示之二官能性環狀胺，可列舉例如：哌

Figure TW201944173A_D0103
、2-甲基哌
Figure TW201944173A_D0104
、2,5-二甲基哌
Figure TW201944173A_D0105
、2,3-二甲基哌
Figure TW201944173A_D0106
、2,5-二吖雙環[2.2.1]庚烷、高哌
Figure TW201944173A_D0107
等。 The reaction can be performed at a temperature of 60 ° C to 160 ° C. At this time, in addition to excessively using a bifunctional cyclic amine represented by Formula 5 as a trapping agent for the acid generated in the system, an inorganic carbonate such as potassium carbonate may be used. Here, examples of the bifunctional cyclic amine represented by Formula 5 include piperidine.
Figure TW201944173A_D0103
2-methylpiperazine
Figure TW201944173A_D0104
2,5-dimethylpiperazine
Figure TW201944173A_D0105
2,3-dimethylpiperazine
Figure TW201944173A_D0106
, 2,5-Diazylbicyclo [2.2.1] heptane, homopiperazine
Figure TW201944173A_D0107
Wait.

[步驟VI]     [Step VI]    

接著，作為最終反應，針對位於[步驟V]所得到之中間體化合物C的結構末端的二級胺，使其與(甲基)丙烯酸酯化合物、異氰酸酯、環氧丙基醚或鹵烷進行反應，藉此可製造以前述通式(1)表示之化合物。具體而言，[步驟VI]可根據與中間體化合物C反應的化合物而分類成以下的(步驟VI-1)~(步驟VI-9)。 Next, as a final reaction, a secondary amine located at the structural end of the intermediate compound C obtained in [Step V] is reacted with a (meth) acrylate compound, isocyanate, epoxypropyl ether, or haloalkane. Thus, a compound represented by the aforementioned general formula (1) can be produced. Specifically, [Step VI] can be classified into the following (Step VI-1) to (Step VI-9) according to the compound that reacts with the intermediate compound C.

(步驟VI-1)     (Step VI-1)    

針對位於前述中間體化合物C中的結構末端的二級胺，使下述反應式中以Hal-R’表示的碳原子數3~18之鹵烷進行反應(此外，前述烷烴亦可具有與反應無關的鹵素原子或羥基)，藉此可製造Y1為不具有取代基或者具有鹵素原子或羥基作為取代基的碳原子數3~18之烷基(y1-1)的以下述通式1-1所表示之化合物。 The secondary amine located at the structural end of the intermediate compound C is reacted with a haloalkane having 3 to 18 carbon atoms represented by Hal-R 'in the following reaction formula (in addition, the alkane may have a reaction with Unrelated halogen atom or hydroxyl group), whereby Y 1 is an alkyl group (y1-1) having 3 to 18 carbon atoms having no substituent or having a halogen atom or a hydroxyl group as a substituent in the following general formula 1- The compound represented by 1.

Figure TW201944173A_D0108
Figure TW201944173A_D0108

(式中，Hal為鹵素原子，R’為可具有鹵素原子或羥基的烷基)。 (In the formula, Hal is a halogen atom, and R 'is an alkyl group which may have a halogen atom or a hydroxyl group).

此處，作為以Hal-R’表示的碳原子數3~18之鹵烷，可列舉：1-氯丙烷、2-氯丙烷、1-氯丁烷、2-氯丁烷、2-甲基-2-氯丙烷、2-甲基-1-氯丙烷、1-氯戊烷、2-氯戊烷、3-氯戊烷、2-氯-2-甲基丁烷、1-氯-2-乙基丁烷、1-氯己烷、2-氯己烷、3-氯己烷、2-氯-甲基-戊烷、1-氯庚烷、2-氯庚烷、3-氯庚烷、1-氯辛烷、2-氯辛烷、3-氯辛烷、1-氯-1,1,3,3-四甲基丁烷、1-氯-2,2,4,4-四甲基丁烷、1-氯-3-甲基庚烷、1-氯-2-乙基己烷、1-氯壬烷、2-氯壬烷、3-氯壬烷、1-氯-1,1,3-三甲基己烷、1-氯 -1,1,3,3-四甲基戊烷、1-氯癸烷、2-氯癸烷、3-氯癸烷、1-氯-1,1,3,3,5,5-六甲基己烷、1-氯-8-甲基-壬烷、1-氯十一烷、2-氯十一烷、3-氯十一烷、1-氯十二烷、2-氯十二烷、3-氯十二烷、1-氯十三烷、2-氯十三烷、3-氯十三烷、1-氯十四烷、2-氯十四烷、3-氯十四烷、1-氯十五烷、2-氯十五烷、3-氯十五烷、1-氯十六烷、2-氯十六烷、3-氯十六烷、1-氯十七烷、2-氯十七烷、3-氯十七烷、1-氯十八烷、2-氯十八烷、3-氯十八烷等的氯烷；1-溴丙烷、2-溴丙烷、1-溴丁烷、2-溴丁烷、2-甲基-2-溴丙烷、2-甲基-1-溴丙烷、1-溴戊烷、2-溴戊烷、3-溴戊烷、2-溴-2-甲基丁烷、1-溴-2-乙基丁烷、1-溴己烷、2-溴己烷、3-溴己烷、2-溴-甲基-戊烷、1-溴庚烷、2-溴庚烷、3-溴庚烷、1-溴辛烷、2-溴辛烷、3-溴辛烷、1-溴-1,1,3,3-四甲基丁烷、1-溴-2,2,4,4-四甲基丁烷、1-溴-3-甲基庚烷、1-溴-2-乙基己烷、1-溴壬烷、2-溴壬烷、3-溴壬烷、1-溴-1,1,3-三甲基己烷、1-溴-1,1,3,3-四甲基戊烷、1-溴癸烷、2-溴癸烷、3-溴癸烷、1-溴-1,1,3,3,5,5-六甲基己烷、1-溴-8-甲基-壬烷、1-溴十一烷、2-溴十一烷、3-溴十一烷、1-溴十二烷、2-溴十二烷、3-溴十二烷、1-溴十三烷、2-溴十三烷、3-溴十三烷、1-溴十四烷、2-溴十四烷、3-溴十四烷、1-溴十五烷、2-溴十五烷、3-溴十五烷、1-溴十六烷、2-溴十六烷、3-溴十六烷、1-溴十七烷、2-溴十七烷、3-溴十七烷、1-溴十八烷、2-溴十八烷、3-溴十八烷等的溴烷；1-碘丙烷、2-碘丙烷、1-碘丁烷、2-碘丁烷、2-甲基-2-碘丙烷、2-甲基-1-碘丙烷、1-碘戊烷、 2-碘戊烷、3-碘戊烷、2-碘-2-甲基丁烷、1-碘-2-乙基丁烷、1-碘己烷、2-碘己烷、3-碘己烷、2-碘-甲基-戊烷、1-碘庚烷、2-碘庚烷、3-碘庚烷、1-碘辛烷、2-碘辛烷、3-碘辛烷、1-碘-1,1,3,3-四甲基丁烷、1-碘-2,2,4,4-四甲基丁烷、1-碘-3-甲基庚烷、1-碘-2-乙基己烷、1-碘壬烷、2-碘壬烷、3-碘壬烷、1-碘-1,1,3-三甲基己烷、1-碘-1,1,3,3-四甲基戊烷、1-碘癸烷、2-碘癸烷、3-碘癸烷、1-碘-1,1,3,3,5,5-六甲基己烷、1-碘-8-甲基-壬烷、1-碘十一烷、2-碘十一烷、3-碘十一烷、1-碘十二烷、2-碘十二烷、3-碘十二烷、1-碘十三烷、2-碘十三烷、3-碘十三烷、1-碘十四烷、2-碘十四烷、3-碘十四烷、1-碘十五烷、2-碘十五烷、3-碘十五烷、1-碘十六烷、2-碘十六烷、3-碘十六烷、1-碘十七烷、2-碘十七烷、3-碘十七烷、1-碘十八烷、2-碘十八烷、3-碘十八烷等的碘烷。 Here, examples of the haloalkane having 3 to 18 carbon atoms represented by Hal-R 'include 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, and 2-methyl. 2-chloropropane, 2-methyl-1-chloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, 2-chloro-2-methylbutane, 1-chloro-2 -Ethylbutane, 1-chlorohexane, 2-chlorohexane, 3-chlorohexane, 2-chloro-methyl-pentane, 1-chloroheptane, 2-chloroheptane, 3-chloroheptane Alkane, 1-chlorooctane, 2-chlorooctane, 3-chlorooctane, 1-chloro-1,1,3,3-tetramethylbutane, 1-chloro-2,2,4,4- Tetramethylbutane, 1-chloro-3-methylheptane, 1-chloro-2-ethylhexane, 1-chlorononane, 2-chlorononane, 3-chlorononane, 1-chloro- 1,1,3-trimethylhexane, 1-chloro-1,1,3,3-tetramethylpentane, 1-chlorodecane, 2-chlorodecane, 3-chlorodecane, 1- Chloro-1,1,3,3,5,5-hexamethylhexane, 1-chloro-8-methyl-nonane, 1-chloroundecane, 2-chloroundecane, 3-chlorodeca Monodecane, 1-chlorododecane, 2-chlorododecane, 3-chlorododecane, 1-chlorotridecane, 2-chlorotridecane, 3-chlorotridecane, 1-chlorotetradecane Alkanes, 2-chlorotetradecane, 3-chlorotetradecane, 1-chloropentadecane, 2-chloropentadecane, 3-chloropentadecane, 1-chlorohexadecane 2-chlorohexadecane, 3-chlorohexadecane, 1-chlorohexadecane, 2-chlorohexadecane, 3-chlorohexadecane, 1-chlorooctadecane, 2-chlorooctadecane, 3 -Chloroanes such as chlorooctadecane; 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 2-methyl-2-bromopropane, 2-methyl-1-bromo Propane, 1-bromopentane, 2-bromopentane, 3-bromopentane, 2-bromo-2-methylbutane, 1-bromo-2-ethylbutane, 1-bromohexane, 2- Bromohexane, 3-bromohexane, 2-bromo-methyl-pentane, 1-bromoheptane, 2-bromoheptane, 3-bromoheptane, 1-bromooctane, 2-bromooctane, 3-bromooctane, 1-bromo-1,1,3,3-tetramethylbutane, 1-bromo-2,2,4,4-tetramethylbutane, 1-bromo-3-methyl Heptane, 1-bromo-2-ethylhexane, 1-bromononane, 2-bromononane, 3-bromononane, 1-bromo-1,1,3-trimethylhexane, 1- Bromine-1,1,3,3-tetramethylpentane, 1-bromodecane, 2-bromodecane, 3-bromodecane, 1-bromo-1,1,3,3,5,5- Hexamethylhexane, 1-bromo-8-methyl-nonane, 1-bromoundecane, 2-bromoundecane, 3-bromoundecane, 1-bromododecane, 2-bromodecane Dioxane, 3-bromododecane, 1-bromotridecane, 2-bromotridecane, 3-bromotridecane, 1-bromotetradecane, 2-bromotetradecane, 3-bromodecane Alkane, 1-bromopentadecane, 2-bromopentadecane, 3-bromopentadecane, 1-bromohexadecane, 2-bromohexadecane, 3-bromohexadecane, 1-bromohexadecane , 2-bromoheptadecane, 3-bromoheptadecane, 1-bromooctadecane, 2-bromooctadecane, 3-bromooctadecane, etc .; 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 2-methyl-2-iodopropane, 2-methyl-1-iodopropane, 1-iodopentane, 2-iodopentane, 3-iodopentane, 2-iodo-2-methylbutane, 1-iodo-2-ethylbutane, 1-iodohexane, 2-iodohexane, 3-iodohexane, 2-iodo-methyl-pentane, 1-iodoheptane, 2-iodoheptane, 3-iodoheptane, 1-iodooctane, 2-iodooctane, 3-iodooctane, 1-iodo-1,1,3,3-tetramethyl Butane, 1-iodo-2,2,4,4-tetramethylbutane, 1-iodo-3-methylheptane, 1-iodo-2-ethylhexane, 1-iodononane, 2-iodononane, 3-iodononane, 1-iodo-1,1,3-trimethylhexane, 1-iodo-1,1,3,3-tetramethylpentane, 1-iododecane Alkane, 2-iododecane, 3-iododecane, 1-iodo-1,1,3,3,5,5-hexamethylhexane, 1-iodo-8-methyl-nonane, 1- Iodoundane, 2-iododecane, 3-iododecane, 1-iododecane, 2-iododecane, 3-iododecane, 1-iododecane, 2- Iodotridecane, 3-iodotridecane, 1-iodotetradecane, 2-iodotetradecane, 3-iodotetradecane, 1-iodopentadecane, 2-iodopentadecane, 3-iodo Pentadecane, 1-iodohexadecane, 2-iodohexadecane, 3-iodohexadecane, 1-iodohexadecane, 2-iodohexadecane, 3-iododecadecane, 1-iododecane Iodane such as octane, 2-iodooctadecane, 3-iodooctadecane and the like.

又，以Hal-R’表示的碳原子數3~18之鹵烷於該烷烴結構上更具有鹵素原子的情況下，可列舉：1-溴-3-氟丙烷、1-溴-3-氯丙烷、1-碘-3-氟丙烷、1-碘-3-氯丙烷、1-溴-2-氟丙烷、1,1,1-三氟-3-碘丙烷、1,1,1,2,2-五氟-3-碘丙烷、1-溴-4-氟丁烷、1-溴-3-氟丁烷、1-溴-4-氯丁烷、1,1,1-三氟-4-碘丁烷、1,1,1,2,2,3,3-七氟-4-碘丁烷、1-溴-5-氟戊烷、1-碘-5-氟戊烷、1,1,1,2,2-五氟-5-碘戊烷、1-溴-6-氟己烷、1-碘-6-氟己烷、1,1,1-三氯-6-碘己烷、1-溴-7-氟庚烷、1-碘-7-氟庚烷、1-溴-8-氟辛烷、1-碘-8-氟辛烷、1-溴-9-氟壬烷、1-碘-9-氟壬烷、1-溴-10-氟癸烷、1-碘-10-氟癸烷、1-溴-12-氟十二烷、1-碘-12- 氟十二烷、1-溴-18-氟十八烷、1-碘-18-氟十八烷、1,1,1-三氯-18-碘十八烷等。 When a haloalkane having 3 to 18 carbon atoms represented by Hal-R 'has a halogen atom in the alkane structure, examples include 1-bromo-3-fluoropropane and 1-bromo-3-chloro Propane, 1-iodo-3-fluoropropane, 1-iodo-3-chloropropane, 1-bromo-2-fluoropropane, 1,1,1-trifluoro-3-iodopropane, 1,1,1,2 1,2-pentafluoro-3-iodopropane, 1-bromo-4-fluorobutane, 1-bromo-3-fluorobutane, 1-bromo-4-chlorobutane, 1,1,1-trifluoro- 4-iodobutane, 1,1,1,2,2,3,3-heptafluoro-4-iodobutane, 1-bromo-5-fluoropentane, 1-iodo-5-fluoropentane, 1 , 1,1,2,2-pentafluoro-5-iodopentane, 1-bromo-6-fluorohexane, 1-iodo-6-fluorohexane, 1,1,1-trichloro-6-iodine Hexane, 1-bromo-7-fluoroheptane, 1-iodo-7-fluoroheptane, 1-bromo-8-fluorooctane, 1-iodo-8-fluorooctane, 1-bromo-9-fluoro Nonane, 1-iodo-9-fluorononane, 1-bromo-10-fluorodecane, 1-iodo-10-fluorodecane, 1-bromo-12-fluorododecane, 1-iodo-12- Fluorododecane, 1-bromo-18-fluorooctadecane, 1-iodo-18-fluorooctadecane, 1,1,1-trichloro-18-iodooctadecane, and the like.

再者，以Hal-R’表示之碳原子數3~18之鹵烷於該烷烴結構上更具有羥基的情況下，可列舉：3-溴-1-丙醇、3-碘-1-丙醇、4-碘-2-甲基-2-丁醇、4-溴-2-甲基-2-丁醇、1-碘-2-甲基-2-丙醇、1-溴-2-甲基-2-丙醇、1-碘-4-丁醇、1-溴-4-丁醇、1-碘-2-丁醇、1-溴-2-丁醇、5-碘-1-戊醇、5-溴-1-戊醇、1-碘-6-己醇、1-溴-6-己醇、5-碘-3-甲基-1-戊醇、5-溴-3-甲基-1-戊醇、1-碘-8-辛醇、1-溴-8-辛醇、1-碘-12-十二醇、1-溴-12-十二醇、1-碘-18-十八醇、1-溴-18-十八醇等。 When a haloalkane having 3 to 18 carbon atoms represented by Hal-R 'has a hydroxyl group in the alkane structure, examples include 3-bromo-1-propanol and 3-iodo-1-propane Alcohol, 4-iodo-2-methyl-2-butanol, 4-bromo-2-methyl-2-butanol, 1-iodo-2-methyl-2-propanol, 1-bromo-2- Methyl-2-propanol, 1-iodo-4-butanol, 1-bromo-4-butanol, 1-iodo-2-butanol, 1-bromo-2-butanol, 5-iodo-1- Amyl alcohol, 5-bromo-1-pentanol, 1-iodo-6-hexanol, 1-bromo-6-hexanol, 5-iodo-3-methyl-1-pentanol, 5-bromo-3- Methyl-1-pentanol, 1-iodo-8-octanol, 1-bromo-8-octanol, 1-iodo-12-dodecanol, 1-bromo-12-dodecanol, 1-iodo- 18-octadecanol, 1-bromo-18-octadecanol and the like.

又，此(步驟VI-1)中的反應可藉由在N,N-二甲基甲醯胺等的極性溶媒中，使用碳酸鉀等的碳酸鹽作為鹼性觸媒而進行；或藉由在二氯甲烷或氯仿等的鹵化溶媒中，使用三乙胺等的三級胺作為鹼性觸媒而進行。 The reaction in this step (Step VI-1) can be performed by using a carbonate such as potassium carbonate as a basic catalyst in a polar solvent such as N, N-dimethylformamide or the like; or by In a halogenated solvent such as dichloromethane or chloroform, a tertiary amine such as triethylamine is used as a basic catalyst.

(步驟VI-2)     (Step VI-2)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與下述反應式中以Hal-Aral表示之鹵化芳香族化合物進行反應，可製造Y1為芳烷基(y1-2)的化合物。 By reacting a secondary amine located at the structural end of the intermediate compound C with a halogenated aromatic compound represented by Hal-Aral in the following reaction formula, Y 1 is an aralkyl group (y1-2). Compound.

Figure TW201944173A_D0109
Figure TW201944173A_D0109

(式中，Hal為鹵素原子，Aral為芳烷基)。 (In the formula, Hal is a halogen atom and Aral is an aralkyl group.)

此處，前述反應式中，作為以Hal-Aral表示之鹵化芳香族化合物，可列舉：氯甲苯、溴甲苯、氯化甲氧基苄基、溴化甲氧基苄基、溴化氯苄基、溴化羥基苄基、碘化苯乙基、溴化苯基苄基、溴化甲氧基苯基苄基、溴化萘基甲基、溴化甲氧基萘基甲基、碘化苯基丙基、碘化苯基丙烯基、溴化苯氧基苄基、溴化甲硫基苄基、溴化聯三苯基甲基等；可在與(步驟VI-1)相同的反應條件下進行。 Here, as the halogenated aromatic compound represented by Hal-Aral in the aforementioned reaction formula, chlorotoluene, bromotoluene, methoxybenzyl chloride, methoxybenzyl bromide, and chlorobenzyl bromide are listed. , Hydroxybenzyl bromide, phenethyl iodide, phenyl benzyl bromide, methoxyphenyl benzyl bromide, naphthyl methyl bromide, methoxy naphthyl methyl bromide, iodine benzene Propylpropyl, phenylpropenyl iodide, phenoxybenzyl bromide, methylthiobenzyl bromide, bitriphenylmethyl bromide, etc .; can be used under the same reaction conditions as (step VI-1) Carry on.

(步驟VI-3)     (Step VI-3)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-3r)表示之鹵化聚醚化合物進行反應，可製造Y1為結構式(y1-3)的化合物。 By making a secondary amine structure is located in the C-terminus of the intermediate compound is reacted with a halogenated polyether compound represented by the following structural formula (y1-3r), Y 1 may be manufactured structural formula (y1 - 3) Compound .

Figure TW201944173A_D0110
Figure TW201944173A_D0110

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子或苯基或碳原子數1~4之烷基，m表示0~20之整數)。 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom or a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20).

Figure TW201944173A_D0111
Figure TW201944173A_D0111

此處，前述結構式(y1-3r)及通式1-3中，作為R8的碳原子數2~4之伸烷基，可列舉：正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基等；又，作為R9中的碳原子數1~4之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基或二級丁基等。又，前述(步驟VI-3)的反應條件可在碳酸鉀等鹼性觸媒的存在下，於20~120℃下進行。 Here, in the structural formula (y1-3r) and the general formula 1-3, examples of the alkylene group having 2 to 4 carbon atoms of R 8 include n-propyl, 1,2-propyl, and Butyl, 2-methyl-propan-1,2-diyl and the like; Examples of the alkyl group having 1 to 4 carbon atoms in R 9 include methyl, ethyl, propyl, and isopropyl , N-butyl, isobutyl, tertiary butyl or secondary butyl, etc. The reaction conditions in the step (Step VI-3) can be performed at 20 to 120 ° C in the presence of a basic catalyst such as potassium carbonate.

(步驟VI-4)     (Step VI-4)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-4r)表示之化合物的(甲基)丙烯醯基進行麥可加成(Michael addition)反應，可製造前述通式(1)中的Y1為結構式(y1-4)的化合物。 The Michael addition reaction of the secondary amine located at the structural end of the intermediate compound C and the (meth) acrylfluorenyl group of the compound represented by the following structural formula (y1-4r) can be performed by A compound in which Y 1 in the aforementioned general formula (1) is a structural formula (y1-4) is produced.

Figure TW201944173A_D0112
Figure TW201944173A_D0112

(式中，R8表示碳原子數2~4之伸烷基，R9表示氫原子、苯基或碳數1~4之烷基，R10表示氫原子或甲基，m表示0~20之整數)。 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, and m represents 0 to 20 Integer).

Figure TW201944173A_D0113
Figure TW201944173A_D0113

此處，前述結構式(y1-4r)及通式1-4中，作為R8的碳原子數2~4之伸烷基，可列舉：正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2-二基等；又，作為R9中的碳原子數1~4之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基或二級丁基等。 Here, in the structural formula (y1-4r) and the general formula 1-4, examples of the alkylene group having 2 to 4 carbon atoms of R 8 include n-propyl, 1,2-propyl, and Butyl, 2-methyl-propan-1,2-diyl and the like; Examples of the alkyl group having 1 to 4 carbon atoms in R 9 include methyl, ethyl, propyl, and isopropyl , N-butyl, isobutyl, tertiary butyl or secondary butyl, etc.

又，(步驟VI-4)中的麥可加成反應可在周知慣用的反應條件下進行。作為一般方法，可列舉於0~150℃下，將前述中間體化合物C與前述具有作為麥可受體之功能的前述結構式(y1-4r)所表示之化合物在反應容器中進行混合的方法，亦可使用觸媒、溶媒。 The Michael addition reaction in (Step VI-4) can be performed under well-known reaction conditions. As a general method, a method of mixing the intermediate compound C and the compound represented by the structural formula (y1-4r) having a function as a Michael acceptor in a reaction vessel at 0 to 150 ° C may be mentioned. You can also use catalysts and solvents.

作為可使用的觸媒，可列舉例如：氫氧化四丁銨、四甲基胍、二吖雙環十一烯、1,4-二吖雙環[2.2.2]、三級丁酸鈉等。 Examples of usable catalysts include tetrabutylammonium hydroxide, tetramethylguanidine, diazinebicycloundecene, 1,4-diazinebicyclo [2.2.2], and sodium tertiary butyrate.

又，作為有機溶媒，可列舉例如：戊烷、己烷、庚烷、環己烷等的飽和烴系溶劑、甲苯、二甲苯等的芳香族烴系溶劑、甲醇、乙醇、異丙醇、2-丁醇、三級丁醇、乙二醇、卡必醇等的醇系溶劑、二甲醚、二乙醚、1,4-二

Figure TW201944173A_D0114
烷、四氫呋喃(THF)等的醚系溶劑、二甲基甲醯胺(DMF)等的醯胺系溶劑、氯仿、二氯甲烷等的鹵素系溶媒、二甲亞碸(DMSO)等。 Examples of the organic solvent include saturated hydrocarbon-based solvents such as pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbon-based solvents such as toluene and xylene; methanol, ethanol, isopropanol; -Alcohol solvents such as butanol, tertiary butanol, ethylene glycol, carbitol, dimethyl ether, diethyl ether, 1,4-dioxo
Figure TW201944173A_D0114
Ether solvents such as alkane and tetrahydrofuran (THF), amine solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, dimethyl sulfoxide (DMSO), and the like.

前述中間體化合物C與前述具有作為麥可受體之功能的前述結構式(y1-4r)所表示之化合物的混合比並無特別限定，但中間體化合物C中的二級胺基(i)與前述結構式(y1-4r)所表示之化合物中的(甲基)丙烯醯基(ii)的當量比[(i)/(ii)]較佳為1/1.5~1/30。若當量比[(i)/(ii)]超過1/1.5，則前述中間體化合物C或其分解物從塗膜發生遷移的可能性提高，若當量比[(i)/(ii)]小於1/30，則有麥可加成反應物的硬化性能差的傾向。從所得到之麥可加成反應物的硬化性能與塗膜溶出物量的觀點來看，當量比[(i)/(ii)]特佳為1/2~1/20。 The mixing ratio of the intermediate compound C and the compound represented by the structural formula (y1-4r) having a function as a Michael acceptor is not particularly limited, but the secondary amine group (i) in the intermediate compound C The equivalent ratio [(i) / (ii)] of the (meth) acrylfluorenyl group (ii) in the compound represented by the aforementioned structural formula (y1-4r) is preferably 1 / 1.5 to 1/30. If the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration of the intermediate compound C or its decomposed product from the coating film increases, and if the equivalent ratio [(i) / (ii)] is less than 1/30, there is a tendency that the hardening property of the Michael addition reactant is poor. From the viewpoints of the hardening performance of the obtained wheat addition reaction product and the amount of coating film eluted matter, the equivalent ratio [(i) / (ii)] is particularly preferably 1/2 to 1/20.

此處，就前述具有作為麥可受體之功能的前述結構式(y1-4r)而言，可列舉例如：(甲基)丙烯酸甲氧基乙酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、丁氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等。又，反應條件可在二吖雙環十一烯(DBU)等的觸媒的存在下，於20~120℃下進行。 Here, as for the said structural formula (y1-4r) which has the said function as a Michael acceptor, a methoxyethyl (meth) acrylate, methoxy polyethylene glycol (methyl ) Acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and the like. The reaction conditions can be carried out at 20 to 120 ° C in the presence of a catalyst such as diazodicycloundecene (DBU).

(步驟VI-5)     (Step VI-5)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-5r)表示之化合物的(甲基)丙烯醯基進行反應，可製造前述通式(1)中的Y1為結構式(y1-5)的化合物。 By reacting the secondary amine located at the structural end of the intermediate compound C with the (meth) acrylfluorenyl group of the compound represented by the following structural formula (y1-5r), the general formula (1) can be produced. Y 1 is a compound of structural formula (y1-5).

Figure TW201944173A_D0115
Figure TW201944173A_D0115

(式中，R10表示氫原子或甲基，R11表示碳原子數1~18之烷基或碳原子數6~18之芳基)。 (In the formula, R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.)

Figure TW201944173A_D0116
Figure TW201944173A_D0116

此處，R11就碳原子數1~18之烷基而言，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、異癸基、1-甲基十一基或1,1,3,3,5,5-六甲基己基等的直鏈狀或分支狀烷基、環庚基、環己基、環戊基等的環烷基等；另一方面，就碳原子數6~18之芳基而言，可列舉：苯基、苄基、苯乙基、聯苯基、萘基、甲苯基、二甲苯基、

Figure TW201944173A_D0117
基、
Figure TW201944173A_D0118
基、氯苯基、溴苯基、氯甲基苯基、羥苯基、甲氧基苯基、乙氧基苯基、苯氧基苯基、乙醯 氧基苯基、苯甲醯氧基苯基、甲硫基苯基、苯硫基苯基、甲胺基苯基、二甲胺基苯基、乙醯基胺基苯基、羧苯基、甲氧基羰基苯基、苯氧基羰基苯基、N-苯基胺甲醯基苯基、氰基苯基、磺苯基、磺酸根基苯基、膦醯基苯基、膦酸根基苯基等。 Here, as the alkyl group having 1 to 18 carbon atoms, R 11 includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and secondary butyl. Base, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen , 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3,3-tetramethyl Butyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1, Linear or branched alkyl groups such as 1,3,3-tetramethylpentyl, isodecyl, 1-methylundecyl, or 1,1,3,3,5,5-hexamethylhexyl Cycloalkyl, cycloheptyl, cyclohexyl, cyclopentyl, etc. On the other hand, for aryl groups having 6 to 18 carbon atoms, examples include phenyl, benzyl, phenethyl, and biphenyl Base, naphthyl, tolyl, xylyl,
Figure TW201944173A_D0117
base,
Figure TW201944173A_D0118
Methyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxyphenyl, benzophenoxy Phenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, phenoxy Carbonylphenyl, N-phenylaminomethylmethylphenyl, cyanophenyl, sulfophenyl, sulfonylphenyl, phosphinophenyl, phosphonophenyl and the like.

(步驟VI-6)     (Step VI-6)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-6r)表示之環氧化合物的環氧基進行反應，可製造Y1為結構式(y1-6)的化合物。 By reacting a secondary amine located at the structural end of the aforementioned intermediate compound C with an epoxy group of an epoxy compound represented by the following structural formula (y1-6r), Y 1 can be produced as a structural formula (y1-6 )compound of.

Figure TW201944173A_D0119
Figure TW201944173A_D0119

(式中，R12表示碳原子數1~18之烷基)。 (In the formula, R 12 represents an alkyl group having 1 to 18 carbon atoms.)

Figure TW201944173A_D0120
Figure TW201944173A_D0120

此處，前述結構式(y1-6r)及通式1-6中，作為R12的碳原子數1~18之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基、1-甲基己基、異庚基、1,1,3,3-四甲基丁基、2,2,4,4-四甲基丁基、1-甲基庚基、3-甲基庚基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、異癸基、1-甲基十一基或1,1,3,3,5,5-六甲基己基等的直鏈狀或分支狀烷基、環庚基、環己基、環戊基等的環烷基等。 Here, in the structural formula (y1-6r) and the general formula 1-6, examples of the alkyl group having 1 to 18 carbon atoms of R 12 include methyl, ethyl, propyl, isopropyl, and n- Butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Pentadecyl, hexadecyl, heptyl, octadecyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, Isoheptyl, 1,1,3,3-tetramethylbutyl, 2,2,4,4-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2-ethyl Hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, isodecyl, 1-methylundecyl or 1,1,3,3,5,5 -Linear or branched alkyl such as hexamethylhexyl, cycloalkyl such as cycloheptyl, cyclohexyl, cyclopentyl and the like.

又，(步驟VI-6)中與環氧化合物的反應，可列舉：於成為0~150℃的溫度條件下，將前述中間體化合物C與以前述結構式(y1-6r)表示之化合物在反應容器中進行混合而反應的方法。此時，亦可使用觸媒、溶媒。 In addition, the reaction with the epoxy compound in (Step VI-6) includes the following: the intermediate compound C and the compound represented by the structural formula (y1-6r) are mixed at a temperature of 0 to 150 ° C; A method of mixing and reacting in a reaction vessel. In this case, a catalyst or a solvent may be used.

作為可使用的觸媒，可列舉例如：三乙胺、二異丙基乙胺、苄基二乙胺、咪唑、溴化四丁銨、三正辛膦、三苯膦等。 Examples of usable catalysts include triethylamine, diisopropylethylamine, benzyldiethylamine, imidazole, tetrabutylammonium bromide, tri-n-octylphosphine, and triphenylphosphine.

又，作為有機溶媒，可列舉例如：甲苯、二甲苯等的芳香族烴系溶劑、二甲醚、二乙醚、1,4-二

Figure TW201944173A_D0121
烷、四氫呋喃(THF)等的醚、丙酮、2-丁酮、甲基異丁酮等的酮系溶劑、二甲基甲醯胺(DMF)等的醯胺系溶劑、氯仿、二氯甲烷等的鹵素系溶媒、二甲亞碸(DMSO)等。 Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, dimethyl ether, diethyl ether, and 1,4-dioxane.
Figure TW201944173A_D0121
Ethers such as alkane, tetrahydrofuran (THF), ketone solvents such as acetone, 2-butanone, methyl isobutyl ketone, fluorene solvents such as dimethylformamide (DMF), chloroform, methylene chloride, etc. Halogen solvents, dimethyl sulfoxide (DMSO), etc.

(步驟VI-7)     (Step VI-7)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-7r)表示之環氧化合物的環氧基進行反應，可製造Y1為結構式(y1-7)的化合物。 By reacting the secondary amine located at the structural end of the aforementioned intermediate compound C with the epoxy group of the epoxy compound represented by the following structural formula (y1-7r), Y 1 can be produced as the structural formula (y1-7 )compound of.

Figure TW201944173A_D0122
Figure TW201944173A_D0122

(式中，R8表示碳原子數2~4之伸烷基，R13表示氫原子、碳原子數1~6之烷基或鹵素原子，m表示0~20之整數)。 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and m represents an integer of 0 to 20).

Figure TW201944173A_D0123
Figure TW201944173A_D0123

此處，前述結構式(y1-7r)及通式1-7中的R8係與結構部位(y1-3)中的R8同義，作為R13的碳原子數1~6之烷基，可列舉：甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基、戊基、己基、2-乙基丁基、異戊基、1-甲基戊基、1,3-二甲基丁基等；作為鹵素原子，可列舉：溴原子、氯原子、氟原子。 Here, R 8 in the structural formula (y1-7r) and the general formula 1-7 is synonymous with R 8 in the structural portion (y1-3), and is an alkyl group having 1 to 6 carbon atoms in R 13 , Examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, and the like; examples of the halogen atom include a bromine atom, a chlorine atom, and a fluorine atom.

又，步驟VI-7中與環氧化合物的反應，可列舉例如：於0~150℃下，將前述中間體化合物C與以前述結構式(y1-7r)表示之化合物在反應容器中進行混合而反應的方法。此時，亦可使用觸媒、溶媒。 The reaction with the epoxy compound in step VI-7 includes, for example, mixing the intermediate compound C and the compound represented by the structural formula (y1-7r) in a reaction container at 0 to 150 ° C. And the method of reaction. In this case, a catalyst or a solvent may be used.

作為可使用的觸媒，可列舉例如：三乙胺、二異丙基乙胺、苄基二乙胺、咪唑、溴化四丁銨、三正辛膦、三苯膦等。 Examples of usable catalysts include triethylamine, diisopropylethylamine, benzyldiethylamine, imidazole, tetrabutylammonium bromide, tri-n-octylphosphine, and triphenylphosphine.

又，作為有機溶媒，可列舉例如：甲苯、二甲苯等的芳香族烴系溶劑、二甲醚、二乙醚、1,4-二

Figure TW201944173A_D0124
烷、四氫呋喃(THF)等的醚系溶劑、丙酮、2-丁酮、甲基異丁酮等的酮系溶劑、二甲基甲醯胺(DMF)等的醯胺系溶劑、氯仿、二氯甲烷等的鹵素系溶媒、二甲亞碸(DMSO)等。 Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, dimethyl ether, diethyl ether, and 1,4-dioxane.
Figure TW201944173A_D0124
Ether solvents such as alkane, tetrahydrofuran (THF), ketone solvents such as acetone, 2-butanone, and methyl isobutyl ketone; amine solvents such as dimethylformamide (DMF), chloroform, dichloro Halogen-based solvents such as methane, dimethyl sulfoxide (DMSO), and the like.

(步驟VI-8)     (Step VI-8)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-8r)表示之化合物的(甲基)丙烯醯基進行反應，可製造前述通式(1)中的Y1為結構式(y1-8)的化合物。 By reacting the secondary amine located at the structural end of the intermediate compound C with the (meth) acrylfluorenyl group of the compound represented by the following structural formula (y1-8r), the general formula (1) can be produced. Y 1 is a compound of structural formula (y1-8).

Figure TW201944173A_D0125
Figure TW201944173A_D0125

(式中，R8表示碳原子數2~4之伸烷基，R10表示氫原子或甲基，R14表示具有p+1個連接鍵的碳原子數5~18之烴基，1表示0~20之整數，p表示1~3之整數)。 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, R 14 represents a hydrocarbon group having 5 to 18 carbon atoms having p + 1 connection bonds, and 1 represents 0. An integer of ~ 20, p represents an integer of 1 to 3).

Figure TW201944173A_D0126
Figure TW201944173A_D0126

此處，前述結構式(y1-8r)及通式1-8中的R8係與結構部位(y1-3)中的R8同義，R14中所謂具有p+1個連接鍵的碳原子數3~25之烴基，可列舉：甘油殘基、三羥甲基丙烷殘基、新戊四醇殘基等的脂肪族多元醇殘基；正伸丙基、1,2-伸丙基、正伸丁基、2-甲基-丙-1,2- 二基、1,5-戊烷二基、1,6-己烷二基、1,7-庚烷二基、1,8-辛烷二基、1,9-壬烷二基、1,10-癸烷二基、3,8-癸烷二基、1,11-十一烷二基、1,12-十二烷二基、1,13-十三烷二基、1,14-十四烷二基、1,15-十五烷二基、1,16-十六烷二基、1,17-十七烷二基、1,18-十八烷二基、1,19-十九烷二基、1,20-二十烷二基、1,21-二十一烷二基、1,22-二十二烷二基、1,23-二十三烷二基、1,24-二十四烷二基、1,25-二十五烷二基。 Here, the R 8 in the aforementioned structural formula (y1-8r) and the general formula 1-8 is synonymous with R 8 in the structural site (y1-3), and R 14 is a so-called carbon atom having a p + 1 connection bond. Examples of the hydrocarbon group of 3 to 25 include: aliphatic polyhydric alcohol residues such as glycerol residues, trimethylolpropane residues, neopentaerythritol residues; ortho-, propane-, and propane Butyl, 2-methyl-propan-1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octane Diyl, 1,9-nonanediyl, 1,10-decanediyl, 3,8-decanediyl, 1,11-undecanediyl, 1,12-dodecanediyl, 1,13-tridecanediyl, 1,14-tetradecanediyl, 1,15-pentadecanediyl, 1,16-hexadecanediyl, 1,17-heptadecanediyl, 1,18-octadecanediyl, 1,19-nonadecanediyl, 1,20-icosanediyl, 1,21-icosanediyl, 1,22-icosanediyl Group, 1,23-icostradecanediyl, 1,24-tecosatecanediyl, 1,25-pentadecanediyl.

此處，所謂殘基表示除了多元醇的羥基以外的烴結構部位。 Here, the term "residue" means a hydrocarbon structure site other than the hydroxyl group of the polyhydric alcohol.

(步驟VI-8)中的麥可加成反應可在周知慣用的反應條件下進行。作為一般方法，可列舉於0~150℃下，將前述中間體化合物C與前述具有作為麥可受體之功能的前述結構式(y1-8r)所表示之化合物在反應容器中進行混合而反應的方法。此時，亦可使用觸媒、溶媒。 The Michael addition reaction in (Step VI-8) can be performed under well-known reaction conditions. As a general method, it is possible to mix and react the intermediate compound C and the compound represented by the structural formula (y1-8r) having a function as a Michael acceptor in a reaction vessel at 0 to 150 ° C. Methods. In this case, a catalyst or a solvent may be used.

作為可使用的觸媒，可列舉例如：氫氧化四丁銨、四甲基胍、二吖雙環十一烯、1,4-二吖雙環[2.2.2]、三級丁酸鈉等。 Examples of usable catalysts include tetrabutylammonium hydroxide, tetramethylguanidine, diazinebicycloundecene, 1,4-diazinebicyclo [2.2.2], and sodium tertiary butyrate.

又，作為有機溶媒，可列舉例如：戊烷、己烷、庚烷、環己烷等的飽和烴系溶劑、甲苯、二甲苯等的芳香族烴系溶劑、甲醇、乙醇、異丙醇、2-丁醇、三級丁醇、乙二醇、卡必醇等的醇系溶劑、二甲醚、二乙醚、1,4-二

Figure TW201944173A_D0127
烷、四氫呋喃(THF)等的醚系溶劑、二甲基甲醯胺(DMF)等的醯胺系溶劑、氯仿、二氯甲烷等的鹵素系溶媒、二甲亞碸(DMSO)等。 Examples of the organic solvent include saturated hydrocarbon-based solvents such as pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbon-based solvents such as toluene and xylene; methanol, ethanol, isopropanol; -Alcohol solvents such as butanol, tertiary butanol, ethylene glycol, carbitol, dimethyl ether, diethyl ether, 1,4-dioxo
Figure TW201944173A_D0127
Ether solvents such as alkane and tetrahydrofuran (THF), amine solvents such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, dimethyl sulfoxide (DMSO), and the like.

前述中間體化合物C與前述具有作為麥可受體之功能的前述結構式(y1-8r)所表示之化合物的混合比並無特別限定，但中間體化合物C中的二級胺基(i)與前述結構式(y1-8r)所表示之化合物中的(甲基)丙烯醯基(ii)的當量比[(i)/(ii)]較佳為1/1.5~1/30。若當量比[(i)/(ii)]超過1/1.5，則前述中間體化合物C或其分解物從塗膜發生遷移的可能性提高，若當量比[(i)/(ii)]小於1/30，則有麥可加成反應物的硬化性能差的傾向。從所得到之麥可加成反應物的硬化性能與塗膜溶出物量的觀點來看，當量比[(i)/(ii)]特佳為1/2~1/20。 The mixing ratio of the intermediate compound C and the compound represented by the structural formula (y1-8r) having the function as a Michael acceptor is not particularly limited, but the secondary amine group (i) in the intermediate compound C The equivalent ratio [(i) / (ii)] of the (meth) acrylfluorenyl group (ii) in the compound represented by the aforementioned structural formula (y1-8r) is preferably 1 / 1.5 to 1/30. If the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration of the intermediate compound C or its decomposed product from the coating film increases, and if the equivalent ratio [(i) / (ii)] is less than 1/30, there is a tendency that the hardening property of the Michael addition reactant is poor. From the viewpoints of the hardening performance of the obtained wheat addition reaction product and the amount of coating film eluted matter, the equivalent ratio [(i) / (ii)] is particularly preferably 1/2 to 1/20.

此處，就前述具有作為麥可受體之功能的前述結構式(y1-8r)表示之化合物的例子而言，可列舉例如：二乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等的二官能丙烯酸酯；三羥甲基丙烷三(甲基)丙烯酸酯及其環氧乙烷或環氧丙烷等的環氧烷(alkylene oxide)改質物；新戊四醇三或四(甲基)丙烯酸酯及其環氧乙烷或環氧丙烷等的環氧烷改質物；二-三羥甲基丙烷四(甲基)丙烯酸酯及其環氧乙烷或環氧丙烷等的環氧烷改質物；二新戊四醇四或五或六(甲基)丙烯酸酯及其己內酯改質物等的多官能(甲基)丙烯酸酯；藉由雙酚A二環氧丙基醚或三羥甲基丙烷三環氧丙基醚等的聚環氧丙基醚與(甲基)丙烯酸的反應而得的環氧(甲基)丙烯酸酯；藉由異佛爾酮二異氰酸酯或六亞甲基二異氰酸 酯三量體等的聚異氰酸酯化合物與(甲基)丙烯酸羥乙酯或新戊四醇三(甲基)丙烯酸酯等具有羥基之丙烯酸酯的反應而得的胺基甲酸酯(甲基)丙烯酸酯(urethane(meth)acrylate)；藉由苯偏三酸或琥珀酸等的多元酸、乙二醇或新戊二醇等的多元醇及(甲基)丙烯酸羥乙酯或新戊四醇三(甲基)丙烯酸酯等具有羥基之(甲基)丙烯酸酯的反應而得的聚酯(甲基)丙烯酸酯；藉由(甲基)丙烯酸環氧丙酯與單官能(甲基)丙烯酸酯之聚合物、及(甲基)丙烯酸的反應而得的高分子量型聚(甲基)丙烯酸酯等，但並不限定於此等。又，此等反應性化合物可單獨使用，亦可混合複數種使用。 Here, examples of the compound represented by the aforementioned structural formula (y1-8r) having a function as a Michael receptor include diethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl Difunctional acrylates such as alcohol di (meth) acrylates; trimethylolpropane tri (meth) acrylates and their alkylene oxide modifications such as ethylene oxide or propylene oxide; new Pentaerythritol tri or tetra (meth) acrylate and its alkylene oxide modified products such as ethylene oxide or propylene oxide; di-trimethylolpropane tetra (meth) acrylate and its ethylene oxide Modified alkylene oxide such as propylene oxide; polyfunctional (meth) acrylates such as dipentaerythritol tetra- or penta- or hexa (meth) acrylate and its caprolactone modified products; etc. by bisphenol A epoxy (meth) acrylate obtained by reacting poly (glycidyl ether) such as diglycidyl ether or trimethylolpropane triglycidyl ether with (meth) acrylic acid; Buddha A polyisocyanate compound such as ketone diisocyanate or hexamethylene diisocyanate trisomer is obtained by reacting a hydroxyl-containing acrylate such as hydroxyethyl (meth) acrylate or neopentaerythritol tri (meth) acrylate. (Urethane (meth) acrylate); by using polyacids such as trimellitic acid or succinic acid, polyols such as ethylene glycol or neopentyl glycol, and (meth) ) A polyester (meth) acrylate obtained by the reaction of a (meth) acrylate having a hydroxyl group, such as hydroxyethyl acrylate or neopentaerythritol tri (meth) acrylate; The high molecular weight poly (meth) acrylate and the like obtained by the reaction of a propyl ester with a polymer of a monofunctional (meth) acrylate and a (meth) acrylic acid are not limited thereto. These reactive compounds may be used alone or in combination.

(步驟VI-9)     (Step VI-9)    

藉由使位於前述中間體化合物C中之結構末端的二級胺與以下述結構式(y1-9r)表示之異氰酸酯化合物的異氰酸酯基進行反應，可製造Y1為結構式(y1-9)的化合物。 By reacting a secondary amine located at the structural end of the intermediate compound C with an isocyanate group of an isocyanate compound represented by the following structural formula (y1-9r), Y 1 having the structural formula (y1-9) can be produced. Compound.

R15-NCO (y1-9r) R 15 -NCO (y1-9r)

(式中，R15表示碳原子數4~18之烷基、碳原子數6~10之脂肪族環狀烴基、芳香族基、丙烯醯氧基乙基)。 (In the formula, R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, an aromatic group, and acryloxyethyl group).

Figure TW201944173A_D0128
Figure TW201944173A_D0128

此處，作為以前述結構式(y1-9r)表示之異氰酸酯化合物，可列舉例如：異氰酸丙酯、異氰酸丁酯、異氰酸己酯、異氰酸十二酯、異氰酸十八酯等的碳原子數4~18之異氰酸烷酯；異氰酸環己酯、異氰酸金剛烷酯等的碳原子數6~10的含異氰酸酯基之脂肪族環狀烴；異氰酸苯酯、異氰酸苄酯、異氰酸苯乙酯、異氰酸甲苯胺酯等含異氰酸酯基之芳香族烴。 Here, examples of the isocyanate compound represented by the structural formula (y1-9r) include propyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, and isocyanate. Alkyl isocyanates having 4 to 18 carbon atoms, such as octadecyl ester; Cyclohexyl isocyanate, amantadyl isocyanate, and other aliphatic cyclic hydrocarbons containing isocyanate groups having 6 to 10 carbon atoms; Isocyanate-containing aromatic hydrocarbons such as phenyl isocyanate, benzyl isocyanate, phenethyl isocyanate, and toluidine isocyanate.

又，(步驟VI-9)中的中間體化合物C與以前述結構式(y1-9r)表示之異氰酸酯化合物的反應，可列舉例如可於0~150℃下，將兩者在反應容器中進行混合而反應的方法，亦可使用觸媒、溶媒。 The reaction between the intermediate compound C in (Step VI-9) and the isocyanate compound represented by the aforementioned structural formula (y1-9r) includes, for example, that they can be carried out in a reaction container at 0 to 150 ° C. A method of mixing and reacting may also use a catalyst or a solvent.

作為可使用的觸媒，可列舉例如：三乙胺、二吖雙環十一烯、二月桂酸二丁基錫、三正辛膦、三苯膦等。 Examples of usable catalysts include triethylamine, diazinebicycloundecene, dibutyltin dilaurate, tri-n-octylphosphine, and triphenylphosphine.

又，作為有機溶媒，可列舉例如：甲苯、二甲苯等的芳香族烴系溶劑、二甲醚、二乙醚、1,4-二

Figure TW201944173A_D0129
烷、四氫呋喃(THF)等的醚系溶劑、丙酮、2-丁酮、甲基異丁酮等的酮系溶劑、二甲基甲醯胺(DMF)等的醯胺系溶劑、氯仿、二氯甲烷等的鹵素系溶媒、二甲亞碸(DMSO)等。 Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, dimethyl ether, diethyl ether, and 1,4-dioxane.
Figure TW201944173A_D0129
Ether solvents such as alkane, tetrahydrofuran (THF), ketone solvents such as acetone, 2-butanone, and methyl isobutyl ketone; amine solvents such as dimethylformamide (DMF), chloroform, dichloride Halogen-based solvents such as methane, dimethyl sulfoxide (DMSO), and the like.

相對於前述含酸基之(甲基)丙烯酸酯樹脂(A)100質量份，前述光聚合起始劑(B)的使用量較佳為1~20質量份的範圍。 The amount of the photopolymerization initiator (B) used is preferably in the range of 1 to 20 parts by mass based on 100 parts by mass of the acid group-containing (meth) acrylate resin (A).

本發明之感光性樹脂組成物，為了進一步提高硬化性能，亦可因應需求使用光敏劑、三級胺類等的光起始助劑。作為前述光敏劑，可列舉例如：2,4-二乙基氧硫

Figure TW201944173A_D0130
、2,4-二異丙基氧硫
Figure TW201944173A_D0131
等的氧硫
Figure TW201944173A_D0132
系、4,4’-雙(二乙胺基)二苯甲酮等的二苯甲酮系、蒽醌等。另一方面，作為三級胺，可列舉例如：對二甲胺基苯甲酸乙酯、對二甲胺基苯甲酸異戊酯、N,N-二甲基芐胺等。又，亦可適當使用1分子內以多元醇等使複數光敏劑、三級胺類分支之高分子量化合物。前述光起始助劑，相對於感光性樹脂組成物的總量，較佳為以0.03~20質量份來使用，更佳為以0.1~10質量份來使用。 In order to further improve the hardening performance of the photosensitive resin composition of the present invention, a photoinitiator such as a photosensitizer or a tertiary amine may be used according to demand. Examples of the photosensitizer include: 2,4-diethyloxysulfur
Figure TW201944173A_D0130
2,4-diisopropyloxysulfur
Figure TW201944173A_D0131
Oxygen and sulfur
Figure TW201944173A_D0132
Benzophenone based on 4,4'-bis (diethylamino) benzophenone, anthraquinone, etc. On the other hand, examples of tertiary amines include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and N, N-dimethylbenzylamine. In addition, a high-molecular-weight compound obtained by branching a plurality of photosensitizers and tertiary amines with a polyhydric alcohol or the like in one molecule may be appropriately used. The photo-starting aid is preferably used in an amount of 0.03 to 20 parts by mass with respect to the total amount of the photosensitive resin composition, and more preferably used in an amount of 0.1 to 10 parts by mass.

又，在不損及本發明之效果的範圍內，亦可併用前述光聚合起始劑(B)以外的其他光聚合起始劑。 Moreover, in the range which does not impair the effect of this invention, you may use together photoinitiator other than the said photoinitiator (B).

作為前述其他光聚合起始劑，可列舉例如：1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、氧硫

Figure TW201944173A_D0133
及氧硫
Figure TW201944173A_D0134
衍生物、2,2'-二甲氧基-1,2-二苯乙烷-1-酮、氧化二苯基(2,4,6-三甲氧基苯甲醯基)膦、氧化2,4,6-三甲基苯甲醯基二苯膦、氧化雙(2,4,6-三甲基苯甲醯基)苯膦、2-甲基-1-(4-甲硫基苯基)-2-
Figure TW201944173A_D0135
啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-
Figure TW201944173A_D0136
啉基苯基)-1-丁酮等。 Examples of the other photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1- [4- (2-hydroxyethyl (Oxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oxygen sulfur
Figure TW201944173A_D0133
Oxygen and sulfur
Figure TW201944173A_D0134
Derivatives, 2,2 '- dimethoxy-1,2-diphenylethane-1-oxide, diphenyl (2,4,6-trimethoxy-benzoyl) phosphine oxide, 2, 4,6-trimethylbenzylidene diphenylphosphine, bis (2,4,6-trimethylbenzylidene) phenylphosphine, 2-methyl-1- (4-methylthiophenyl) )-2-
Figure TW201944173A_D0135
Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-
Figure TW201944173A_D0136
Phenylphenyl) -1-butanone and the like.

作為前述其他光聚合起始劑的市售品，可列舉例如：「Omnirad-1173」、「Omnirad-184」、「Omnirad-127」、「Omnirad-2959」、「Omnirad-369」、「Omnirad-379」、「Omnirad-907」、「Omnirad-4265」、「Omnirad-1000」、「Omnirad-651」、「Omnirad-TPO」、「Omnirad-819」、「Omnirad-2022」、「Omnirad-2100」、「Omnirad-754」、「Omnirad-784」、「Omnirad-500」、「Omnirad-81」(IGM公司製)、「kayacure-DETX」、「kayacure-MBP」、「kayacure-DMBI」、「kayacure-EPA」、「kayacure-OA」(日本化藥股份有限公司製)、「Vicure-10」、「Vicure-55」(Stauffer Chemical公司製)、「Trigonal P1」(AKZO公司製)、「Sandoray 1000」(SANDOZ公司製)、「Deap」(APJOHN公司製)、「Quantacure-PDO」、「Quantacure-ITX」、「Quantacure-EPD」(Ward Blenkinsop公司製)、「Runtecure-1104」(Runtec公司製)等。 Examples of commercially available products of the other photopolymerization initiators include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad- 379 "," Omnirad-907 "," Omnirad-4265 "," Omnirad-1000 "," Omnirad-651 "," Omnirad-TPO "," Omnirad-819 "," Omnirad-2022 "," Omnirad-2100 " , "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "kayacure-DETX", "kayacure-MBP", "kayacure-DMBI", "kayacure -EPA "," kayacure-OA "(manufactured by Nippon Kayaku Co., Ltd.)," Vicure-10 "," Vicure-55 "(manufactured by Stauffer Chemical)," Trigonal P1 "(manufactured by AKZO)," Sandoray 1000 " "(Made by SANDOZ)," Deap "(made by APJOHN)," Quantacure-PDO "," Quantacure-ITX "," Quantacure-EPD "(made by Ward Blenkinsop)," Runtecure-1104 "(made by Runtec) Wait.

本發明之感光性樹脂組成物亦可含有前述含酸基之(甲基)丙烯酸酯樹脂(A)以外的其他樹脂成分。作為前述其他樹脂成分，可列舉例如：對於雙酚型環氧樹脂、酚醛清漆型環氧樹脂等的環氧樹脂，使(甲基)丙烯酸、二羧酸酐、因應需求的不飽和單羧酸酐等進行反應而得之樹脂中具有羧基與(甲基)丙烯醯基的樹脂、各種(甲基)丙烯酸酯單體等。 The photosensitive resin composition of this invention may contain other resin components other than the said acid group containing (meth) acrylate resin (A). Examples of the other resin components include epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy resins, in which (meth) acrylic acid, dicarboxylic anhydrides, and unsaturated monocarboxylic anhydrides according to demand are used. Among the resins obtained by the reaction are resins having a carboxyl group and a (meth) acrylfluorene group, various (meth) acrylate monomers, and the like.

作為前述(甲基)丙烯酸酯單體，可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯 酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸酯辛酯等的脂肪族單(甲基)丙烯酸酯化合物；(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、金剛烷基單(甲基)丙烯酸酯等的脂環型單(甲基)丙烯酸酯化合物；(甲基)丙烯酸環氧丙酯、丙烯酸四氫糠酯等的雜環型單(甲基)丙烯酸酯化合物；(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苯基苄酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基乙氧基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸苯氧基苄酯、(甲基)丙烯酸芐基芐酯、(甲基)丙烯酸苯基苯氧基乙酯等芳香族單(甲基)丙烯酸酯化合物等的單(甲基)丙烯酸酯化合物；於前述各種單(甲基)丙烯酸酯單體的分子結構中導入有(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等聚氧伸烷基鏈的(聚)氧伸烷基改質單(甲基)丙烯酸酯化合物；於前述各種單(甲基)丙烯酸酯化合物的分子結構中導入有(聚)內酯結構的內酯改質單(甲基)丙烯酸酯化合物；乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等的脂肪族二(甲基)丙烯酸酯化合物；1,4-環己烷二甲醇二(甲基)丙烯酸酯、降莰烷二(甲基)丙烯酸酯、降莰烷二甲醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯等的脂環型二(甲基)丙烯酸酯化合物；聯苯酚二(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯等 的芳香族二(甲基)丙烯酸酯化合物；於前述各種二(甲基)丙烯酸酯化合物的分子結構中導入有(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的聚氧伸烷基改質二(甲基)丙烯酸酯化合物；於前述各種二(甲基)丙烯酸酯化合物的分子結構中導入有(聚)內酯結構的內酯改質二(甲基)丙烯酸酯化合物；三羥甲基丙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等的脂肪族三(甲基)丙烯酸酯化合物；於前述脂肪族三(甲基)丙烯酸酯化合物的分子結構中導入有(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的(聚)氧伸烷基改質三(甲基)丙烯酸酯化合物；於前述脂肪族三(甲基)丙烯酸酯化合物的分子結構中導入有(聚)內酯結構的內酯改質三(甲基)丙烯酸酯化合物；新戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等的4官能以上之脂肪族聚(甲基)丙烯酸酯化合物；於前述脂肪族聚(甲基)丙烯酸酯化合物的分子結構中導入有(聚)氧伸乙基鏈、(聚)氧伸丙基鏈、(聚)氧四亞甲基鏈等(聚)氧伸烷基鏈的4官能以上之(聚)氧伸烷基改質聚(甲基)丙烯酸酯化合物；於前述脂肪族聚(甲基)丙烯酸酯化合物的分子結構中導入有(聚)內酯結構的4官能以上之內酯改質聚(甲基)丙烯酸酯化合物等。 Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) ) Aliphatic mono (meth) acrylate compounds such as amyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate; (meth) Alicyclic mono (meth) acrylate compounds such as cyclohexyl acrylate, isoamyl (meth) acrylate, adamantyl mono (meth) acrylate, etc .; glycidyl (meth) acrylate, tetraacrylate Heterocyclic mono (meth) acrylate compounds such as hydrogen furfuryl ester; benzyl (meth) acrylate, phenyl (meth) acrylate, phenyl benzyl (meth) acrylate, phenoxy (meth) acrylate Ester, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, benzene (meth) acrylate Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds such as oxybenzyl ester, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate; Into the molecular structure of the aforementioned various mono (meth) acrylate monomers, polyoxyalkylenes such as (poly) oxyethylene chain, (poly) oxypropylene chain, and (poly) oxytetramethylene chain are introduced. (Poly) oxyalkylene groups of the base chain modified mono (meth) acrylate compounds; lactone modified monomers with a (poly) lactone structure introduced into the molecular structure of the aforementioned various mono (meth) acrylate compounds (Meth) acrylate compounds; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Aliphatic di (meth) acrylate compounds such as neopentyl glycol di (meth) acrylate; 1,4-cyclohexanedimethanol di (meth) acrylate, norbornane di (meth) acrylic acid Alicyclic di (methyl) such as esters, norbornane dimethanol di (meth) acrylate, dicyclopentyl di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, etc. Acrylate compounds; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate, bisphenol di (meth) acrylate, and the like; In the molecular structure of the compound, poly (oxyalkylene) chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains, etc. are introduced. Di (meth) acrylate compound; lactone modified with (poly) lactone structure introduced into the molecular structure of each of the aforementioned di (meth) acrylate compounds; modified di (meth) acrylate compound; trimethylol Aliphatic tri (meth) acrylate compounds such as propane tri (meth) acrylate, glycerol tri (meth) acrylate, etc .; introduced into the molecular structure of the aforementioned aliphatic tri (meth) acrylate compound ( (Poly) oxyalkylene chain modified by (poly) oxyalkylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. Acrylate compounds; lactone modified (()) lactone compounds with a (poly) lactone structure introduced into the molecular structure of the aforementioned aliphatic tri (meth) acrylate compounds; neopentaerythritol tetrakis (methyl) ) Acrylic ester, di-trimethylolpropane tetra (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, etc. Ester compound; (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain, etc. are introduced into the molecular structure of the aforementioned aliphatic poly (meth) acrylate compound ( (Poly) oxyalkylene chain with more than four functional (poly) oxyalkylene groups modified poly (meth) acrylate compound; (Poly (poly) methacrylate) is introduced into the molecular structure of the aforementioned aliphatic poly (meth) acrylate compound ) A 4-functional or more lactone-modified poly (meth) acrylate compound with a lactone structure.

以調節塗布黏度等為目的，本發明之感光性樹脂組成物亦可含有有機溶劑，其種類、添加量可因應期望的性能而適當選擇及調整。 For the purpose of adjusting coating viscosity and the like, the photosensitive resin composition of the present invention may also contain an organic solvent, and its type and addition amount may be appropriately selected and adjusted according to desired performance.

作為前述有機溶劑，可列舉例如：甲乙酮、丙酮、異丁酮等的酮溶劑；四氫呋喃、二

Figure TW201944173A_D0137
(dioxolane)等的環狀醚溶劑；乙酸甲酯、乙酸乙酯、乙酸丁酯等的酯溶劑；甲苯、二甲苯、溶劑石油腦等的芳香族溶劑；環己烷、甲基環己烷等的脂環族溶劑；卡必醇、賽路蘇、甲醇、異丙醇、丁醇、丙二醇單甲醚等的醇溶劑；烷二醇單烷基醚、二烷二醇單烷基醚、二烷二醇單烷基醚乙酸酯等的二醇醚溶劑等。此等有機溶劑可單獨使用亦可併用2種以上。 Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; tetrahydrofuran, and
Figure TW201944173A_D0137
(dioxolane) and other cyclic ether solvents; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; cyclohexane, methylcyclohexane, etc. Alicyclic solvents; alcohol solvents such as carbitol, celex, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc .; alkanediol monoalkyl ether, dioxane monoalkyl ether, Glycol ether solvents such as alkanediol monoalkyl ether acetate and the like. These organic solvents may be used alone or in combination of two or more.

又，本發明之感光性樹脂組成物中亦可因應需求含有無機微粒子或聚合物微粒子、顏料、消泡劑、黏度調整劑、調平劑、阻燃劑及保存穩定劑等的各種添加劑。 In addition, the photosensitive resin composition of the present invention may contain various additives such as inorganic fine particles or polymer fine particles, pigments, antifoaming agents, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers as required.

本發明之硬化物可藉由對前述感光性樹脂組成物照射活性能量線而得。作為前述活性能量線，可列舉例如：紫外線、電子束、α線、β線、γ線等的游離輻射線。又，使用紫外線作為前述活性能量線的情況下，於效率佳地進行利用紫外線之硬化反應的面上，可在氮氣等惰性氣體環境下照射，亦可在空氣環境下照射。 The cured product of the present invention can be obtained by irradiating the photosensitive resin composition with active energy rays. Examples of the active energy ray include free radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case where ultraviolet rays are used as the active energy rays, the surface on which the hardening reaction using ultraviolet rays is efficiently performed may be irradiated in an inert gas environment such as nitrogen, or may be irradiated in an air environment.

作為紫外線產生源，從實用性、經濟性方面來看，一般係使用紫外線燈。具體而言，可列舉：低壓汞燈、高壓汞燈、超高壓汞燈、氙燈、鎵燈、金屬鹵化物燈、太陽光、LED等。 As a source of ultraviolet rays, in terms of practicality and economy, ultraviolet lamps are generally used. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

又，使本發明之感光性樹脂組成物硬化而得的硬化物具有優異的耐熱性，不易發生逸氣，因此可 適用於作為例如半導體裝置用途中的阻焊劑、層間絕緣材料、封裝材料、底部填充材料(underfill material)、電路元件等的封裝接著層、或積體電路元件與電路基板的接著層。又，適合用於以LCD、OELD為代表之薄型顯示器用途中的薄膜電晶體保護膜、液晶彩色濾光片保護膜、彩色濾光片用顏料光阻、黑色矩陣(black matrix)用光阻、間隔物等。 In addition, the cured product obtained by curing the photosensitive resin composition of the present invention has excellent heat resistance and is less prone to outgassing. Therefore, it is suitable for use as, for example, a solder resist, an interlayer insulating material, a packaging material, and a bottom for semiconductor device applications. An underfill material, a packaging bonding layer for a circuit element, or the like, or a bonding layer for an integrated circuit element and a circuit substrate. In addition, it is suitable for thin-film transistor protective films, liquid crystal color filter protective films, color filter pigment photoresistors, black matrix photoresistors for thin display applications typified by LCD and OELD. Spacers, etc.

本發明之阻焊劑用樹脂材料，可因應需求於前述感光性樹脂組成物中使用例如硬化劑、硬化促進劑、有機溶劑、無機微粒子或聚合物微粒子、顏料、消泡劑、黏度調整劑、調平劑、阻燃劑、保存穩定劑等的各種添加劑等。 The resin material for a solder resist of the present invention can be used in the photosensitive resin composition according to need, for example, a hardener, a hardening accelerator, an organic solvent, an inorganic fine particle or a polymer fine particle, a pigment, a defoamer, a viscosity adjuster, Various additives such as leveling agents, flame retardants, and storage stabilizers.

作為前述硬化劑，只要是具有可與前述含酸基之(甲基)丙烯酸酯樹脂(A)中的羧基反應的官能基者，則並無特別限制，可列舉例如環氧樹脂。作為前述環氧樹脂，可列舉例如：雙酚型環氧樹脂、伸苯醚型環氧樹脂、伸萘醚型環氧樹脂、聯苯型環氧樹脂、三苯甲烷型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、萘酚-苯酚共縮合酚醛清漆型環氧樹脂、萘酚-甲酚共縮合酚醛清漆型環氧樹脂、苯酚芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂、雙環戊二烯-酚加成反應型環氧樹脂等。此等環氧樹脂可單獨使用亦可併用2種以上。又，此等之中，從硬化物之耐熱性優異來看，較佳為苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧 樹脂、雙酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、萘酚-苯酚共縮合酚醛清漆型環氧樹脂、萘酚-甲酚共縮合酚醛清漆型環氧樹脂等的酚醛清漆型環氧樹脂，特佳為軟化點在50~120℃之範圍者。 The hardener is not particularly limited as long as it has a functional group capable of reacting with a carboxyl group in the acid group-containing (meth) acrylate resin (A), and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol epoxy resin, phenylene ether epoxy resin, naphthyl ether epoxy resin, biphenyl epoxy resin, triphenylmethane epoxy resin, and phenol novolac. Varnish type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, naphthol-cresol Phenol co-condensation novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more. Among these, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol novolac-type epoxy resin, and naphthol novolac are preferable from the viewpoint of excellent heat resistance of the cured product. Novolac-type epoxy resin, naphthol-phenol co-condensation novolac-type epoxy resin, naphthol-cresol co-condensation novolac-type epoxy resin, and other novolac-type epoxy resins, particularly preferably having a softening point of 50 to 120 ° C Range of those.

前述所謂硬化促進劑係促進前述硬化劑的硬化反應者，使用環氧樹脂作為前述硬化劑的情況下，可列舉例如：磷系化合物、三級胺、咪唑、有機酸金屬鹽、路易士酸、胺錯鹽等。此等硬化促進劑可單獨使用亦可併用2種以上。又，前述硬化促進劑的添加量，例如，相對於前述硬化劑100質量份，較佳為在1~10質量份的範圍內使用。 The so-called hardening accelerator is used to accelerate the hardening reaction of the hardener. When epoxy resin is used as the hardener, examples thereof include phosphorus compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acid, Amine salt and so on. These hardening accelerators may be used alone or in combination of two or more. The amount of the hardening accelerator added is, for example, preferably within a range of 1 to 10 parts by mass based on 100 parts by mass of the hardening agent.

作為前述有機溶劑，只要是可溶解前述含酸基之(甲基)丙烯酸酯樹脂(A)、硬化劑等的各種成分者，則並無特別限定，可列舉例如：甲乙酮、丙酮、異丁酮等的酮溶劑；四氫呋喃、二

Figure TW201944173A_D0138
等的環狀醚溶劑；乙酸甲酯、乙酸乙酯、乙酸丁酯等的酯溶劑；甲苯、二甲苯、溶劑石油腦等的芳香族溶劑；環己烷、甲基環己烷等的脂環族溶劑；卡必醇、賽路蘇、甲醇、異丙醇、丁醇、丙二醇單甲醚等的醇溶劑；烷二醇單烷基醚、二烷二醇單烷基醚、二烷二醇單烷基醚乙酸酯等的二醇醚溶劑等。此等有機溶劑可單獨使用亦可併用2種以上。 The organic solvent is not particularly limited as long as it can dissolve various components such as the acid group-containing (meth) acrylate resin (A) and hardener, and examples thereof include methyl ethyl ketone, acetone, and isobutyl ketone. Ketone solvents such as tetrahydrofuran
Figure TW201944173A_D0138
And other cyclic ether solvents; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic cyclohexane, methylcyclohexane, and the like Family solvents; alcohol solvents such as carbitol, celex, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc .; alkanediol monoalkyl ether, dioxane monoalkyl ether, dioxane glycol Glycol ether solvents such as monoalkyl ether acetate and the like. These organic solvents may be used alone or in combination of two or more.

本發明之阻焊構件，例如，可將前述阻焊劑用樹脂材料塗布於基材上，於60~100℃左右的溫度範圍內使有機溶媒揮發乾燥後，透過形成有期望圖案的光罩以活性能量線進行曝光，並以鹼水溶液將未曝光部進 行顯影，再於140~180℃左右的溫度範圍內進行加熱硬化而得。 For the solder resist member of the present invention, for example, the aforementioned resin material for solder resist can be coated on a substrate, and the organic solvent can be volatilized and dried in a temperature range of about 60 to 100 ° C, and then activated through a photomask formed with a desired pattern. It is obtained by performing energy-ray exposure, developing an unexposed portion with an alkaline aqueous solution, and then performing heat curing in a temperature range of about 140 to 180 ° C.

[實施例]     [Example]    

以下，藉由實施例與比較例具體說明本發明。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

(合成例1：含酸基之(甲基)丙烯酸酯樹脂(A-1)的合成)     (Synthesis Example 1: Synthesis of (meth) acrylate resin (A-1) containing acid group)    

於具備溫度計、攪拌器及回流冷卻器的燒瓶中置入101質量份的二乙二醇單甲醚乙酸酯，將428質量份的鄰甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製「EPICLON N-680」，環氧當量：214g/eq)溶解，並加入4質量份的作為抗氧化劑之二丁基羥基甲苯、0.4質量份的作為熱聚合抑制劑之對甲氧基苯酚(methoquinone)後，添加144質量份的丙烯酸、1.6質量份的三苯膦，一邊吹入空氣一邊於120℃下進行酯化反應10小時。之後，加入311質量份的二乙二醇單甲醚乙酸酯、160質量份的四氫酞酐，並於110℃下使其反應2.5小時，得到含酸基之(甲基)丙烯酸酯樹脂(1)。此含酸基之(甲基)丙烯酸酯樹脂(1)的固體成分酸價為85mgKOH/g。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 101 parts by mass of diethylene glycol monomethyl ether acetate was placed, and 428 parts by mass of o-cresol novolac epoxy resin (manufactured by DIC Corporation) "EPICLON N-680", epoxy equivalent: 214 g / eq) was dissolved, and 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of p-methoxyphenol (methoquinone) as a thermal polymerization inhibitor were added. ), 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, and the esterification reaction was performed at 120 ° C for 10 hours while blowing air. Thereafter, 311 parts by mass of diethylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added, and they were reacted at 110 ° C. for 2.5 hours to obtain an acid group-containing (meth) acrylate resin. (1). The acid value of the solid content of this acid group containing (meth) acrylate resin (1) was 85 mgKOH / g.

(合成例2：含酸基之(甲基)丙烯酸酯樹脂(A-2)的合成)     (Synthesis Example 2: Synthesis of (meth) acrylate resin (A-2) containing acid group)    

於具備溫度計、攪拌器、及回流冷卻器的燒瓶中加入379質量份的二乙二醇單甲醚乙酸酯、185質量份的異佛爾酮二異氰酸酯之異三聚氰酸酯改質物(EVONIK公司製「VESTANAT T-1890/100」，異氰酸酯基含量17.2 質量%)、146質量份的苯偏三酸酐、1.6質量份的二丁基羥基甲苯並使其溶解。在氮氣環境下，於160℃下使其反應5小時，確認異氰酸酯基含量成為0.1質量%以下。接著，添加0.3質量份的對甲氧基苯酚、112質量份的新戊四醇聚丙烯酸酯混合物(東亞合成股份有限公司製「ARONIX M-306」，新戊四醇三丙烯酸酯含量約67%，羥價159.7mgKOH/g)及3.1質量份的三苯膦，一邊吹入空氣一邊於110℃下使其反應5小時。接著，添加125質量份的甲基丙烯酸環氧丙酯，於110℃下使其反應5小時。進一步加入87質量份的琥珀酸酐，於110℃下使其反應5小時，得到含酸基之(甲基)丙烯酸酯樹脂(A-2)。此含酸基之(甲基)丙烯酸酯樹脂(A-2)的固體成分酸價為80mgKOH/g。 In a flask equipped with a thermometer, a stirrer, and a reflux cooler, 379 parts by mass of diethylene glycol monomethyl ether acetate and 185 parts by mass of isophorone diisocyanate isocyanate modified product ( "VESTANAT T-1890 / 100" manufactured by EVONIK Corporation, with an isocyanate group content of 17.2% by mass), 146 parts by mass of trimellitic anhydride, and 1.6 parts by mass of dibutylhydroxytoluene were dissolved. It was made to react at 160 degreeC for 5 hours in nitrogen atmosphere, and it confirmed that the isocyanate group content was 0.1 mass% or less. Next, 0.3 parts by mass of p-methoxyphenol and 112 parts by mass of neopentaerythritol polyacrylate mixture ("ARONIX M-306" manufactured by Toa Synthesis Co., Ltd. were added, and the content of neopentaerythritol triacrylate was about 67%. (Hydroxyl value: 159.7 mgKOH / g) and 3.1 parts by mass of triphenylphosphine, and reacted at 110 ° C. for 5 hours while blowing air. Next, 125 parts by mass of glycidyl methacrylate was added, and the mixture was reacted at 110 ° C. for 5 hours. Further, 87 parts by mass of succinic anhydride was added and reacted at 110 ° C. for 5 hours to obtain an acid group-containing (meth) acrylate resin (A-2). The acid value of the solid content of this acid group containing (meth) acrylate resin (A-2) was 80 mgKOH / g.

(合成例3：光聚合起始劑(M31)的合成)     (Synthesis Example 3: Synthesis of Photopolymerization Initiator (M31))     [步驟I]     [Step I]    

Figure TW201944173A_D0139
Figure TW201944173A_D0139

於具備攪拌機、溫度計、氮氣導入管、鹼阱(alkali trap)及滴液漏斗的1L燒瓶中置入121.8g的氯化鋁(無水)與300mL的脫水二氯甲烷，在氮氣流下，使用冰浴進行冰冷。於其中添加200g的2-溴丁醯溴。使用 滴液漏斗，耗費20分鐘將83.6g之氟苯與100mL之脫水二氯甲烷的混合溶液滴入先前的燒瓶中。滴入結束後，撤去冰浴，直接繼續攪拌2小時。攪拌結束後，將反應液投入1L的冰水中，繼續攪拌2小時。靜置後進行分液，並回收下層。以2N鹽酸清洗2次，以飽和碳酸氫鈉水溶液清洗1次，並以飽和食鹽水清洗2次。以硫酸鎂使其乾燥一天一夜後，將二氯甲烷減壓餾去，得到2-溴-1-(4-氟苯基)-1-丁酮(101)。 In a 1-liter flask equipped with a stirrer, thermometer, nitrogen introduction tube, alkali trap, and dropping funnel, 121.8 g of aluminum chloride (anhydrous) and 300 mL of dehydrated dichloromethane were placed, and an ice bath was used under a nitrogen stream. Be ice cold. 200 g of 2-bromobutyridine bromide was added thereto. Using a dropping funnel, it took 20 minutes to drop a mixed solution of 83.6 g of fluorobenzene and 100 mL of dehydrated dichloromethane into the previous flask. After the dripping was completed, the ice bath was removed and the stirring was continued for 2 hours. After the stirring was completed, the reaction solution was poured into 1 L of ice water, and stirring was continued for 2 hours. After standing, liquid separation was performed, and the lower layer was recovered. It was washed twice with 2N hydrochloric acid, once with a saturated sodium bicarbonate aqueous solution, and twice with saturated brine. After drying with magnesium sulfate for one day and one night, dichloromethane was distilled off under reduced pressure to obtain 2-bromo-1- (4-fluorophenyl) -1-butanone (101).

產量：214.3g、產率：100% Yield: 214.3g, Yield: 100%

[步驟II]     [Step II]    

Figure TW201944173A_D0140
Figure TW201944173A_D0140

於具備攪拌機、溫度計的2L燒瓶中置入157.7g的中間體(101)與750mL的甲乙酮，使用冰浴進行冰冷。使用滴液漏斗，耗費30分鐘於其中滴入174g的50質量%二甲胺水溶液。滴下結束後，撤去冰浴，直接繼續攪拌一天一夜。使用薄層層析法確認中間體(101)消失後，減壓餾去甲乙酮與二甲胺，將甲苯投入殘渣。以水清洗2次，再以飽和食鹽水清洗1次後，回收上層，以硫酸鎂使其乾燥一天一夜。將甲苯減壓餾去，得到中間體(102)。 In a 2 L flask equipped with a stirrer and a thermometer, 157.7 g of the intermediate (101) and 750 mL of methyl ethyl ketone were placed, and ice-cooled using an ice bath. Using a dropping funnel, 174 g of a 50% by mass dimethylamine aqueous solution was added dropwise thereto over 30 minutes. After dripping, remove the ice bath and continue to stir day and night. After confirming the disappearance of the intermediate (101) by thin layer chromatography, methyl ethyl ketone and dimethylamine were distilled off under reduced pressure, and toluene was added to the residue. After washing twice with water and once with saturated saline, the upper layer was recovered and dried with magnesium sulfate for one day and one night. The toluene was distilled off under reduced pressure to obtain an intermediate (102).

產量：133.3g、產率：99% Yield: 133.3g, Yield: 99%

[步驟III]     [Step III]    

Figure TW201944173A_D0141
Figure TW201944173A_D0141

於具備攪拌機、溫度計、冷卻管的500mL燒瓶中置入79.5g的中間體(102)、87.0g的4-(溴甲基)苯甲酸甲酯(103)及120mL的異丙醇(以下簡稱為「IPA」)，於50℃下攪拌一天一夜。之後，添加105mL的8M氫氧化鈉水溶液，於50℃下攪拌1小時。攪拌結束後，餾去IPA，使用12N鹽酸製備成pH5.5後，以乙酸乙酯進行萃取。於萃取液中加入己烷，過濾析出之結晶，得到中間體(104)。 In a 500 mL flask equipped with a stirrer, thermometer, and cooling tube, 79.5 g of intermediate (102), 87.0 g of methyl 4- (bromomethyl) benzoate (103), and 120 mL of isopropyl alcohol (hereinafter referred to as "IPA"), and stirred at 50 ° C for one day and one night. Thereafter, 105 mL of an 8 M aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 ° C. for 1 hour. After the stirring was completed, IPA was distilled off, and the pH was adjusted to 5.5 using 12N hydrochloric acid, followed by extraction with ethyl acetate. Hexane was added to the extract, and the precipitated crystal was filtered to obtain an intermediate (104).

產量：94.5g、產率：65.5% Yield: 94.5g, yield: 65.5%

[步驟IV]     [Step IV]    

Figure TW201944173A_D0142
Figure TW201944173A_D0142

於具備攪拌機、溫度計、滴液漏斗的1000mL燒瓶中置入35.0g的2-氯-4.6-二甲氧基-1,3,5-三

Figure TW201944173A_D0143
與400mL的脫水二氯甲烷，使用冰浴進行冰冷。使用滴液 漏斗，耗費10分鐘於其中滴入80.8g的N-甲基
Figure TW201944173A_D0144
啉。滴下結束後，添加76.0g的中間體(104)，在冰冷下攪拌1小時。使用滴液漏斗，耗費20分鐘於其中滴入200mL的溶解有9.5g的哌
Figure TW201944173A_D0145
之脫水二氯甲烷。撤去冰浴，在室溫下繼續攪拌1小時。以薄層層析法確認反應完成，加入水使反應停止。將反應物移至分液漏斗，回收下層的有機層。再以蒸餾水清洗2次後，以硫酸鎂使其乾燥一天一夜。減壓餾去二氯甲烷，將所得到之粗製生成物以乙醇進行再結晶，得到中間體(105)。 In a 1000 mL flask equipped with a stirrer, a thermometer, and a dropping funnel, 35.0 g of 2-chloro-4.6-dimethoxy-1,3,5-tri
Figure TW201944173A_D0143
It was ice-cooled with 400 mL of dehydrated dichloromethane using an ice bath. Using a dropping funnel, it took 10 minutes to drop 80.8 g of N-methyl
Figure TW201944173A_D0144
Morpho. After the completion of the dropping, 76.0 g of the intermediate (104) was added, and the mixture was stirred under ice-cooling for 1 hour. Using a dropping funnel, it took 20 minutes to add 200 mL of 9.5 g of piperazine dissolved therein.
Figure TW201944173A_D0145
It was dehydrated with dichloromethane. The ice bath was removed and stirring was continued for 1 hour at room temperature. The reaction was confirmed to be complete by thin layer chromatography, and water was added to stop the reaction. The reaction product was transferred to a separating funnel, and the lower organic layer was recovered. After washing twice with distilled water, it was dried with magnesium sulfate day and night. Dichloromethane was distilled off under reduced pressure, and the obtained crude product was recrystallized from ethanol to obtain Intermediate (105).

產量：57.5g、產率：78% Yield: 57.5g, Yield: 78%

[步驟V]     [Step V]    

Figure TW201944173A_D0146
Figure TW201944173A_D0146

於具備攪拌機、溫度計、冷卻管的500mL燒瓶中置入38.0g的中間體(105)、22.2g的哌

Figure TW201944173A_D0147
及120mL的二甲亞碸(DMSO)，並於100℃下攪拌40小時。反應結束後，添加蒸餾水與二氯甲烷，將二氯甲烷層以水清洗3次、以飽和食鹽水清洗1次，並以硫酸鎂使其乾燥一天一夜。將二氯甲烷減壓餾去，得到中間體(106)。 In a 500 mL flask equipped with a stirrer, thermometer, and cooling tube, 38.0 g of intermediate (105) and 22.2 g of piperine were placed.
Figure TW201944173A_D0147
And 120 mL of dimethylarsine (DMSO), and stirred at 100 ° C for 40 hours. After the reaction was completed, distilled water and dichloromethane were added, and the dichloromethane layer was washed three times with water and once with saturated brine, and dried with magnesium sulfate for one day and one night. Dichloromethane was distilled off under reduced pressure to obtain Intermediate (106).

產量：43.9g、產率：98% Yield: 43.9g, Yield: 98%

[步驟VI]     [Step VI]    

於具備攪拌機、冷凝器及溫度計的300mL燒瓶中加入17.4g的中間體(106)、25.7g的環氧乙烷改質三羥甲基丙烷三丙烯酸酯(MIWON公司製M3130)、43mg的對甲氧苯酚及150mL的乙醇，並於50℃下攪拌24小時。藉由減壓餾去將溶媒去除，得到以下述結構式表示之光聚合起始劑(M31)。 A 300 mL flask equipped with a stirrer, condenser, and thermometer was charged with 17.4 g of intermediate (106), 25.7 g of ethylene oxide modified trimethylolpropane triacrylate (M3130 manufactured by MIWON Corporation), and 43 mg of p-formyl Oxyphenol and 150 mL of ethanol were stirred at 50 ° C. for 24 hours. The solvent was removed by distillation under reduced pressure to obtain a photopolymerization initiator (M31) represented by the following structural formula.

產量：42.7g、產率：99% Yield: 42.7g, Yield: 99%

Figure TW201944173A_D0148
Figure TW201944173A_D0148

(合成例4：光聚合起始劑(M32)的合成)     (Synthesis Example 4: Synthesis of a photopolymerization initiator (M32))     [步驟III]     [Step III]    

Figure TW201944173A_D0149
Figure TW201944173A_D0149

於具備攪拌機、溫度計、冷卻管的500mL燒瓶中，置入41.9g的經由合成例3之步驟I及步驟II 所得到之中間體(102)、53.5g的2-[4-(溴甲基)苯基]丙酸(107)及100mL的IPA，於室溫下添加27.5mL的8M氫氧化鈉水溶液，再於50℃下攪拌2小時，形成四級銨鹽。接著，添加41mL的8M氫氧化鈉水溶液，於50℃下攪拌1小時。攪拌結束後，餾去IPA，使用6N鹽酸製備成pH5.5後，以甲苯進行萃取。將萃取液進行水洗，減壓餾去溶媒，並以矽膠層析法將所得到之粗反應物進行精製，得到中間體(108)。 In a 500 mL flask equipped with a stirrer, a thermometer, and a cooling tube, 41.9 g of the intermediate (102) obtained in Step I and Step II of Synthesis Example 3 and 53.5 g of 2- [4- (bromomethyl) were placed. Phenyl] propionic acid (107) and 100 mL of IPA, 27.5 mL of an 8 M sodium hydroxide aqueous solution was added at room temperature, and then stirred at 50 ° C. for 2 hours to form a quaternary ammonium salt. Next, 41 mL of an 8 M aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 ° C. for 1 hour. After the stirring was completed, IPA was distilled off, and the pH was adjusted to 5.5 using 6N hydrochloric acid, followed by extraction with toluene. The extract was washed with water, the solvent was distilled off under reduced pressure, and the obtained crude reaction product was purified by silica gel chromatography to obtain an intermediate (108).

產量：39.0g、產率：52.5% Yield: 39.0g, Yield: 52.5%

[步驟IV]     [Step IV]    

Figure TW201944173A_D0150
Figure TW201944173A_D0150

於具備攪拌機、溫度計、滴液漏斗的500mL燒瓶中加入19.0g的中間體(108)、80mL的二氯甲烷及0.5mL的N,N-二甲基甲醯胺，於其中緩慢地滴入6.7g的亞硫醯氯，攪拌30分鐘。使用滴液漏斗，滴入50mL的溶解有2.2g的哌

Figure TW201944173A_D0151
之脫水二氯甲烷的溶液，接著，滴下11.4g的三乙胺，於室溫下攪拌1小時。以薄層層析法確認反應完成，加入水使反應停止。將反應物移至分液漏斗，回收下層的有機層。再以蒸餾水清洗2次後，以硫酸鎂使其乾燥一天一夜。減壓餾去二氯甲烷，將所得到之粗製生成物以乙醇進行再結晶，得到中間體(109)。 In a 500 mL flask equipped with a stirrer, a thermometer, and a dropping funnel, 19.0 g of intermediate (108), 80 mL of dichloromethane, and 0.5 mL of N, N-dimethylformamide were slowly added. g of thionyl chloride and stirred for 30 minutes. Using a dropping funnel, drip 50 mL of 2.2 g of piperon
Figure TW201944173A_D0151
The solution of dehydrated dichloromethane was then added with 11.4 g of triethylamine, and the mixture was stirred at room temperature for 1 hour. The reaction was confirmed to be complete by thin layer chromatography, and water was added to stop the reaction. The reaction product was transferred to a separating funnel, and the lower organic layer was recovered. After washing twice with distilled water, it was dried with magnesium sulfate day and night. Dichloromethane was distilled off under reduced pressure, and the obtained crude product was recrystallized from ethanol to obtain Intermediate (109).

產量：17.2g、產率：85% Yield: 17.2g, Yield: 85%

[步驟V]     [Step V]    

Figure TW201944173A_D0152
Figure TW201944173A_D0152

於具備攪拌機、溫度計、冷卻管的300mL燒瓶中置入14.8g的中間體(109)、8.6g的哌

Figure TW201944173A_D0153
、5.5g的無水碳酸鉀及30mL的二甲亞碸(DMSO)，於100℃下攪拌24小時。反應結束後，添加蒸餾水與二氯甲烷，將二氯甲烷層以水清洗3次、以飽和食鹽水清洗1次，並以硫酸鎂使其乾燥一天一夜。將二氯甲烷減壓餾去，得到中間體(110)。 In a 300 mL flask equipped with a stirrer, thermometer, and cooling tube, 14.8 g of intermediate (109) and 8.6 g of piperine were placed.
Figure TW201944173A_D0153
, 5.5 g of anhydrous potassium carbonate and 30 mL of dimethylarsin (DMSO), and stirred at 100 ° C for 24 hours. After the reaction was completed, distilled water and dichloromethane were added, and the dichloromethane layer was washed three times with water and once with saturated brine, and dried with magnesium sulfate for one day and one night. Dichloromethane was distilled off under reduced pressure to obtain Intermediate (110).

產量：18.0g、產率：97.5% Yield: 18.0g, Yield: 97.5%

[步驟VI]     [Step VI]    

於具備攪拌機、冷凝器及溫度計的300mL燒瓶中加入18.5g的中間體(110)、25.7g的環氧乙烷改質三羥甲基丙烷三丙烯酸酯(MIWON公司製「M3130」)、44mg的對甲氧苯酚及150mL的乙醇，並於50℃下攪拌24小時。藉由減壓餾去將溶媒去除，得到以下述結構式表示之光聚合起始劑(M32)。 A 300 mL flask equipped with a stirrer, condenser, and thermometer was charged with 18.5 g of intermediate (110), 25.7 g of ethylene oxide modified trimethylolpropane triacrylate ("M3130" manufactured by MIWON Corporation), and 44 mg of P-methoxyphenol and 150 mL of ethanol were stirred at 50 ° C. for 24 hours. The solvent was removed by distillation under reduced pressure to obtain a photopolymerization initiator (M32) represented by the following structural formula.

產量：43.4g、產率：98.3% Yield: 43.4g, Yield: 98.3%

Figure TW201944173A_D0154
Figure TW201944173A_D0154

(實施例1：感光性樹脂組成物(1)的製備)     (Example 1: Preparation of photosensitive resin composition (1))    

將100質量份的合成例1所得到的含酸基之(甲基)丙烯酸酯樹脂(A-1)、24.6質量份的作為硬化劑之鄰甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製「EPICLON N-680」)、6.3質量份的二新戊四醇六丙烯酸酯、10質量份的合成例3所得到之光聚合起始劑(M31)、13.3質量份的二乙二醇單甲醚乙酸酯、0.5質量份的2-乙基-4-甲基咪唑、0.7質量份的酞花青綠進行摻合，並藉由輥磨機進行揉合，得到感光性樹脂組成物(1)。 100 parts by mass of an acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and 24.6 parts by mass of an o-cresol novolac-type epoxy resin as a hardener (DIC Corporation) ("EPICLON N-680"), 6.3 parts by mass of dipentaerythritol hexaacrylate, 10 parts by mass of the photopolymerization initiator (M31) obtained in Synthesis Example 3, and 13.3 parts by mass of diethylene glycol monomer Methyl ether acetate, 0.5 parts by mass of 2-ethyl-4-methylimidazole, and 0.7 parts by mass of phthalocyanine green were blended and kneaded by a roll mill to obtain a photosensitive resin composition (1 ).

(實施例2及3：感光性樹脂組成物(2)及(3)的製備)     (Examples 2 and 3: Preparation of photosensitive resin compositions (2) and (3))    

除了將實施例13所使用的含酸基之(甲基)丙烯酸酯樹脂(A-1)及光聚合起始劑(M31)替換成表1所示的組成以外，以與實施例1相同的方式得到感光性樹脂組成物(2)及(3)。 Except that the acid group-containing (meth) acrylate resin (A-1) and the photopolymerization initiator (M31) used in Example 13 were replaced with the compositions shown in Table 1, the same procedure as in Example 1 was used. In this way, photosensitive resin compositions (2) and (3) were obtained.

(比較例1及2：感光性樹脂組成物(C1)及(C2)的製備)     (Comparative Examples 1 and 2: Preparation of Photosensitive Resin Compositions (C1) and (C2))    

以表13所示的摻合量使用2-甲基-1-(4-甲硫基苯基)-2-

Figure TW201944173A_D0155
啉基丙烷-1-酮(IGM公司製「Omnirad907」)或2-苄基-2-二甲胺基-1-(4-
Figure TW201944173A_D0156
啉基苯基)-1-丁酮(IGM公司製「Omnirad369」)代替實施例1所使用的光聚合起始劑(M31)，除此以外，以與實施例1相同的方式得到感光性樹脂組成物(C1)及(C2)。 Use 2-methyl-1- (4-methylthiophenyl) -2- at the blending amounts shown in Table 13.
Figure TW201944173A_D0155
Phenylpropane-1-one ("Omnirad907" manufactured by IGM) or 2-benzyl-2-dimethylamino-1- (4-
Figure TW201944173A_D0156
A photosensitive resin was obtained in the same manner as in Example 1 except that the phosphinophenyl) -1-butanone ("Omnirad369" manufactured by IGM Corporation) was used instead of the photopolymerization initiator (M31) used in Example 1. Compositions (C1) and (C2).

使用上述實施例1~3所得到之感光性樹脂組成物(1)~(3)、以及比較例1及2所得到之感光性樹脂組成物(C1)及(C2)，進行下述評價。 The photosensitive resin compositions (1) to (3) obtained in the above Examples 1 to 3 and the photosensitive resin compositions (C1) and (C2) obtained in Comparative Examples 1 and 2 were used to perform the following evaluations.

[光感度的評價方法]     [Evaluation method of light sensitivity]    

使用塗布器(applicator)，以膜厚成為50μm的方式，將各實施例及比較例所得到之感光性樹脂組成物塗布於玻璃基材上，並於80℃下使其乾燥30分鐘。接著，使Kodak公司製「梯型板(step tablet)No.2」載置於經乾燥之塗膜上，使用金屬鹵化物燈照射500mJ/cm2的紫外線。以1%的碳酸鈉水溶液於30℃下將其進行顯影180秒鐘，基於梯型板法，以梯型板的殘留段數進行評價。此外，殘留段數越多表示光感度越高。 The photosensitive resin composition obtained by each Example and the comparative example was apply | coated to the glass substrate so that film thickness might become 50 micrometers using an applicator, and it dried at 80 degreeC for 30 minutes. Next, "step tablet No. 2" manufactured by Kodak was placed on the dried coating film, and 500 mJ / cm 2 of ultraviolet rays were irradiated with a metal halide lamp. This was developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 180 seconds, and the number of remaining sections of the ladder plate was evaluated based on the ladder plate method. In addition, the larger the number of remaining segments, the higher the light sensitivity.

[鹼顯影性的評價方法]     [Evaluation method of alkali developability]    

使用塗布器，以膜厚成為50μm的方式，將各實施例及比較例所得到之感光性樹脂組成物塗布於玻璃基材上後，於80℃下分別使其乾燥30分鐘、40分鐘、50分鐘、60分鐘、70分鐘、80分鐘、90分鐘、100分鐘， 作成乾燥時間不同的樣本。以1%碳酸鈉水溶液於30℃下將此等進行顯影180秒鐘，將基板上未殘留殘渣的樣本於80℃下的乾燥時間作為乾燥管理範圍，以下述評價基準進行評價。此外，乾燥管理範圍越長表示鹼顯影性越優異。 Using a coater, the photosensitive resin composition obtained in each example and comparative example was coated on a glass substrate so that the film thickness became 50 μm, and then dried at 80 ° C. for 30 minutes, 40 minutes, and 50 minutes. Minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, and 100 minutes. Samples with different drying times were prepared. These were developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 180 seconds, and the drying time at 80 ° C. of the samples without residues on the substrate was taken as the drying management range, and evaluated based on the following evaluation criteria. In addition, the longer the drying management range, the better the alkali developability.

○：乾燥管理範圍為60分鐘以上。 ○: The drying management range is 60 minutes or more.

×：乾燥管理範圍小於60分鐘。 ×: The drying management range is less than 60 minutes.

將實施例1~3所製備之感光性樹脂組成物(1)~(3)、以及比較例1及2所製備之感光性樹脂組成物(C1)及(C2)的組成及評價結果示於表13。 The compositions and evaluation results of the photosensitive resin compositions (1) to (3) prepared in Examples 1 to 3 and the photosensitive resin compositions (C1) and (C2) prepared in Comparative Examples 1 and 2 are shown in Table 13.

(實施例4：感光性樹脂組成物(4)的製備)     (Example 4: Preparation of photosensitive resin composition (4))    

將100質量份的合成例1所得到之含酸基之(甲基)丙烯酸酯樹脂(A-1)、24.6質量份的作為硬化劑之鄰甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製「EPICLON N-680」)、10質量份的合成例3所得到之光聚合起始劑(M31)、13.3質量份的二乙二醇單甲醚乙酸酯進行摻合，得到感光性樹脂組成物(4)。 100 parts by mass of an acid group-containing (meth) acrylate resin (A-1) obtained in Synthesis Example 1 and 24.6 parts by mass of an o-cresol novolac-type epoxy resin as a hardener (DIC Corporation) "EPICLON N-680"), 10 parts by mass of the photopolymerization initiator (M31) obtained in Synthesis Example 3, and 13.3 parts by mass of diethylene glycol monomethyl ether acetate were blended to obtain a photosensitive resin Composition (4).

(實施例5及6：感光性樹脂組成物(5)及(6)的製備)     (Examples 5 and 6: Preparation of photosensitive resin compositions (5) and (6))    

除了將實施例4所使用的含酸基之(甲基)丙烯酸酯樹脂(A-1)及光聚合起始劑(M31)替換成表14所示的組成以外，以與實施例4相同的方式得到感光性樹脂組成物(5)及(6)。 Except that the acid group-containing (meth) acrylate resin (A-1) and the photopolymerization initiator (M31) used in Example 4 were replaced with the compositions shown in Table 14, the same procedure as in Example 4 was used. In this way, photosensitive resin compositions (5) and (6) were obtained.

(比較例3及4：感光性樹脂組成物(C3)及(C4)的製備)     (Comparative Examples 3 and 4: Preparation of photosensitive resin compositions (C3) and (C4))    

以表14所示的摻合量使用2-甲基-1-(4-甲硫基苯基)-2-

Figure TW201944173A_D0158
啉基丙烷-1-酮(IGM公司製「Omnirad907」)或2-苄基-2-二甲胺基-1-(4-
Figure TW201944173A_D0159
啉基苯基)-1-丁酮(IGM公司製「Omnirad369」)代替實施例4所使用的光聚合起始劑(M31)，除此以外，以與實施例4相同的方式得到感光性樹脂組成物(C3)及(C4)。 2-methyl-1- (4-methylthiophenyl) -2- was used at the blending amount shown in Table 14.
Figure TW201944173A_D0158
Phenylpropane-1-one ("Omnirad907" manufactured by IGM) or 2-benzyl-2-dimethylamino-1- (4-
Figure TW201944173A_D0159
A photosensitive resin was obtained in the same manner as in Example 4 except that the phenylphenyl) -1-butanone ("Omnirad369" manufactured by IGM) was used in place of the photopolymerization initiator (M31) used in Example 4. Compositions (C3) and (C4).

使用上述實施例4~6所得到之感光性樹脂組成物(4)~(6)、以及比較例3及4所得到之感光性樹脂組成物(C3)及(C4)，進行下述評價。 The photosensitive resin compositions (4) to (6) obtained in the above Examples 4 to 6 and the photosensitive resin compositions (C3) and (C4) obtained in Comparative Examples 3 and 4 were used to perform the following evaluations.

[耐熱性的評價方法]     [Evaluation method of heat resistance]    

使用塗布器，以膜厚成為50μm的方式，將各實施例及比較例所得到之感光性樹脂組成物塗布於玻璃基材上，並於80℃下使其乾燥30分鐘。接著，使用金屬鹵化物燈照射500mJ/cm2的紫外線後，於200℃下加熱1小時，將硬化物從玻璃基材剝離，得到硬化物。從前述硬化物切出6mm×35mm的試片，使用黏彈性測量裝置(DMA：Rheometric公司製固體黏彈性測量裝置「RSAII」，拉伸法：頻率1Hz，升溫速度3℃/分鐘)，將彈性係數變化成為最大的溫度作為玻璃轉移溫度，進行評價。此外，玻璃轉移溫度越高表示耐熱性越優異。 The photosensitive resin composition obtained by each Example and the comparative example was apply | coated to the glass substrate so that film thickness might become 50 micrometers using the coater, and it dried at 80 degreeC for 30 minutes. Next, 500 mJ / cm 2 of ultraviolet rays were irradiated with a metal halide lamp, and then heated at 200 ° C. for 1 hour to peel the cured product from the glass substrate to obtain a cured product. A 6 mm × 35 mm test piece was cut out from the hardened material, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric, tensile method: frequency 1 Hz, heating rate 3 ° C./minute) was used to elasticity The temperature at which the coefficient change became maximum was evaluated as the glass transition temperature. In addition, a higher glass transition temperature indicates better heat resistance.

[逸氣的測量方法]     [Measurement of Yiqi]    

使用塗布器，以膜厚成為50μm的方式，將各實施例及比較例所得到之感光性樹脂組成物塗布於玻璃基材上，並於80℃下使其乾燥30分鐘。接著，使用金屬鹵化物燈照射500mJ/cm2的紫外線後，於200℃下加熱1小時，將硬化物從玻璃基材剝離，得到硬化物。從前述硬化物採集粉末樣本，置入GERSTEL公司製加熱脫附裝置(TDU)。之後，於-60℃下，分別使用液氮捕集(1)熱萃取溫度150℃下的逸氣成分10分鐘、(2)熱萃取溫度260℃下的逸氣成分10分鐘。以Agilent Technologies公司製氣相層析法質量分析裝置(6890N/5973N)將捕集之逸氣成分進行分離分析，並藉由正十二烷換算進行定量，並藉由以下評價基準進行評價。 The photosensitive resin composition obtained by each Example and the comparative example was apply | coated to the glass substrate so that film thickness might become 50 micrometers using the coater, and it dried at 80 degreeC for 30 minutes. Next, 500 mJ / cm 2 of ultraviolet rays were irradiated with a metal halide lamp, and then heated at 200 ° C. for 1 hour to peel the cured product from the glass substrate to obtain a cured product. A powder sample was collected from the hardened material and placed in a thermal desorption unit (TDU) manufactured by GERSTEL. Then, at -60 ° C, liquid nitrogen was used to capture (1) the outgas component at a thermal extraction temperature of 150 ° C for 10 minutes and (2) the outgas component at a thermal extraction temperature of 260 ° C for 10 minutes. The captured off-gas components were separated and analyzed by a gas chromatography mass analyzer (6890N / 5973N) manufactured by Agilent Technologies, and were quantified by n-dodecane conversion, and evaluated by the following evaluation criteria.

◎：幾乎未確認到逸氣成分。 ：: Hardly any outgassing component was recognized.

○：稍微確認到逸氣成分。 ○: The outgas component was slightly confirmed.

△：確認到逸氣成分。 Δ: An outgassing component was confirmed.

×：確認到大量逸氣成分。 ×: A large amount of outgassing components were confirmed.

將實施例4~6所製備之感光性樹脂組成物(4)~(6)、以及比較例3及4所製備之感光性樹脂組成物(C3)及(C4)的組成及評價結果示於表14。 The compositions and evaluation results of the photosensitive resin compositions (4) to (6) prepared in Examples 4 to 6 and the photosensitive resin compositions (C3) and (C4) prepared in Comparative Examples 3 and 4 are shown in FIG. Table 14.

此外，表13及14中的「硬化劑」表示鄰甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製「EPICLON N-680」，環氧當量：214g/當量)。 In addition, the "hardener" in Tables 13 and 14 represents an o-cresol novolac epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214 g / equivalent).

表13及14中的「有機溶劑」表示二乙二醇單甲醚乙酸酯。 The "organic solvent" in Tables 13 and 14 means diethylene glycol monomethyl ether acetate.

Claims (5)

一種感光性樹脂組成物，其係含有含酸基之(甲基)丙烯酸酯樹脂(A)及光聚合起始劑(B)的感光性樹脂組成物，其特徵為：該光聚合起始劑(B)係以下述通式(1)表示之化合物；
Figure TW201944173A_C0001
 [通式(1)中，R 1表示碳原子數1~10之烷基，R 2表示碳原子數1~12之烷基、碳原子數2~4之羥烷基、經碳原子數1或2之烷氧基所取代的碳原子數2~4之烷基的任一者，R 3表示碳原子數1~12之烷基、碳原子數2~4之羥烷基、甲氧基乙基或乙氧基乙基，又，R 2與R 3亦可成為一體而為與氮原子一起形成環結構的伸烷基，R 2與R 3亦可成為一體而為與氮原子一起形成
Figure TW201944173A_C0002
啉骨架、N-甲基哌
Figure TW201944173A_C0003
骨架或2,6-二甲基
Figure TW201944173A_C0004
啉骨架的環結構形成部位，R 4~R 7分別獨立表示氫原子、碳原子數1~8之烷基或苯基，Y 1表示不具有取代基或者具有鹵素原子或羥基作為取代基的碳原子數3~19之烷基(y1-1)、碳原子數7~19之芳烷基(y1-2)、以下述結構式(y1-3)表示之結構 部位(y1-3)、以下述結構式(y1-4)表示之結構部位(y1-4)、以下述結構式(y1-5)表示之結構部位(y1-5)、以下述結構式(y1-6)表示之結構部位(y1-6)、以下述結構式(y1-7)表示之結構部位(y1-7)、以下述結構式(y1-8)表示之結構部位(y1-8)、或以下述結構式(y1-9)表示之結構部位(y1-9)：
Figure TW201944173A_C0005
 (式中，R 8表示碳原子數2~4之伸烷基，R 9表示氫原子或苯基或碳原子數1~4之烷基，m表示0~20之整數)；
Figure TW201944173A_C0006
 (式中，R 8表示碳原子數2~4之伸烷基，R 9表示氫原子、苯基或碳數1~4之烷基，R 10表示氫原子或甲基，m表示0~20之整數)；
Figure TW201944173A_C0007
 (式中，R 10表示氫原子或甲基，R 11表示碳原子數1~18之烷基或碳原子數6~18之芳基)；
Figure TW201944173A_C0008
 (式中，R 12表示碳原子數1~18之烷基)；
Figure TW201944173A_C0009
 (式中，R 8表示碳原子數2~4之伸烷基，R 13表示氫原子、碳原子數1~6之烷基或鹵素原子，m表示0~20之整數)；
Figure TW201944173A_C0010
 (式中，R 8分別獨立表示碳原子數2~4之伸烷基，R 10表示氫原子或甲基，R 14表示具有p+1個連接鍵的碳原子數3~25之烴基，l表示0~20之整數，p表示1~3之整數)；
Figure TW201944173A_C0011
 (式中，R 15表示碳原子數4~18之烷基、碳原子數6~10之脂肪族環狀烴基、芳香族基)；X 1表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，X 2表示氫原子或甲基，X 3表示氫原子、甲基或乙基，或者X 2及X 3在虛線部形成共價鍵並且一體地表示伸乙基、1,3-伸丙基、1,2-伸丙基、2,3-伸丙基，或者X 1、X 2及X 3一體地表示以下述結構式(X-1)所表示之與氮原子一起構成雙環的4價之脂肪族烴基，
Figure TW201944173A_C0012
 Y 2表示在其結構部位末端具有氮原子或氧原子的具有(n+1)個連接鍵之有機連結基，Y 3表示單鍵、碳原子數1~3之伸烷基或碳原子數1~3之亞烷基，且n表示1~3之整數]。 A photosensitive resin composition comprising a (meth) acrylate resin (A) containing an acid group and a photopolymerization initiator (B), which is characterized in that: the photopolymerization initiator (B) is a compound represented by the following general formula (1);
Figure TW201944173A_C0001
 [In the general formula (1), R 1 represents an alkyl group having 1 to 10 carbon atoms, R 2 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and a carbon atom having 1 Or an alkoxy group substituted by 2 or 2 alkyl groups having 2 to 4 carbon atoms, R 3 represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, or a methoxy group Ethyl or ethoxyethyl, and R 2 and R 3 may be integrated to form an alkylene group that forms a ring structure with a nitrogen atom. R 2 and R 3 may also be integrated to form a group with a nitrogen atom.
Figure TW201944173A_C0002
Porphyrin skeleton, N-methyl piperazine
Figure TW201944173A_C0003
Backbone or 2,6-dimethyl
Figure TW201944173A_C0004
A ring structure forming site of a morpholine skeleton. R 4 to R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and Y 1 represents a carbon having no substituent or a halogen atom or a hydroxyl group as a substituent. Alkyl group (y1-1) having 3 to 19 atoms, aralkyl group (y1-2) having 7 to 19 carbon atoms, structural site (y1-3) represented by the following structural formula (y1-3), and the following The structural part (y1-4) represented by the structural formula (y1-4), the structural part (y1-5) represented by the following structural formula (y1-5), and the structural part represented by the following structural formula (y1-6) (y1-6), the structural part (y1-7) represented by the following structural formula (y1-7), the structural part (y1-8) represented by the following structural formula (y1-8), or the following structural formula ( y1-9) indicates the structural part (y1-9):
Figure TW201944173A_C0005
 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom or a phenyl group or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 0 to 20);
Figure TW201944173A_C0006
 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, and m represents 0 to 20 Integer);
Figure TW201944173A_C0007
 (Wherein R 10 represents a hydrogen atom or a methyl group, and R 11 represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms);
Figure TW201944173A_C0008
 (Wherein R 12 represents an alkyl group having 1 to 18 carbon atoms);
Figure TW201944173A_C0009
 (In the formula, R 8 represents an alkylene group having 2 to 4 carbon atoms, R 13 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m represents an integer of 0 to 20);
Figure TW201944173A_C0010
 (In the formula, R 8 independently represents an alkylene group having 2 to 4 carbon atoms, R 10 represents a hydrogen atom or a methyl group, R 14 represents a hydrocarbon group having 3 to 25 carbon atoms having p + 1 connection bonds, and l Represents an integer from 0 to 20, and p represents an integer from 1 to 3);
Figure TW201944173A_C0011
 (Wherein R 15 represents an alkyl group having 4 to 18 carbon atoms, an aliphatic cyclic hydrocarbon group having 6 to 10 carbon atoms, and an aromatic group); X 1 represents an ethylidene group, a 1,3-propylidene group, 1,2-propenyl, 2,3-propenyl, X 2 represents a hydrogen atom or a methyl group, X 3 represents a hydrogen atom, a methyl group, or an ethyl group, or X 2 and X 3 form a covalent bond at the dotted line and integrally extending represents an ethyl, propyl 1,3-stretched, stretch-propyl 1,2, 2,3-stretch propyl, or X 1, X 2 and X 3 are integrally represented by the following structural formula (X A tetravalent aliphatic hydrocarbon group represented by -1) which forms a bicyclic ring with a nitrogen atom,
Figure TW201944173A_C0012
 Y 2 represents an organic linking group having (n + 1) connecting bonds having a nitrogen atom or an oxygen atom at the end of its structural portion, Y 3 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or 1 carbon atom An alkylene group of ~ 3, and n represents an integer of 1 to 3]. 一種硬化物，其特徵為：其係如請求項1之感光性樹脂組成物的硬化反應物。     A cured product, which is a cured reaction product of the photosensitive resin composition as claimed in claim 1.     一種絕緣材料，其特徵為包含如請求項1之感光性樹脂組成物。     An insulating material comprising the photosensitive resin composition as claimed in claim 1.     一種阻焊劑用樹脂材料，其特徵為包含如請求項1之感光性樹脂組成物。     A resin material for a solder resist, comprising the photosensitive resin composition according to claim 1.     一種阻焊構件，其特徵為包含如請求項4之阻焊劑用樹脂材料。     A solder resist member comprising a resin material for a solder resist as claimed in claim 4.    
TW108111835A 2018-04-10 2019-04-03 Photosensitive resin composition, cured product, insulating material, resin material for solder resists and resist member TW201944173A (en)

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