JP-7857398-B2 - Alkali-soluble resin, alkali-soluble resin composition, and method for producing the same

JP7857398B2JP 7857398 B2JP7857398 B2JP 7857398B2JP-7857398-B2

Inventors

寺田拓真
大槻信章
木村純也

Assignees

株式会社日本触媒

Dates

Publication Date: 20260512
Application Date: 20230320
Priority Date: 20220325

Claims (4)

A method for producing an alkali-soluble resin having a structure represented by the following formula (1), The method for producing the alkali-soluble resin is a step (a-1) of reacting a bifunctional epoxy compound having a Cardner color number of less than 12 according to JIS K 0071-2 and a melting point of 90°C or higher with a bisphenol compound. The reaction product obtained in step (a-1) is reacted with an unsaturated monobasic acid in step (a-2), and The process includes step (a-3) of reacting the reaction product obtained in step (a-2) with a polybasic acid anhydride, The alkali-soluble resin obtained by this manufacturing method has an ammonium salt compound content of 0.06% by mass or less relative to 100% by mass of the alkali-soluble resin. The difunctional epoxy compound is a compound represented by the following formula (4): A method for producing an alkali-soluble resin, characterized in that the bisphenol compound is a compound represented by the following formula (5). (In formula (1), R1 , R2 , and R3 are the same or different, representing a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R4 represents a directly bonded or divalent organic group. R5 , R6 , R7 , and R8 are the same or different, representing a hydrogen atom or Y, and at least one of R5 to R8 is Y. The Y is the group represented by the following formula (2). R9 and R10 are the same or different, representing substituents. W represents a divalent organic group. X represents -SO2- . l represents the number of R9s and is an integer from 0 to 4. m represents the number of R10s and is an integer from 0 to 4. If there are multiple R9s and R10s , they may be the same or different. n represents an integer of 1 or more.) (In formula (2), R 11 represents a divalent organic group which may have substituents.) (In formula (4), W represents a divalent organic group.) (In formula (5), X represents -SO₂- . R₁₇ and R₁₇ are identical or different substituents. l represents the number of R₁₇ atoms and is an integer from 0 to 4. m represents the number of R₁₇ atoms and is an integer from 0 to 4. If there are multiple R₁₇ and R₁₇ atoms, they may be identical or different.)
A method for producing an alkali-soluble resin composition comprising an alkali-soluble resin represented by the following formula (1) and an acid group-containing epoxy (meth)acrylate, A method for producing the alkali-soluble resin composition is a step (b-1) of reacting a bifunctional epoxy compound having a Cardner color number of less than 12 according to JIS K 0071-2 and a melting point of 90°C or higher with a bisphenol compound. Step (b-2) involves adding epoxy resin to the reactant obtained in step (b-1). The mixture obtained in step (b-2) is reacted with an unsaturated monobasic acid in step (b-3), and The process includes step (b-4) of reacting the reaction mixture obtained in step (b-3) with a polybasic acid anhydride, The alkali-soluble resin composition obtained by this manufacturing method has an ammonium salt compound content of 0.06% by mass or less relative to 100% by mass of the alkali-soluble resin. The difunctional epoxy compound is a compound represented by the following formula (4): A method for producing an alkali-soluble resin composition, characterized in that the bisphenol compound is a compound represented by the following formula (5). (In formula (1), R1 , R2 , and R3 are the same or different, representing a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R4 represents a directly bonded or divalent organic group. R5 , R6 , R7 , and R8 are the same or different, representing a hydrogen atom or Y, and at least one of R5 to R8 is Y. The Y is the group represented by the following formula (2). R9 and R10 are the same or different, representing substituents. W represents a divalent organic group. X represents -SO2- . l represents the number of R9s and is an integer from 0 to 4. m represents the number of R10s and is an integer from 0 to 4. If there are multiple R9s and R10s , they may be the same or different. n represents an integer of 1 or more.) (In formula (2), R 11 represents a divalent organic group which may have substituents.) (In formula (4), W represents a divalent organic group.) (In formula (5), X represents -SO₂- . R₁₇ and R₁₇ are identical or different substituents. l represents the number of R₁₇ atoms and is an integer from 0 to 4. m represents the number of R₁₇ atoms and is an integer from 0 to 4. If there are multiple R₁₇ and R₁₇ atoms, they may be identical or different.)
The method for producing the alkali-soluble resin composition according to claim 2, characterized in that the epoxy resin is an aromatic epoxy resin.
The method for producing the alkali-soluble resin composition according to claim 3, characterized in that the aromatic epoxy resin is a bisphenol A type epoxy resin.

Description

The present invention relates to alkali-soluble resins and alkali-soluble resin compositions. More specifically, the present invention relates to alkali-soluble resins, alkali-soluble resin compositions, and methods for producing the same, which can provide cured products with excellent heat-resistant coloring properties and a high refractive index. Regarding photosensitive resin compositions containing alkali-soluble resins, various applications are being considered for various optical components and electrical/electronic equipment, such as color filters used in liquid crystal display devices and solid-state image sensors, inks, printing plates, printed circuit boards, semiconductor elements, photoresists, organic insulating films, and organic protective films. Resins and resin compositions with excellent properties required for each application are being developed. In recent years, there has been a growing trend towards miniaturization, thinning, and energy efficiency of optical components, electrical and electronic equipment, and consequently, higher performance is required for the various components used. To meet these demands, research is being conducted on alkali-soluble resins and photosensitive resin compositions that serve as materials for various components. To date, various photosensitive resin compositions containing alkali-soluble resins have been developed to meet diverse requirements. For example, Patent Document 1 describes an image-forming photosensitive resin composition containing an acid-modified vinyl ester obtained by synthesizing from an epoxy compound, a phenol compound, an unsaturated monobasic acid, and a polybasic acid anhydride, wherein at least a portion of the epoxy compound is a crystalline epoxy with a melting point of 90°C or higher, and at least a portion of the phenol compound is one having a bisphenol S skeleton. Furthermore, for example, Patent Document 2 discloses an acid-modified vinyl ester synthesized from a difunctional epoxy compound, a difunctional phenol compound, an unsaturated monomer having a functional group that can react with an unsaturated monobasic acid and/or a phenolic hydroxyl group, and a polybasic acid anhydride, and in which at least a part of the difunctional epoxy compound or difunctional phenol compound has a biphenyl skeleton, and an epoxy acrylate, and a photosensitive resin composition for image formation. Japanese Patent Publication No. 2008-250306Japanese Patent Publication No. 2008-250307 The present invention will be described in detail below. Furthermore, combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments of the present invention. Furthermore, in this specification, "(meth)acrylate" means "acrylate and/or methacrylate," and "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid." 1. Alkali-Soluble Resin The alkali-soluble resin of the present invention is an alkali-soluble resin having a structure represented by the following formula (1), characterized in that the content of the ammonium salt compound is 0.06% by mass or less with respect to 100% by mass of the alkali-soluble resin. (In formula (1), R1 , R2 , and R3 are the same or different, representing a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R4 represents a directly bonded or divalent organic group. R5 , R6 , R7 , and R8 are the same or different, representing a hydrogen atom or Y, and at least one of R5 to R8 is Y. The above Y is the group represented by formula (2) below. R9 and R10 are the same or different, representing substituents. W represents a divalent organic group. X represents a directly bonded or divalent organic group. l represents the number of R9s and is an integer from 0 to 4. m represents the number of R10s and is an integer from 0 to 4. If there are multiple R9s and R10s , they may be the same or different. n represents an integer of 1 or more.) (In formula (2), R 11 represents a divalent organic group which may have substituents.) The alkali-soluble resin of the present invention can produce a cured product with excellent heat-resistant coloring because the ammonium salt compound content is below a predetermined range, resulting in a small nitrogen content that can cause discoloration during heat curing, thus suppressing discoloration during heat curing. Furthermore, the high refractive index of the alkali-soluble resin of the present invention is thought to be due to the presence of a rigid skeleton in the main chain, such as a biphenyl skeleton or a skeleton in which aromatic rings are linked by divalent organic groups, which allows for the formation of a dense cured film through π-π stacking action. The alkali-soluble resin of the present invention has a structure represented by the above formula (1). In formula (1) above, R1 , R2 , and R3 are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon