WO2021253478A1 - PHOTOSENSITIVE PHOTORESIST RESIN MONOMER CONTAINING POLYCYCLIC β-KETONE STRUCTURE, AND METHOD FOR SYNTHESIZING SAME - Google Patents

PHOTOSENSITIVE PHOTORESIST RESIN MONOMER CONTAINING POLYCYCLIC β-KETONE STRUCTURE, AND METHOD FOR SYNTHESIZING SAME Download PDF

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WO2021253478A1
WO2021253478A1 PCT/CN2020/098451 CN2020098451W WO2021253478A1 WO 2021253478 A1 WO2021253478 A1 WO 2021253478A1 CN 2020098451 W CN2020098451 W CN 2020098451W WO 2021253478 A1 WO2021253478 A1 WO 2021253478A1
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resin monomer
polycyclic
photoresist resin
monomer containing
photosensitive photoresist
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PCT/CN2020/098451
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French (fr)
Chinese (zh)
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傅志伟
贺宝元
邵严亮
潘新刚
薛富奎
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徐州博康信息化学品有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms

Definitions

  • the invention relates to the field of photoresist resin monomers, in particular to a photosensitive resin monomer and a synthesis method thereof.
  • Photolithography technology refers to the use of the chemical sensitivity of photolithography materials (specifically photoresist) under the action of visible light, ultraviolet rays, electron beams, etc., through the process of exposure, development, etching, etc., to design on the mask Graphic microfabrication technology in which the graphic is transferred to the substrate.
  • Photolithography material also known as photoresist
  • photoresist is the most critical functional chemical material involved in photolithography technology.
  • the main components are resin, photoacid generator, and corresponding additives and solvents.
  • Such materials are chemically sensitive to light (including visible light, ultraviolet rays, electron beams, etc.), and their solubility in the developer changes after a photochemical reaction.
  • photoresist is divided into positive photoresist and negative photoresist: After exposure, the solubility of photoresist in the developer increases, and the same pattern as the mask is obtained, which is called positive photoresist.
  • Resist After exposure, the solubility of the photoresist in the developer is reduced or even insoluble, resulting in a pattern that is opposite to the mask, which is called a negative photoresist.
  • the photosensitive resin monomer is an important part of the photoresist polymer resin. Its main function is to produce a difference in polarity before and after exposure, resulting in different solubility in the polar developer.
  • the present invention provides a photosensitive photoresist resin monomer with a new structure. body.
  • the technical problem to be solved by the present invention is to overcome the defects of the prior art and provide a novel photosensitive photoresist resin monomer containing a polycyclic ⁇ -ketone structure and a synthesis method thereof.
  • the present invention provides the following technical solutions:
  • the present invention provides a photosensitive photoresist resin monomer containing a polycyclic ⁇ -ketone structure, characterized in that the structural formula of the photoresist resin monomer is: Wherein R 1 is methyl or H, R 2 and R 3 are each independently hydrogen, alkyl, or cycloalkyl, R 4 is alkyl or cycloalkyl, and R 2 and R 4 , R 3 and R 4 or R 2 and R 3 may be connected by a covalent bond to form a cyclic structure, and n is an integer of 1-10.
  • the specific structure of the resin monomer includes:
  • the present invention also correspondingly provides a method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic ⁇ -ketone structure.
  • the synthesis route of the resin monomer is as follows:
  • the double bond in the initial raw material A is oxidized by an oxidizing agent to form an intermediate B of a three-membered epoxy group;
  • Intermediate B is hydrolyzed with three-membered epoxy groups under acidic conditions to generate intermediate C with an o-dihydroxy structure
  • the oxidant in the synthesis step a is m-chloroperoxybenzoic acid or hydrogen peroxide.
  • the acid in the synthesis step b is sulfuric acid.
  • organic bases are selected as the bases, including triethylamine, diisopropylamine, and pyridine.
  • R 4 OH and R 2 COR 3 generate halide F under the action of hydrogen halide and sodium sulfate, and toluene is selected as the solvent.
  • the initial raw material A includes:
  • the present invention provides a new photoresist resin monomer.
  • the resin monomer contains a photosensitive group and polymerizes with other resin monomers to form a photoresist resin polymer, which will remove the hemiacetal (ketone) protection after exposure.
  • the activation energy of the hemiacetal (ketone) is relatively low, and the sensitivity is higher. After deprotection, it forms a hydroxyl structure, which increases its polarity. It is dissolved in an alkaline developer (usually TMAH).
  • TMAH alkaline developer
  • the resin monomer has exposure The solubility difference is large before and after, which can reduce roughness, improve sensitivity and resolution, and is beneficial to the formation of uniform photolithographic patterns.
  • the resin monomer has a multi-ring structure and is more resistant to etching.
  • the ketone structure enhances its affinity Water-based, it helps to improve alkali solubility.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)

Abstract

Disclosed is a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure, which relates to the field of photoresist resin monomers. Structural formula (I) thereof is shown as follows: R1 is methyl or H, R2 and R3 are independently hydrogen, an alkyl and a cycloalkyl respectively, R4 is an alkyl or cycloalkyl, and R2 and R4, R3 and R4, or R2 and R3 can form a ring structure by means of covalent bond linkage; and n is an integer from 1 to 10. The resin monomer has a large solubility difference before and after exposure, can reduce roughness and improve sensitivity and resolution, is conducive to forming a photoetched pattern with good uniformity, and has a good etching resistance.

Description

一种含多环β-酮结构的光敏型光刻胶树脂单体及其合成方法Photosensitive photoresist resin monomer containing polycyclic β-ketone structure and synthesis method thereof 技术领域Technical field
本发明涉及光刻胶树脂单体领域，尤其涉及光敏型树脂单体及其合成方法。The invention relates to the field of photoresist resin monomers, in particular to a photosensitive resin monomer and a synthesis method thereof.
背景技术Background technique
光刻技术是指利用光刻材料(特指光刻胶)在可见光、紫外线、电子束等作用下的化学敏感性，通过曝光、显影、刻蚀等工艺过程，将设计在掩膜版上的图形转移到衬底上的图形微细加工技术。Photolithography technology refers to the use of the chemical sensitivity of photolithography materials (specifically photoresist) under the action of visible light, ultraviolet rays, electron beams, etc., through the process of exposure, development, etching, etc., to design on the mask Graphic microfabrication technology in which the graphic is transferred to the substrate.
光刻材料(特指光刻胶)，又称光致抗蚀剂，是光刻技术中涉及的最关键的功能性化学材料，主要成分是树脂、光酸产生剂、以及相应的添加剂和溶剂，这类材料具有光(包括可见光、紫外线、电子束等)化学敏感性，经光化学反应，本身在显影液中的溶解性发生变化。根据光化学反应机理不同，光刻胶分为正性光刻胶与负性光刻胶：曝光后，光刻胶在显影液中溶解性增加，得到与掩膜版相同图形的称为正性光刻胶；曝光后，光刻胶在显影液中溶解性降低甚至不溶，得到与掩膜版相反图形的称为负性光刻胶。Photolithography material (specifically photoresist), also known as photoresist, is the most critical functional chemical material involved in photolithography technology. The main components are resin, photoacid generator, and corresponding additives and solvents. Such materials are chemically sensitive to light (including visible light, ultraviolet rays, electron beams, etc.), and their solubility in the developer changes after a photochemical reaction. According to the different photochemical reaction mechanism, photoresist is divided into positive photoresist and negative photoresist: After exposure, the solubility of photoresist in the developer increases, and the same pattern as the mask is obtained, which is called positive photoresist. Resist: After exposure, the solubility of the photoresist in the developer is reduced or even insoluble, resulting in a pattern that is opposite to the mask, which is called a negative photoresist.
光敏树脂单体是光刻胶聚合树脂的重要组成部分，主要作用是曝光前后产生极性差，从而导致在极性显影剂中溶解度不同，本发明提供一种新型结构的光敏型光刻胶树脂单体。The photosensitive resin monomer is an important part of the photoresist polymer resin. Its main function is to produce a difference in polarity before and after exposure, resulting in different solubility in the polar developer. The present invention provides a photosensitive photoresist resin monomer with a new structure. body.
发明内容Summary of the invention
本发明要解决的技术问题是克服现有技术的缺陷，提供一种新型的含多环β-酮结构的光敏型光刻胶树脂单体及其合成方法。The technical problem to be solved by the present invention is to overcome the defects of the prior art and provide a novel photosensitive photoresist resin monomer containing a polycyclic β-ketone structure and a synthesis method thereof.
为了解决上述技术问题，本发明提供了如下的技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
本发明提供一种含多环β-酮结构的光敏型光刻胶树脂单体，其特征在于， 所述光刻胶树脂单体的结构式为：
Figure PCTCN2020098451-appb-000001
其中R 1为甲基或者H，R 2、R 3分别独立的为氢、烷基、环烷基，R 4为烷基或者环烷基，且R 2和R 4、R 3和R 4或者R 2和R 3可以通过共价键连接形成环状结构，n为1-10的整数。 The present invention provides a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure, characterized in that the structural formula of the photoresist resin monomer is:
Figure PCTCN2020098451-appb-000001
Wherein R 1 is methyl or H, R 2 and R 3 are each independently hydrogen, alkyl, or cycloalkyl, R 4 is alkyl or cycloalkyl, and R 2 and R 4 , R 3 and R 4 or R 2 and R 3 may be connected by a covalent bond to form a cyclic structure, and n is an integer of 1-10.
作为本发明的一种优选技术方案，所述树脂单体的具体结构包括：As a preferred technical solution of the present invention, the specific structure of the resin monomer includes:
Figure PCTCN2020098451-appb-000002
Figure PCTCN2020098451-appb-000002
本发明还相应的提供一种含多环β-酮结构的光敏型光刻胶树脂单体的合成方法，所述树脂单体的合成路线如下：The present invention also correspondingly provides a method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure. The synthesis route of the resin monomer is as follows:
Figure PCTCN2020098451-appb-000003
Figure PCTCN2020098451-appb-000003
其中X为卤素，具体步骤：Where X is a halogen, the specific steps:
a.初始原料A中的双键被氧化剂氧化后形成三元环氧基团的中间体B；a. The double bond in the initial raw material A is oxidized by an oxidizing agent to form an intermediate B of a three-membered epoxy group;
b.中间体B酸性条件下三元环氧基团水解生成邻二羟基结构的中间体C；b. Intermediate B is hydrolyzed with three-membered epoxy groups under acidic conditions to generate intermediate C with an o-dihydroxy structure;
c.中间体C在碱性条件下，与一当量的(甲基)丙烯酰氯酯化生成(甲基)丙烯酸酯结构的中间体D；c. Intermediate C is esterified with one equivalent of (meth)acryloyl chloride under alkaline conditions to generate intermediate D of (meth)acrylate structure;
d.中间体D在碱性条件下与卤代物F反应生成树脂单体E。d. Intermediate D reacts with halide F under alkaline conditions to generate resin monomer E.
作为本发明的一种优选技术方案，合成步骤a的氧化剂为间氯过氧苯甲酸或者过氧化氢。As a preferred technical solution of the present invention, the oxidant in the synthesis step a is m-chloroperoxybenzoic acid or hydrogen peroxide.
作为本发明的一种优选技术方案，合成步骤b的酸为硫酸。As a preferred technical solution of the present invention, the acid in the synthesis step b is sulfuric acid.
作为本发明的一种优选技术方案，合成步骤c和步骤d中碱性条件，所述碱均选择有机碱，包括三乙胺、二异丙基胺、吡啶。As a preferred technical solution of the present invention, in the basic conditions of synthesis step c and step d, organic bases are selected as the bases, including triethylamine, diisopropylamine, and pyridine.
作为本发明的一种优选技术方案，所述卤代物F的合成方法：As a preferred technical solution of the present invention, the method for synthesizing the halogenated compound F:
Figure PCTCN2020098451-appb-000004
Figure PCTCN2020098451-appb-000004
其中X为卤素，R 4OH与R 2COR 3在卤化氢、硫酸钠作用下生成卤代物F，溶剂选择甲苯。 Where X is a halogen, R 4 OH and R 2 COR 3 generate halide F under the action of hydrogen halide and sodium sulfate, and toluene is selected as the solvent.
作为本发明的一种优选技术方案，所述初始原料A包括：
Figure PCTCN2020098451-appb-000005
Figure PCTCN2020098451-appb-000006
As a preferred technical solution of the present invention, the initial raw material A includes:
Figure PCTCN2020098451-appb-000005
Figure PCTCN2020098451-appb-000006
与现有技术相比，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
本发明提供了一种新的光刻胶树脂单体，树脂单体含有光敏基团，与其它树脂单体聚合形成光刻胶树脂聚合物，在曝光后会脱去半缩醛(酮)保护基，半缩醛(酮)的活化能比较低，敏感性更高，脱保护后形成羟基结构，从而极性增大，溶解于碱性显影剂(一般为TMAH)，该树脂单体具有曝光前 后溶解度差异大，能够降低粗糙度，提高灵敏度和分辨率，有利于形成均一性良好的光刻图案，并且该树脂单体具有多环结构，更具耐刻蚀性能，酮结构增强了其亲水性，有利于提高碱溶性。The present invention provides a new photoresist resin monomer. The resin monomer contains a photosensitive group and polymerizes with other resin monomers to form a photoresist resin polymer, which will remove the hemiacetal (ketone) protection after exposure. The activation energy of the hemiacetal (ketone) is relatively low, and the sensitivity is higher. After deprotection, it forms a hydroxyl structure, which increases its polarity. It is dissolved in an alkaline developer (usually TMAH). The resin monomer has exposure The solubility difference is large before and after, which can reduce roughness, improve sensitivity and resolution, and is beneficial to the formation of uniform photolithographic patterns. Moreover, the resin monomer has a multi-ring structure and is more resistant to etching. The ketone structure enhances its affinity Water-based, it helps to improve alkali solubility.
具体实施方式detailed description
以下结合附图对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。The preferred embodiments of the present invention will be described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described here are only used to illustrate and explain the present invention, and are not used to limit the present invention.
实施例1Example 1
Figure PCTCN2020098451-appb-000007
Figure PCTCN2020098451-appb-000007
将螺[4.5]癸-2-烯-1,4-二酮A(50g，305mmol)加入到二氯甲烷(1.2L)中，冰水浴冷却到0℃，加入间氯过氧苯甲酸(62g，359mmol)，反应液升到室温搅拌反应16小时，过滤，滤液加入饱和碳酸氢钠溶液中和，水相用二氯甲烷(200mL×3)萃取，有机相用饱和食盐水清洗，分液，无水硫酸钠干燥后真空旋干得到油状化合物B(46.8g，260mmol，85.3％)。Spiro[4.5]dec-2-ene-1,4-dione A (50g, 305mmol) was added to dichloromethane (1.2L), cooled to 0°C in an ice water bath, and m-chloroperoxybenzoic acid (62g , 359mmol), the reaction solution was raised to room temperature and stirred for 16 hours, filtered, the filtrate was neutralized by adding saturated sodium bicarbonate solution, the aqueous phase was extracted with dichloromethane (200mL×3), the organic phase was washed with saturated brine, and the layers were separated. After drying with anhydrous sodium sulfate, it was spin-dried in vacuo to obtain an oily compound B (46.8 g, 260 mmol, 85.3%).
将化合物B(46.8g，260mmol)加入到3M的硫酸(500mL)中，加热回流搅拌反应16小时，反应液冷却到5摄氏度，搅拌下加入碳酸钠粉末调节pH到弱碱性，将溶剂旋干，固体加入THF(500mL)搅拌，过滤除去固体，溶剂旋干得到化合物C(39.5g，199mmol，76.7％)。Compound B (46.8g, 260mmol) was added to 3M sulfuric acid (500mL), heated under reflux and stirred for 16 hours, the reaction solution was cooled to 5 degrees Celsius, and sodium carbonate powder was added with stirring to adjust the pH to weakly alkaline, and the solvent was spin-dried THF (500 mL) was added to the solid and stirred, the solid was removed by filtration, and the solvent was spin-dried to obtain compound C (39.5 g, 199 mmol, 76.7%).
将化合物C(39.5g，199mmol)加入到二氯甲烷(1.2L)，加入三乙胺(40g，395mmol)，冰水冷却到0摄氏度，慢慢滴加丙烯酰氯(18.4g，203mmol)，滴加结束后升到室温搅拌5小时，反应结束，加水(500mL)淬灭，水相用二氯甲烷(200mL×3)萃取，合并有机相，有机相用饱和食盐水洗涤，无水硫酸钠干燥，真空旋干得到化合物D(48.8g，193mmol，97.1％)Compound C (39.5g, 199mmol) was added to dichloromethane (1.2L), triethylamine (40g, 395mmol) was added, ice water was cooled to 0 degrees Celsius, acryloyl chloride (18.4g, 203mmol) was slowly added dropwise, After the addition, the temperature was raised to room temperature and stirred for 5 hours. The reaction was completed and quenched by adding water (500 mL). The aqueous phase was extracted with dichloromethane (200 mL×3). The organic phases were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. And spin dry in vacuo to obtain compound D (48.8g, 193mmol, 97.1%)
将化合物D(10g，40mmol)加入到乙腈(200mL)中，加入三乙胺(8g，79mmol)，冰水冷却到0℃，慢慢加入(1-氯乙基)-环己基醚(6.5g，40mmol)的乙腈溶液(80mL)，升到50℃搅拌反应12小时，冰水冷却下加入饱和碳酸氢钠溶液淬灭反应，浓缩除去乙腈，加入乙酸乙酯(200mL)和水(150mL)，分液，水相用乙酸乙酯(100mL×3)萃取三次，合并有机相，有机相用饱和食盐水洗涤，无水硫酸钠干燥，真空旋干得到粗品，粗品蒸馏纯化得到树脂单体E-1(12.4g，33mmol，82.7％)。Compound D (10g, 40mmol) was added to acetonitrile (200mL), triethylamine (8g, 79mmol) was added, ice water was cooled to 0°C, and (1-chloroethyl)-cyclohexyl ether (6.5g) was slowly added , 40mmol) acetonitrile solution (80mL), heated to 50°C and stirred for 12 hours. Under ice-water cooling, saturated sodium bicarbonate solution was added to quench the reaction, concentrated to remove acetonitrile, ethyl acetate (200mL) and water (150mL) were added, Separate the liquids, extract the aqueous phase with ethyl acetate (100 mL×3) three times, combine the organic phases, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, and spin-dry in vacuo to obtain the crude product. The crude product is purified by distillation to obtain the resin monomer E- 1 (12.4 g, 33 mmol, 82.7%).
实施例2Example 2
Figure PCTCN2020098451-appb-000008
Figure PCTCN2020098451-appb-000008
将化合物D(10g，40mmol)和3,4-二氢-2H-吡喃(3.4g，40mmol)加入到乙腈(100mL)中，加入甲磺酸(0.5g，5mmol)，反应液室温下搅拌反应16小时，加入饱和碳酸氢钠溶液淬灭反应，真空浓缩除去乙腈溶剂，加水(100mL),水相用乙酸乙酯(100mL×3)萃取，合并有机相，有机相用饱和食盐水洗涤，无水硫酸钠干燥得到粗品，粗品蒸馏纯化得到树脂单体E-2(12.6g，37mmol，94.5％)。Compound D (10g, 40mmol) and 3,4-dihydro-2H-pyran (3.4g, 40mmol) were added to acetonitrile (100mL), methanesulfonic acid (0.5g, 5mmol) was added, and the reaction solution was stirred at room temperature After reacting for 16 hours, the reaction was quenched by adding saturated sodium bicarbonate solution, concentrated in vacuo to remove the acetonitrile solvent, water (100 mL) was added, the aqueous phase was extracted with ethyl acetate (100 mL×3), the organic phases were combined, and the organic phase was washed with saturated brine. Anhydrous sodium sulfate was dried to obtain a crude product, and the crude product was purified by distillation to obtain resin monomer E-2 (12.6 g, 37 mmol, 94.5%).
实施例3Example 3
Figure PCTCN2020098451-appb-000009
Figure PCTCN2020098451-appb-000009

Claims (8)

  1. 一种含多环β-酮结构的光敏型光刻胶树脂单体，其特征在于，所述光刻胶树脂单体的结构式为：
    Figure PCTCN2020098451-appb-100001
    其中R 1为甲基或者H，R 2、R 3分别独立的为氢、烷基、环烷基，R 4为烷基或者环烷基，且R 2和R 4、R 3和R 4或者R 2和R 3可以通过共价键连接形成环状结构，n为1-10的整数。     A photosensitive photoresist resin monomer containing a polycyclic β-ketone structure, characterized in that the structural formula of the photoresist resin monomer is:
    Figure PCTCN2020098451-appb-100001
    Wherein R 1 is methyl or H, R 2 and R 3 are each independently hydrogen, alkyl, or cycloalkyl, R 4 is alkyl or cycloalkyl, and R 2 and R 4 , R 3 and R 4 or R 2 and R 3 may be connected by a covalent bond to form a cyclic structure, and n is an integer of 1-10.
  2. 根据权利要求1所述的一种含多环β-酮结构的光敏型光刻胶树脂单体，其特征在于，所述树脂单体的具体结构包括：The photosensitive photoresist resin monomer containing a polycyclic β-ketone structure according to claim 1, wherein the specific structure of the resin monomer comprises:
    Figure PCTCN2020098451-appb-100002
    Figure PCTCN2020098451-appb-100002
  3. 一种含多环β-酮结构的光敏型光刻胶树脂单体的合成方法，其特征在于，所述树脂单体的合成路线如下：A method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure, wherein the synthesis route of the resin monomer is as follows:
    Figure PCTCN2020098451-appb-100003
    Figure PCTCN2020098451-appb-100003
    其中X为卤素，具体步骤：Where X is a halogen, the specific steps:
    a.初始原料A中的双键被氧化剂氧化后形成三元环氧基团的中间体B；a. The double bond in the initial raw material A is oxidized by an oxidizing agent to form an intermediate B of a three-membered epoxy group;
    b.中间体B酸性条件下三元环氧基团水解生成邻二羟基结构的中间体C；b. Intermediate B is hydrolyzed with three-membered epoxy groups under acidic conditions to generate intermediate C with an o-dihydroxy structure;
    c.中间体C在碱性条件下，与一当量的(甲基)丙烯酰氯酯化生成(甲基)丙烯酸酯结构的中间体D；c. Intermediate C is esterified with one equivalent of (meth)acryloyl chloride under alkaline conditions to generate intermediate D of (meth)acrylate structure;
    d.中间体D在碱性条件下与卤代物F反应生成树脂单体E。d. Intermediate D reacts with halide F under alkaline conditions to generate resin monomer E.
  4. 根据权利要求3所述的一种含多环β-酮结构的光敏型光刻胶树脂单体的合成方法，其特征在于，合成步骤a的氧化剂为间氯过氧苯甲酸或者过氧化氢。The method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure according to claim 3, wherein the oxidant in the synthesis step a is m-chloroperoxybenzoic acid or hydrogen peroxide.
  5. 根据权利要求3所述的一种含多环β-酮结构的光敏型光刻胶树脂单体的合成方法，其特征在于，合成步骤b的酸为硫酸。The method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure according to claim 3, wherein the acid in the synthesis step b is sulfuric acid.
  6. 根据权利要求3所述的一种含多环β-酮结构的光敏型光刻胶树脂单体的合成方法，其特征在于，合成步骤c和步骤d中碱性条件，所述碱均选择有机碱，包括三乙胺、二异丙基胺、吡啶。The method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure according to claim 3, characterized in that, in the synthesis step c and step d, in the alkaline conditions, the alkali is selected as organic Bases include triethylamine, diisopropylamine, and pyridine.
  7. 根据权利要求3所述的一种含多环β-酮结构的光敏型光刻胶树脂单体的合成方法，其特征在于，所述卤代物F的合成方法：The method for synthesizing a photosensitive photoresist resin monomer containing a polycyclic β-ketone structure according to claim 3, wherein the method for synthesizing the halogenated compound F:
    Figure PCTCN2020098451-appb-100004
    Figure PCTCN2020098451-appb-100004
    其中X为卤素，R 4OH与R 2COR 3在卤化氢、硫酸钠作用下生成卤代物F，溶剂选择甲苯。 Where X is a halogen, R 4 OH and R 2 COR 3 generate halide F under the action of hydrogen halide and sodium sulfate, and toluene is selected as the solvent.
  8. 根据权利要求3所述的一种含多环β-酮结构的光敏型光刻胶树脂单体，其特征在于，所述初始原料A包括：
    Figure PCTCN2020098451-appb-100005
    A photosensitive photoresist resin monomer containing a polycyclic β-ketone structure according to claim 3, wherein the initial raw material A comprises:
    Figure PCTCN2020098451-appb-100005
PCT/CN2020/098451 2020-06-16 2020-06-28 PHOTOSENSITIVE PHOTORESIST RESIN MONOMER CONTAINING POLYCYCLIC β-KETONE STRUCTURE, AND METHOD FOR SYNTHESIZING SAME WO2021253478A1 (en)

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CN111138288A (en) * 2019-12-28 2020-05-12 上海博栋化学科技有限公司 Photoresist resin monomer containing five-membered ring β -ketone structure and synthetic method thereof

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