JP-7855675-B2 - Polymers and their photosensitive resin compositions

Inventors

• 松浦 洋樹
• 寺田 拓真

Assignees

• 株式会社日本触媒

Dates

Publication Date

20260508

Application Date

20230217

Priority Date

20220225

Claims (10)

1. A polymer having an acid group, The polymer has structural units having a ring structure in the main chain, structural units derived from monomers of a homopolymer represented by the following general formula (1) with a Tg of -20°C or lower , and structural units having an alicyclic structure in the side chain , and substantially does not have ethylenically unsaturated double bonds in the side chain. The structural unit having a ring structure in the main chain is at least one selected from the group consisting of N-benzylmaleimide monomer units and dialkyl-2,2'-(oxydimethylene)diacrylate monomer units. The acid group is a polymer in which the number of atoms between it and the main chain is 6 or less . (In the formula, R1 represents a hydrogen atom or a methyl group. R2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.)
2. A polymer having an acid group, The polymer has structural units having a ring structure in the main chain, structural units derived from monomers of a homopolymer represented by the following general formula (1) with a Tg of -20°C or lower , and structural units having an alicyclic structure in the side chain . The structural unit having a ring structure in the main chain is at least one selected from the group consisting of N-benzylmaleimide monomer units and dialkyl-2,2'-(oxydimethylene)diacrylate monomer units. The acid group has a spacing of 6 or fewer atoms from the main chain. A polymer in which the content of structural units represented by the following general formula (2) is 5% by mass or less relative to 100% by mass of the total structural units of the polymer. (In the formula, R1 represents a hydrogen atom or a methyl group. R2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.) (In the formula, R3 and R4 are the same or different, representing a hydrogen atom or a methyl group. Z represents a divalent organic group.)
3. The polymer according to claim 1 or 2, wherein the acid group is a carboxyl group derived from (meth)acrylic acid.
4. The polymer according to claim 1 or 2, wherein the Tg of the homopolymer represented by the general formula (1) is -60°C to -20°C.
5. The polymer according to claim 1 or 2, wherein the content of monomer-derived structural units of the homopolymer represented by the general formula (1) having a Tg of -20°C or lower is 35% to 80% by mass, relative to 100% by mass of the total structural units of the polymer.
6. A photosensitive resin composition comprising the polymer and polyfunctional monomer described in claim 1 or 2.
7. The photosensitive resin composition according to claim 6 , further comprising a photopolymerization initiator and a colorant.
8. The photosensitive resin composition according to claim 6 , which is a resist for color filters.
9. A cured film obtained by curing the photosensitive resin composition according to claim 6 .
10. A component for a display device having the cured film described in claim 9 .

Description

The present invention relates to polymers and photosensitive resin compositions thereof. More specifically, it relates to polymers and photosensitive resin compositions comprising polymers and polyfunctional monomers. Curable resin compositions that can be cured by heat or active energy rays are being explored for various applications in 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, and photoresists. As a result, curable resin compositions with excellent properties required for each application are being developed. As a colored resin composition with excellent contact hole formation and pattern formation properties, for example, Patent Document 1 describes a colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin, further containing (D) a specific antioxidant and (E) a specific ultraviolet absorber. As a particularly preferred binder resin, a resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, or an alkali-soluble resin (C-1) obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction is described. Patent Document 1 requires that the pattern diameter when the color filter resist is cured be brought close to the mask diameter at the time of exposure. Furthermore, as a photosensitive resin composition with excellent dispersibility with organic pigments, for example, Patent Document 2 describes a photosensitive resin composition that includes a polymer obtained by polymerizing monomer components that include (meth)acrylic acid esters having hydrocarbon groups with 8 to 20 carbon atoms and (meth)acrylic acid as essential, and the polymer is an alkali-soluble resin that has not only alkali-soluble groups but also radically polymerizable unsaturated groups introduced. Patent Document 2 requires high curability of the binder for the resist. Japanese Patent Publication No. 2015-98537Japanese Patent Publication No. 2011-145553 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)acrylic acid" means "acrylic acid and/or methacrylic acid," and "(meth)acrylate" means "acrylate and/or methacrylate." Furthermore, in this specification, the numerical range "Min to Max" means from the minimum value Min upwards and up to the maximum value Max. In addition, when suitable numerical values are described in steps for the upper and lower limits, a numerical range obtained by appropriately combining the upper and lower limits described separately is also a suitable numerical range. 1. Polymer The polymer of the present invention is a polymer (also referred to as "polymer-1") having an acidic group (preferably having an acidic group in the side chain) and a ring structure in the main chain, and a monomer-derived structural unit represented by the following general formula (1) and having a homopolymer Tg (glass transition temperature) of -5°C or lower, substantially without ethylenically unsaturated double bonds in the side chain, and the number of atoms between the acidic group and the main chain is 6 or less. (In the formula, R1 represents a hydrogen atom or a methyl group. R2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.) Furthermore, the polymer of the present invention is a polymer (also referred to as "polymer-2") having an acidic group (preferably having an acidic group in the side chain) and a ring structure in the main chain, and a monomer derived from which the homopolymer is represented by the following general formula (1) and whose Tg of the homopolymer is -5°C or lower, wherein the acidic group has a distance of 6 or fewer atoms from the main chain, and the content of the structural unit represented by the following general formula (2) is 5% by mass or less with respect to 100% by mass of the total structural units of the polymer. (In the formula, R1 represents a hydrogen atom or a methyl group. R2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.) (In the formula, R3 and R4 are the same or different, representing a hydrogen atom or a methyl group. Z represents a divalent organic group.) Because polymer-1 and polymer-2 of the present invention have the above configuration, they can be developed quickly, form fine patterns, and produce cured products (cured films, fine line patterns) with excellent adhesion. The polymer of the present invention is thought to have improved developability, pattern formation, and adhesion due to the