JP2023091438A - Polymer, polymer solution, photosensitive resin composition, and cured product - Google Patents

Abstract

To provide a polymer that has improved heat properties, resulting in excellent processability and patternability in photolithography, well-balanced sensitivity, alkali solubility and thermal yellowing resistance, as well as superior cured resin sensitivity.SOLUTION: A polymer comprises structural units represented by a predetermined formula (NB) and a predetermined formula (AK), and structural units represented by a predetermined formula (1), illustrated below, or a predetermined formula (2). In the formula (1), Rp is a group having two or more (meth)acryloyl groups, and R21 and R22 independently represent a hydrogen atom or a C1-3 organic group.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polymer, a polymer solution containing the polymer, a photosensitive resin composition containing the polymer solution, and a cured product of the photosensitive resin composition.

A liquid crystal display device and a solid-state imaging device usually have a color filter and a black matrix. Color filters and black matrices have a structure in which structures such as a colored pattern and a protective film are formed on a substrate. Among these structures, a method of forming a colored pattern or a protective film by photolithography using a photosensitive resin composition has become mainstream. Various studies have been made on photosensitive resin compositions. For example, in Patent Document 1, at least in the side chain, an alkaline compound having a group having an acidic group and two or more different polymerizable unsaturated groups A photosensitive resin composition is described that includes a soluble resin, a polymerizable compound, and a photoinitiator. Further, in Examples of Patent Document 1, it is described that a methacrylic acid/allyl methacrylate/glycidyl adduct was synthesized as an alkali-soluble resin, and a photosensitive resin composition was prepared using this.

WO2012/147706

A photosensitive resin composition for forming a color filter or a black matrix uses a resin having a property of being cured by a polymerization reaction caused by light. Color filters and black matrices are produced by patterning a photosensitive resin composition by exposure and development, followed by curing. In photosensitive resin compositions, "increase in sensitivity" seems to be a general issue, but with the increasing complexity and spread of display devices and imaging devices, there is a demand for a higher level of sensitivity. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the productivity can be improved. In addition, the photosensitive resin composition is required to have excellent processability in development processing using an alkaline developer. Furthermore, the cured product of the photosensitive resin composition is required to have high transparency. In addition, especially when dyes and pigments are contained in the photosensitive resin composition, the bottom surface of the pattern is less likely to receive light than the top surface of the pattern during exposure, curing due to exposure becomes insufficient, and the side portion of the bottom surface of the pattern dissolves during development. phenomena may occur. At that time, if the pattern is melted by heat during curing after development, the melted portion on the bottom side of the pattern can be filled, so the cured product of the photosensitive resin composition is required to have a low softening point and melting point. be done.

The present inventors have improved the polymer used in the photosensitive resin composition and the formulation of the composition to have a low softening point and melting point, thereby improving workability and pattern formability in photolithography processing. The present inventors have found that a cured resin product having excellent sensitivity, alkali solubility and heat-resistant yellowing resistance in a good balance can be obtained, leading to the present invention.

式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２であり、

式（ＡＫ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の少なくとも１つは、炭素数３以上の直鎖状もしくは分枝鎖状のアルキル基であり、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の残りは、それぞれ独立して、水素原子、または炭素数１～３０の直鎖もしくは分枝鎖のアルキル基であり、

式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基であり、

式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基である、ポリマーが提供される。 According to the invention,
a structural unit represented by the formula (NB);
a structural unit represented by the formula (AK);
at least one structural unit selected from structural units represented by formula (1) and structural units represented by formula (2);
A polymer comprising

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms,

In formula (1), R ^p is a group having two or more (meth)acryloyl groups, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (2), R ^s is a group having one (meth)acryloyl group, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, polymer is provided.

式（Ｐ２）において、
ｍは、０～５の整数であり、
ｎは、１～６の整数であり、
ｍ＋ｎは、２～６であり、
ｐ、ｑおよびｒはそれぞれ、Ａ、ＢおよびＣのモル含有率を示し、ｐ＋ｑ＋ｒ＝１であり、ｐは０より大きく、ｑは０より大きく、ｒは０以上であり、ｐ、ｑまたはｒは、ｎ個の［ ］内の構造単位毎に同一でも異なっていてもよく、
Ｘは、水素または炭素数１以上３０以下の有機基であり、
Ｙは、２官能以上のチオール基含有化合物から誘導される２～６価の炭素数１以上３０以下の有機基であり、
Ａは、式（ＮＢ）で表される構造単位を表し、
Ｂは、式（１）で表される構造単位、および式（２）で表される構造単位から選択される少なくとも１つの構造単位を含み、
Ｃは、式（ＡＫ）で表される構造単位を表し、
複数存在するＡ同士、Ｂ同士、Ｃ同士は同一であっても異なっていてもよく、
Ｄは、［ ］ｎ内の構造とは異なる構造を表し、

式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２であり、

式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基であり、

式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基であり、

式（ＡＫ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の少なくとも１つは、炭素数３以上の直鎖状もしくは分枝鎖状のアルキル基であり、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の残りは、それぞれ独立して、水素原子、または炭素数１～３０の直鎖もしくは分枝鎖のアルキル基である、ポリマーが提供される。 Further, according to the present invention, a polymer having a structure represented by formula (P2),

In formula (P2),
m is an integer from 0 to 5,
n is an integer from 1 to 6,
m+n is 2 to 6;
p, q and r denote the molar contents of A, B and C respectively, p+q+r=1, p is greater than 0, q is greater than 0, r is 0 or greater, p, q or r may be the same or different for each structural unit in n [ ],
X is hydrogen or an organic group having 1 to 30 carbon atoms,
Y is a divalent to hexavalent organic group having 1 or more and 30 or less carbon atoms derived from a compound containing a thiol group having two or more functions,
A represents a structural unit represented by formula (NB),
B contains at least one structural unit selected from structural units represented by formula (1) and structural units represented by formula (2),
C represents a structural unit represented by formula (AK),
A plurality of A's, B's, and C's may be the same or different,
D represents a structure different from the structure in [ ]n,

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (1), R ^p is a group having two or more (meth)acryloyl groups, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (2), R ^s is a group having one (meth)acryloyl group, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

The present invention also provides a polymer solution containing the above polymer.

Further, according to the present invention, there is provided a photosensitive resin composition containing the above polymer solution and a photopolymerization initiator.

Moreover, according to this invention, the hardened|cured material formed from the said photosensitive resin composition is provided.

式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２であり、

式（ＡＫ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の少なくとも１つは、炭素数３以上の直鎖状もしくは分枝鎖状のアルキル基であり、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の残りは、それぞれ独立して、水素原子、または炭素数１～３０の直鎖もしくは分枝鎖のアルキル基であり、

式（ＭＡ）中、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基である、ポリマーが提供される。 Also according to the present invention,
a structural unit represented by the formula (NB);
a structural unit represented by the formula (AK);
A polymer comprising a structural unit represented by the formula (MA),

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms,

A polymer is provided in which R ²¹ and R ²² in formula (MA) are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

式（Ｐ４）において、
ｍは、０～５の整数であり、
ｎは、１～６の整数であり、
ｍ＋ｎは、２～６であり、
ｐ、ｑおよびｒはそれぞれ、Ａ、ＢおよびＣのモル含有率を示し、ｐ＋ｑ＋ｒ＝１であり、ｐは０より大きく、ｑは０より大きく、ｒは０以上であり、ｐ、ｑまたはｒは、ｎ個の［ ］内の構造単位毎に同一でも異なっていてもよく、
Ｘは、水素または炭素数１以上３０以下の有機基であり、
Ｙは、２官能以上のチオール基含有化合物から誘導される２～６価の炭素数１以上３０以下の有機基であり、
Ａは、式（ＮＢ）で表される構造単位を表し、
Ｂ'は、式（ＭＡ）で表される構造単位を表し、
Ｃは、式（ＡＫ）で表される構造単位を表し、
複数存在するＡ同士、Ｂ同士、Ｃ同士は同一であっても異なっていてもよく、
Ｄは、［ ］ｎ内の構造とは異なる構造を表し、

式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２であり、

式（ＭＡ）中、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基であり、

式（ＡＫ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の少なくとも１つは、炭素数３以上の直鎖状もしくは分枝鎖状のアルキル基であり、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の残りは、それぞれ独立して、水素原子、または炭素数１～３０の直鎖もしくは分枝鎖のアルキル基である、ポリマーが提供される。 Furthermore, according to the present invention, a polymer having a structure represented by formula (P4),

In formula (P4),
m is an integer from 0 to 5,
n is an integer from 1 to 6,
m+n is 2 to 6;
p, q and r denote the molar contents of A, B and C respectively, p+q+r=1, p is greater than 0, q is greater than 0, r is 0 or greater, p, q or r may be the same or different for each structural unit in n [ ],
X is hydrogen or an organic group having 1 to 30 carbon atoms,
Y is a divalent to hexavalent organic group having 1 or more and 30 or less carbon atoms derived from a compound containing a thiol group having two or more functions,
A represents a structural unit represented by formula (NB),
B' represents a structural unit represented by the formula (MA),
C represents a structural unit represented by formula (AK),
A plurality of A's, B's, and C's may be the same or different,
D represents a structure different from the structure in [ ]n,

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

According to the present invention, the softening point and melting point are low, so that the pattern formability after curing is excellent, and the composition has high alkali solubility, so that the developability is excellent, yellowing is reduced, and heat discoloration is high. Provided is a polymer for use in a photosensitive resin composition that has properties and good sensitivity.

1 is a diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging device; FIG. 13 is a ¹³ C-NMR chart of starting polymer 5. FIG. 4 is a TMA chart of Raw Polymer 5. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description thereof will be omitted as appropriate. Also, all drawings are for illustration purposes only. The shape and dimensional ratio of each member in the drawings do not necessarily correspond to the actual article. In this specification, the notation "a to b" in the description of numerical ranges means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% to 90%".

In the description of a group (atomic group) in the present specification, a description without indicating whether it is substituted or unsubstituted includes both groups having no substituents and groups having substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The notation "(meth)acryl" used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate".
In particular, the "(meth)acryloyl group" used herein refers to an acryloyl group represented by -C(=O)-CH=CH2 and -C(=O)-C(CH ₃ )=CH ₂ Represents a concept that includes the represented methacryloyl group.

[Polymer P]
The polymer of the present invention (herein referred to as "polymer P") is described. Unless otherwise specified, structural units or compounds represented by the same structural formula have common definitions and preferred aspects are the same across all embodiments.

[First embodiment]
(Polymer P (I))
The polymer in the first embodiment of the present invention (hereinafter referred to as "polymer P(I)") comprises a structural unit represented by (NB), a structural unit represented by formula (AK), and a structural unit represented by formula ( 1) and at least one structural unit selected from structural units represented by formula (2).

式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２である。

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.

式（ＡＫ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の少なくとも１つは、炭素数３以上の直鎖状もしくは分枝鎖状のアルキル基であり、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の残りは、それぞれ独立して、水素原子、または炭素数１～３０の直鎖もしくは分枝鎖のアルキル基である。

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基である。

In formula (1), R ^p is a group having two or more (meth)acryloyl groups, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基である。

In formula (2), R ^s is a group having one (meth)acryloyl group, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

Polymer P(I) of the present embodiment has a norbornene-derived structural unit represented by formula (NB). Structural units derived from norbornene monomers are chemically robust. Therefore, the polymer P(I) containing this as a structural unit undergoes little weight loss and is stable when subjected to heat treatment.

Further, the polymer P(I) of the present embodiment has a structural unit derived from a long-chain alkene represented by formula (AK). By introducing a structural unit (AK) derived from a long-chain alkene into the polymer P(I), the softening point and melting point of the polymer P(I) can be lowered without changing sensitivity, alkali solubility and heat yellowing. can be lowered. As a result, the polymer P(I) having a structural unit (AK) derived from a long-chain alkene is easily melted by heat during curing, and has excellent workability and pattern formability in photolithography. Therefore, the photosensitive resin composition containing the polymer P(I) can be suitably used for producing films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

Further, the polymer P(I) of the present embodiment contains a structural unit represented by formula (1) and/or a structural unit represented by formula (2). In other words, the polymer P(I) contains either one or both of the structural unit represented by formula (1) and the structural unit represented by formula (2). Thereby, the photosensitive resin composition containing the polymer P(I) has excellent sensitivity when subjected to photolithography. This is probably because the (meth)acryloyl group contained in the structural unit represented by formula (1) or formula (2) accelerates the curing reaction (polymerization reaction).

In a preferred embodiment, polymer P(I) contains a structural unit represented by general formula (1) as an essential constituent. Since the structural unit represented by formula (1) has at least one (meth)acryloyl group, the polymer P(I) containing it has high sensitivity in photolithographic processing.

In the structural unit represented by the above formula (NB) that constitutes the polymer P(I), the organic group having 1 to 30 carbon atoms that can constitute R ¹ to R ⁴ includes a substituted or unsubstituted, linear or branched-chain alkyl having 1 to 30 carbon atoms, more specifically, alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, alkoxy group, heterocycle groups, carboxy groups, and the like.

Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

Alkenyl groups include, for example, allyl groups, pentenyl groups, and vinyl groups.
Examples of alkynyl groups include ethynyl groups.
The alkylidene group includes, for example, a methylidene group and an ethylidene group.
Aryl groups include, for example, tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.

The aralkyl group includes, for example, a benzyl group and a phenethyl group.
Examples of the alkaryl group include tolyl group and xylyl group.
Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, and neopentyloxy groups. , n-hexyloxy group and the like.
Heterocyclic groups include, for example, an epoxy group and an oxetanyl group.

R ¹ , R ² , R ³ and R ⁴ in the structural unit represented by formula (NB) are preferably hydrogen or alkyl groups, more preferably hydrogen.
The hydrogen atoms in the organic groups having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ may be substituted with arbitrary atomic groups. For example, it may be substituted with a fluorine atom, a hydroxy group, a carboxy group, or the like. More specifically, a fluorinated alkyl group or the like may be selected as the organic group having 1 to 30 carbon atoms for R ¹ , R ² , R ³ and R ⁴ .
In the structural unit represented by formula (NB), _a1 is preferably 0 or 1, more preferably 0.

The ratio of the structural unit represented by the formula (NB) in the total structural units constituting the polymer P(I) is preferably 25 to 75 mol%, more preferably 30 to 65 mol%, and still more preferably 35 to 75 mol%. 60 mol %.

In the structural unit represented by formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, preferably , a linear or branched alkyl group having 4 or more carbon atoms, more preferably 5 or more carbon atoms, still more preferably 6 or more carbon atoms. The rest of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.
The upper limit of the carbon number of the linear or branched alkyl group having 3 or more carbon atoms that constitutes at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is, for example, 30 or less carbon atoms, It preferably has 25 or less carbon atoms, more preferably 20 or less carbon atoms.
Among them, the structural unit represented by the formula (AK) can be easily introduced into the polymer P(I), so that the molecular design is easy, and the obtained polymer P(I) has a low softening point without impairing the heat yellowing resistance. and a low melting point, one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the structural unit represented by formula (AK) is a linear or branched chain having 3 or more carbon atoms It is preferably an alkyl group and the remaining three of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms. More preferably, in the structural unit represented by formula (AK), one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms.
The softening of the resulting polymer P(I) increases with the number of carbon atoms in the linear or branched alkyl group having 3 or more carbon atoms that constitutes at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ . point and melting point tend to be lower. Thus, depending on the softening point or melting point desired in the application of polymer P(I), the number of carbon atoms in the structural units of formula (AK) can be selected.

The ratio of the structural unit represented by the formula (AK) in the total structural units constituting the polymer P(I) is preferably 2 to 30 mol%, more preferably 3 to 28 mol%, still more preferably 5 to 25. in mol %. By setting the ratio of the structural unit represented by the formula (AK) in the polymer P(I) to the above range, the polymer P(I) has a low softening point and a low melting point, and has a good balance of sensitivity, alkali solubility and heat discoloration resistance. A highly improved polymer P(I) can be obtained.

Polymer P(I) is a structural unit containing two or more (meth)acryloyl groups (-C(=O)-CH=CH ₂ ) represented by formula (1), or represented by formula (2) or a structural unit containing one (meth)acryloyl group, or a combination thereof. By containing such structural units, the polymer P(I) has better sensitivity in exposure processing.

In formula (1) or formula (2), the organic group having 1 to 3 carbon atoms that can constitute R ²¹ and R ²² includes methyl group, ethyl group, n-propyl group and isopropyl group. Both R ²¹ and R ²² are preferably hydrogen atoms.

In the structural unit represented by formula (1), R ^p is a group containing 2 or more (meth)acryloyl groups, preferably a group containing 2 to 6 (meth)acryloyl groups, more preferably It is a group containing 3 to 5 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups contained in ^Rp , the sensitivity of the polymer P(I) containing this in exposure processing can be further enhanced. In addition, it becomes easier to achieve both sensitivity and alkali solubility of the polymer P(I) to a higher degree. Furthermore, the heat resistance of the polymer P(I) can be improved.

R ^p in formula (1) is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and is selected from these At least one type is included. With such a group, there is a tendency to easily obtain the various effects described above.

In formula (1b),
k is 2 or 3,
R is a hydrogen atom or a methyl group, multiple R may be the same or different,
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -ZX- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms ), and multiple X ¹ may be the same or different,
X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, Z' is -O- or -COO-),
X ² is a k+1 valent organic group having 1 to 12 carbon atoms.
R is preferably a hydrogen atom from the viewpoint of further improvement of sensitivity (ease of polymerization).
Although k may be 2 or 3, it is preferably 3 from the standpoints of availability of raw materials and further improvement of sensitivity.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched.
When X ¹ is an alkylene group having 1 to 6 carbon atoms, X ¹ is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, still more preferably -CH _2- (methylene group).

When X ¹ is a group represented by -ZX- (Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms), X has 1 to 6 carbon atoms Alkylene groups can be straight or branched.
The alkylene group having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH ₂ -CH ₂ -( ethylene group) or —CH ₂ —CH(CH ₃ )—.

When X ¹ ' is an alkylene group having 1 to 6 carbon atoms, specific aspects thereof are the same as those of X ¹ .
When X ¹ ' is a group represented by -X'-Z'-, specific aspects of X' are the same as X above.

Examples of the k+1-valent organic group having 1 to 12 carbon atoms for X ² include any group obtained by removing k+1 hydrogen atoms from any organic compound. The “any organic compound” used herein is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, more preferably 100 or less.
X ² is, for example, a group obtained by removing k+1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing k+1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. In addition, the hydrocarbon here may contain an oxygen atom (for example, an ether bond, a hydroxy group, etc.). Also, the hydrocarbon is preferably a saturated hydrocarbon.
Alternatively, X ² may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include groups containing an alicyclic structure, groups containing a heterocyclic structure (eg, isocyanuric acid structure), and the like.

In formula (1c),
k, R, X ¹ and X ² are respectively synonymous with R, k, X ¹ and X ² in formula (1b); X ¹ may be the same or different,
X ³ is a divalent organic group having 1 to 6 carbon atoms,
X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁶ is a divalent organic group having 1 to 6 carbon atoms.

Specific aspects and preferred aspects of R, k, X ¹ and X ² are the same as those described for formula (1b).
Examples of the divalent organic group having 1 to 6 carbon atoms of X ³ and X ⁶ include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. can be done. In addition, the hydrocarbon here may contain an oxygen atom (for example, an ether bond, a hydroxy group, etc.). Also, the hydrocarbon is preferably a saturated hydrocarbon.
Examples of the divalent organic group having 1 to 6 carbon atoms for X ⁴ and X ⁵ include linear or branched alkylene groups. The number of carbon atoms in the linear or branched alkylene group is preferably 1-3.

In formula (1d), n is an integer of 2-5, preferably 2 or 3.
Specific aspects and preferred aspects of R are the same as those described for formula (1b).

When polymer P(I) contains structural units represented by formula (1), the ratio of structural units represented by formula (1) to all structural units of polymer P(I) is preferably 3. ~40 mol%, more preferably 3 to 30 mol%.

In the structural unit represented by formula (2) that can constitute the polymer P(I), R ^S is a group containing only one (meth)acryloyl group. In particular, in the design of ordinary photosensitive resin compositions, when the curability is increased in order to increase the sensitivity, the curing progresses too much and the developability tends to deteriorate. Polymer P(I) may contain either or both structural units represented by formula (1) and structural units represented by formula (2), since curing tends to be insufficient in some cases. This is preferable because both sensitivity and developability can be achieved with a good balance.

R ^s is, for example, a group represented by formula (2a) below.

In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group. The total carbon number of X ¹⁰ is preferably 1-30, more preferably 1-20, even more preferably 1-10.
As the divalent organic group for X ¹⁰ , for example, an alkylene group is preferable. A part of --CH ₂ -- in this alkylene group may be an ether group (--O--). The alkylene group may be linear or branched, but is more preferably linear.

More preferably, the divalent organic group for X ¹⁰ is a linear alkylene group having 3 to 6 carbon atoms in total. By appropriately selecting the number of carbon atoms in ^X10 (chain length of ^X10 ), the structural unit represented by formula (2) is more likely to participate in the cross-linking reaction, and the sensitivity can be enhanced.

The divalent organic group (eg, alkylene group) of X ¹⁰ may be substituted with any substituent. Examples of substituents include alkyl groups, aryl groups, alkoxy groups, and aryloxy groups.
Also, the divalent organic group of X ¹⁰ may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

When the polymer P(I) contains the structural unit represented by formula (2), the proportion of the structural unit represented by formula (2) in the total structural units of the polymer P is preferably 5 to 30 mol%. , more preferably 10 to 20 mol %.

Further, when the polymer P(I) contains both the structural unit represented by the formula (1) and the structural unit represented by the formula (2), the formula (1) in the polymer P(I) The total ratio of the structural unit represented by the formula (2) to the structural unit represented by the formula (2) is preferably 5 to 40 mol%, more preferably 10, based on the total structural units constituting the polymer P(I). to 35 mol %, more preferably 15 to 30 mol %.

The polymer P(I) of the present embodiment may contain a structural unit represented by formula (3) in addition to the structural units described above. Polymer P(I) has high alkali solubility by containing the structural unit represented by Formula (3). As a result, the photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to photolithography using an alkaline aqueous solution as a developer. The proportion of the structural unit represented by formula (3) in the total structural units of the polymer P(I) is preferably 1-10 mol %, more preferably 2-7 mol %.

Polymer P(I) of the present embodiment may contain a structural unit represented by formula (MA) in addition to the structural units described above. The structural unit represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P(I) has excellent developability. When polymer P(I) contains structural units represented by formula (MA), the number of structural units represented by formula (MA) in all structural units of polymer P(I) is preferably 3 to 40. mol %, more preferably 10 to 30 mol %.

The content (ratio) of each structural unit contained in the polymer P(I) is determined by the charged amount (molar amount) of raw materials used when synthesizing the polymer, the amount of raw materials remaining after synthesis, various spectra (e.g., IR Spectra, ¹ H-NMR spectrum, ¹³ C-NMR spectrum) can be estimated/calculated from the presence of peaks, peak areas, and the like.

The weight average molecular weight Mw of polymer P(I) is, for example, 2,000 to 30,000. The weight average molecular weight Mw of polymer P(I) is preferably 2,500 to 25,000, more preferably 3,000 to 20,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust sensitivity and solubility in an alkaline developer.
Further, the degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P(I) of the present embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and further Preferably, it is 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer P can be made uniform, which is preferable. These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer P(I) is preferably 100-250°C, more preferably 120-230°C. When the structural unit of formula (NB) is mainly included, the glass transition temperature tends to be high, while when the structural unit of formula (AK) is included, the glass transition temperature tends to be low. The polymer P of the present embodiment has a preferable glass transition temperature by containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (AK). This is preferable in that the pattern formed on the substrate can exist stably in manufacturing liquid crystal display devices and solid-state imaging devices. The glass transition temperature can be determined by, for example, differential thermal analysis (DTA).

The acid value of the polymer P(I) is, for example, 70 mgKOH/g or more and 150 mgKOH/g or less, preferably 80 mgKOH/g or more and 140 mgKOH/g or less. Further, the double bond equivalent of the polymer P1 is, for example, 100 g/mol or more and 900 g/mol or less, preferably 200 g/mol or more and 850 g/mol or less, more preferably 200 g/mol or more and 800 g. / mol or less.
Favorable developability can be obtained because the acid value of the polymer P(I) is 70 mgKOH/g or more. Further, when the double bond equivalent is 900 g/mol or less, the sensitivity of the photosensitive resin composition containing the polymer P(I) can be increased.

If the acid value of the polymer P(I) is too high, the exposed portion is likely to dissolve during development with an alkaline developer, resulting in an increase in the amount of exposure required for photocuring, or an undesirable pattern shape. There is concern that it will be enough. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH/g.
In addition, if the double bond equivalent of the polymer P(I) is too small (that is, if the density of the double bonds in the polymer is too high), the unexposed areas and underexposed areas will dissolve during development with an alkaline developer. It tends to be difficult to remove, and a residual film tends to occur during development. On the other hand, if the double bond equivalent is too small, the molecular weight will excessively increase due to cross-linking, and there is a concern that the solubility will be excessively lowered. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g/mol.

By providing the above configuration, the polymer P(I) of the present embodiment can have an alkali dissolution rate of 120 nm/s or more, preferably 150 nm/s or more, more preferably , 200 nm/s or more, and more preferably 300 nm/s or more. Although the upper limit is not particularly limited, it can be, for example, 2000 nm/s or less. In the specification of the present application, the alkali dissolution rate is a value measured under the following conditions.
(Method for Measuring Alkali Dissolution Rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid concentration of 30 mass %. Next, the resulting polymer solution is spin-coated on the wafer, the PGMEA is dried, and pre-baked at 100° C. for 2 minutes to form a resin film with a film thickness of 2 μm±0.2. This resin film, together with the wafer, is immersed in a 2.0% by mass sodium carbonate aqueous solution at a temperature of 23°C. The immersed wafer was visually observed to measure the time required for the resin film to dissolve and the interference pattern to disappear. Calculate the dissolution rate (μm/sec).

By adjusting the acid value and/or double bond equivalent of polymer P(I), both sensitivity and developability can be achieved at a higher level.

The acid value and double bond equivalent of polymer P(I) can be determined by spectral measurement or the like. For example, it can be determined by the following procedure (more specifically, see Examples).
(1) From the ¹ H-NMR chart of the polymer, the area (integral value) of the peaks corresponding to the hydrogen atoms of the carboxy group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond is obtained.
(2) Based on the area obtained in (1) and the area of the peak derived from the standard substance, the amount of carboxy groups and the amount of carbon-carbon double bonds are obtained.
(3) Convert the amount of carboxy groups obtained in (2) into an acid value (mgKOH/g). Also, the amount of the polymerizable carbon-carbon double bond obtained in (2) is converted into a double bond equivalent (g/mol).

The acid value and double bond equivalent of the polymer P(I) are contained in the ratio of the structural units introduced into the polymer P(I), particularly the structural units represented by formula (1) or formula (2) (meta ) can be adjusted to a desired value by appropriately designing the number of polymerizable carbon-carbon double bonds possessed by the acryloyl group.

The content (ratio) of each structural unit contained in the polymer P(I) of the present embodiment is the amount (molar amount) of raw materials charged during polymer synthesis, the amount of raw materials remaining after synthesis, and the peak area of various spectra. (eg, peak area of ¹ H-NMR), etc. can be estimated/calculated.

Polymer P(I) of the present embodiment has a low softening point of 110° C. or less due to the inclusion of the structural unit represented by formula (AK). The softening point of polymer P(I) is preferably 100° C. or lower, more preferably 90° C. or lower. Moreover, the polymer P(I) of the present embodiment has a low melting point of 140° C. or lower due to the inclusion of the structural unit represented by the formula (AK). The melting point of polymer P(I) is preferably 130° C. or lower, more preferably 120° C. or lower.
In the specification of the present application, the softening point and melting point of a polymer are values measured under the following conditions.
(Method for measuring softening point)
0.1 to 1.0 mg of the polymer to be measured is placed in an aluminum sample pan, and the softening point is measured using a differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., "EXSTAR TMA/SS6100") under a nitrogen atmosphere. It was measured. The measurement mode was compression, the load was 30 mN, and the temperature was raised in the range of 30° C. to 200° C. at a rate of 3° C./min. When the sample softens due to heating, the sample deforms and is detected as a displacement (μm), which is an extension of the straight portion without displacement on the low temperature side, or a tangent to the portion with the lowest displacement speed and a tangent to the portion with the highest displacement speed. was taken as the softening point.
(Measuring method of melting point)
1 to 2 mg of the polymer to be measured is placed in an aluminum sample pan, and under a nitrogen atmosphere, using a differential thermal analyzer (manufactured by Hitachi High-Technologies Corporation, "STA7200RV"), image observation is performed from 30 ° C. The temperature was raised at a temperature elevation rate of 10°C/min. The temperature at which the sample started to melt was visually confirmed and taken as the melting point.

(Method for producing polymer P(I))
Polymer P(I) can be produced (synthesized) by any method. Typically, polymer P(I) can be produced by the following steps aI, aII, and aIII.
Step aI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AK), and a structural unit represented by formula (MA);
Step aII: The raw material polymer obtained in Step aI, a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound), and/or a hydroxy group and one (meth)acryloyl A compound having a group (monofunctional (meth)acrylic compound) is reacted in the presence of a basic catalyst to obtain a structural unit represented by the formula (NB), a structural unit represented by the formula (AK), and Preparing a polymer P(I) comprising structural units of formula (1) and/or structural units of formula (2) and optionally further comprising structural units of formula (MA) can be manufactured by

When the polymer P(I) further comprises a structural unit represented by formula (3), step aIII below is carried out.
Step aIII: In step aII, a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (1) and/or a structural unit represented by formula (2) A structural unit and a polymer precursor containing a structural unit represented by formula (MA) (corresponding to polymer P(I) in step aII above) are prepared, and then the polymer precursor is treated in the presence of a base catalyst, Treatment with water to obtain polymer P(I).

In step aII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, first the polyfunctional (meth)acrylic compound is reacted with the raw material polymer obtained in step aI to obtain It is preferable to react a monofunctional (meth)acrylic compound with the reaction mixture.

Each step will be described below.
(Step aI)
The step of preparing a raw material polymer containing a structural unit represented by the formula (NB), a structural unit represented by the formula (AK), and a structural unit represented by the formula (MA) in step aI includes the formula (NBm ), a monomer represented by the formula (AKm), and a monomer represented by the formula (MAm) are polymerized (addition polymerization). Here, the definitions of R ¹ , R ² , R ³ and R ⁴ and a ₁ in formula (NBm) are the same as those in formula (NB). The definitions of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in formula (AKm) are the same as in formula (AK). The definitions of R ²¹ and R ²² in formula (MAm) are the same as those in formula (MA).

Monomers represented by the formula (NBm) include, for example, norbornene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl -2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5 -(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene -2-methyl carboxylate, 5-norbornene-2,3-dicarboxylic anhydride and the like. At the time of polymerization, the monomer represented by the formula (NBm) may be used alone or in combination of two or more.

In long-chain alkenes as monomers represented by the formula (AKm), the configuration with respect to the double bond may be either cis or trans. Examples of long-chain alkenes represented by the formula (AKm) include 1-hexene, 1-heptadecene, 1-octene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1- Linear 1-alkenes such as hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-tricosene; branched 1-alkenes such as 3,5,5-trimethyl-1-hexene; 4-octene, 3-octene, 2-decene, 5-methyl-2-heptene, 5-methyl-3-heptene, 2,4,4-trimethyl-2-pentene, 3-methyl-2-heptene, cis-9 - Linear or branched alkenes such as tricosene.

Although the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators that can be used include azo compounds and organic peroxides.
Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis(2-methylpropionate), 1,1′-azobis(cyclohexanecarbonitrile) (ABCN), and the like. can be mentioned.
Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).
As for the polymerization initiator, only one type may be used, or two or more types may be used in combination.

As the solvent used for the polymerization reaction, for example, organic solvents such as diethyl ether, tetrahydrofuran, toluene and methyl ethyl ketone can be used. The polymerization solvent may be a single solvent or a mixed solvent.

The raw material polymer is synthesized by dissolving the monomer represented by the formula (NBm), the monomer represented by the formula (AKm), the monomer represented by the formula (MAm), and a polymerization initiator in a solvent, and adding them to a reaction vessel. It is carried out by charging and then heating to proceed addition polymerization. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.
The total amount (NBm+AKm) of the monomer represented by the formula (NBm) and the monomer represented by the formula (AKm) when charged into the reaction vessel, and the molar ratio of the monomer represented by the formula (MAm) are NBm+AKm):(MAm)=0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1. The molar ratio of the monomer represented by the formula (AKm) to the monomer represented by the formula (NBm) is preferably (AKm):(NBm) = 0.5:9.5 to 5:5, A ratio of 1:9 to 4:6 is more preferred.
A "raw material polymer" can be obtained by such a process.
The raw material polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. Typically they are random or alternating copolymers. Maleic anhydride is generally known as a monomer having strong alternating copolymerizability.

After synthesis of the starting polymer, a step of removing low-molecular-weight components such as unreacted monomers, oligomers and residual polymerization initiators may be carried out.
Specifically, the organic phase containing the synthesized starting polymer and low-molecular-weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. By filtering and drying the precipitate, the purity of the starting polymer can be increased.

(Step aII)
In step aII, the raw material polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and/or a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain Part of the structural unit represented by the formula (MA) is ring-opened to form the structural unit represented by the formula (1) and/or the structural unit represented by the formula (2), and the formula (NB ), a structural unit represented by the formula (AK), and a structural unit represented by the formula (1) and/or a structural unit represented by the formula (2), optionally represented by the formula ( A polymer precursor containing structural units represented by MA) is obtained. The polymer precursor obtained here can be used as the polymer P(I) of the present embodiment, but is referred to as a polymer precursor for convenience of explanation.

More specifically, first, a solution is prepared by dissolving a raw material polymer in a suitable organic solvent. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) can be used. , but not limited to these, various organic solvents used in synthesizing organic compounds and polymers can be used.

A structural unit represented by formula (NB), a structural unit represented by formula (AK), and a polymer precursor containing both a structural unit represented by formula (1) and a structural unit represented by formula (2) When obtaining a body, a polyfunctional (meth)acrylic compound is then added to the above solution. Additionally, a basic catalyst is added. Then, the solution is appropriately mixed to form a uniform solution, thereby obtaining a polymer precursor containing at least the structural unit of formula (NB), the structural unit of formula (AK), and the structural unit of formula (1) (Step aII-i ).

Examples of polyfunctional (meth)acrylic compounds that can be used here include compounds represented by formula (1b-m), compounds represented by formula (1c-m), and compounds represented by formula (1d-m). compounds that are The definitions and specific embodiments of k, R, X ¹ , X ¹ ' and X ² in formula (1b-m) are the same as in formula (1b) above. The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in formula (1c-m) are the same as in formula (1c) above. n and R in formula (1dm) are the same as in formula (1d) above.

Then, the polymer obtained in step aII-i is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a structural unit of formula (NB), a structural unit of formula (AK), A polymer precursor comprising structural units of formula (1) and structural units of formula (2) can be obtained (step aII-ii).

As the basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, an amine compound such as triethylamine, pyridine, dimethylaminopyridine, or a nitrogen-containing heterocyclic compound can be used as a catalyst. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass with respect to 100 parts by mass of the starting polymer. It should be noted that if the basic catalyst is used excessively, the amount of acid required for neutralization increases, which may complicate purification.

The above solution is preferably heated at 60 to 80° C. for about 3 to 9 hours to open the structural unit of formula (MA) contained in the raw material polymer/form the structural unit of formula (1). be.

Incidentally, for example, during the above heating, by additionally adding a monofunctional (meth)acrylic compound having a hydroxy group to the reaction system, the structural unit of the formula (MA) contained in the raw material polymer is ring-opened/ Formation of structural units of formula (2) is carried out to produce polymer P(I) having structural units represented by formula (2).

From the viewpoint of reaction steric hindrance, a monofunctional (meth)acrylic compound having a hydroxy group tends to react more easily with a raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxy group. Therefore, when preparing a polymer precursor having a structural unit of formula (2), a monofunctional (meth)acrylic compound having a hydroxy group is not charged into the reaction system from the beginning, but is additionally added into the reaction system. is preferred.
Monofunctional (meth)acrylic compounds having a hydroxy group include, for example, compounds represented by the following formulas (2a-m).
In formulas (2a-m), the definitions of X ¹⁰ and R are the same as in formula (2a).

Specific examples of compounds represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2- to mention hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. can be done.

Including any one of structural units represented by formula (NB), structural units represented by formula (AK), and structural units represented by formula (1) and structural units represented by formula (2) When obtaining a polymer precursor, either step aII-i or step aII-ii may be carried out after step (I).

(Step aIII)
When carrying out step aIII, a step of treating the polymer precursor obtained in step aII with water in the presence of a basic catalyst is used. In step aIII, the structural unit represented by formula (MA) contained in the polymer precursor obtained in step aII is ring-opened to form the structural unit represented by formula (3), resulting in formula (NB) A structural unit represented by the formula (AK), a structural unit represented by the formula (1) and/or a structural unit represented by the formula (2), and a structural unit represented by the formula (3) Polymers P(I) can be prepared that contain structural units of When some of the structural units of formula (MA) are ring-opened and some of the structural units of formula (MA) remain unopened, the polymer P(I) is represented by formula (MA) Further includes a structural unit represented by

Basic catalysts used in step aIII include amine compounds such as triethylamine, pyridine and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

In step aIII, water is added to the reaction system containing the polymer precursor obtained in step aII, and the obtained reaction solution is preferably heated at 60 to 80° C. for about 0.25 to 6 hours. , the structural unit represented by the formula (MA) contained in this polymer is ring-opened to generate the structural unit represented by the formula (3). As the basic catalyst, the catalyst remaining in the reaction system obtained in step aII can be used as it is. Therefore, step aIII is preferably carried out in situ by adding water to the reaction mixture obtained in step aII without any post-treatment.

The polymer P(I) of the present embodiment can be obtained by the above steps, but from the viewpoint of the effect of the present invention, the following steps may be performed as appropriate in order to remove unnecessary components other than the desired polymer. can also

First, the above reaction solution diluted with an organic solvent and added with an acid (for example, formic acid) is vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. An organic solution of the polymer is thus obtained.

The resulting organic solution of polymer P(I) is purified using a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the resulting organic solution of polymer P(I) is added to an excess amount of toluene or water to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is further washed several times with toluene or water.
Furthermore, in order to remove formic acid and a basic catalyst, an operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (about 1 to 3 times).
A high-purity polymer can be obtained by drying the polymer powder washed with ion-exchanged water, for example, at 30 to 60° C. for 16 hours or longer.
In the liquid-liquid extraction method, water is added to the resulting organic solution of polymer P(I) and vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. Further water is added to the organic solution of the polymer after the water has been removed and stirred vigorously with a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. An organic solution of the polymer is thus obtained. If necessary, the steps of adding water and removing the aqueous phase may be further performed.
The resulting organic solution of polymer P(I) is heated with a rotary evaporator under reduced pressure to concentrate, and then the operation of adding a final solvent (such as PGMEA) and diluting is repeated to obtain a polymer solution dissolved in the final solvent. can be obtained. In addition, purification may be performed by a reprecipitation method after solvent replacement.

Moreover, the polymer solution may contain the polyfunctional (meth)acrylic compound and/or the monofunctional (meth)acrylic compound used when synthesizing the polymer P(I). When the polymer solution contains these (meth) acrylic compounds, the peak area derived from the polyfunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart is 3 to 50% with respect to the peak area of the polymer P. An amount, particularly preferably an amount of 4 to 30%, more preferably an amount of 5 to 20%, the peak area derived from the monofunctional (meth) acrylic compound, the polymer P The amount is preferably 0.2 to 30%, particularly preferably 0.5 to 20%, more preferably 0.7 to 10%, with respect to the peak area of . As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[Second embodiment]
(Polymer P(II))
The polymer in the second embodiment of the invention (referred to herein as "polymer P(II)") has a structure represented by formula (P2). The polymer P (II) is represented as “Y” in the formula (P2) and is typically a divalent to hexavalent organic group having 1 to 30 carbon atoms derived from a difunctional or higher thiol group-containing compound. Specifically, it has a structure in which polymer chains composed of structural unit A, structural unit B, and structural unit C are bonded.

In formula (P2),
m is an integer of 0 to 5, preferably 0 or 1, more preferably 0;
n is an integer of 1-6, preferably 3-6.
m+n is 2-6, preferably 3-6.
p, q and r denote the molar contents of A, B and C respectively, p+q+r=1.
p is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, more preferably 0.35 to 0.60.
q is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, more preferably 0.25 to 0.45.
r is greater than 0, preferably 0.03 to 0.3, more preferably 0.04 to 0.28, particularly preferably 0.05 to 0.25.
p, q or r may be the same or different for every n structural units in [ ].
X is hydrogen or an organic group having 1 to 30 carbon atoms.
Y is a divalent to hexavalent organic group having 1 or more and 30 or less carbon atoms derived from a thiol group-containing compound having a functionality of 2 or more.
A is a structural unit represented by formula (NB).
B represents at least one structural unit selected from structural units represented by formula (1) and structural units represented by formula (2).
C represents a structural unit represented by formula (AK).
Multiple A's, B's, and C's may be the same or different.
D is any structure different from the structure in [ ]n, eg, one or two of A, B, and C above.

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.

In formula (1), R ^p is a group having two or more (meth)acryloyl groups, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In formula (2), R ^s is a group having one (meth)acryloyl group, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

Polymer P(II) having a structure represented by formula (P2) may contain a structural unit represented by formula (3) as structural unit B.

In formula (3), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

The polymer P(II) having the structure represented by formula (P2) may contain, as structural unit B, a structural unit represented by formula (MA).

In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In one embodiment, polymer P(II) may have a structure represented by formula (P'). Here, the formula (P') corresponds to the mode in which m is 0 in the above formula (P2).

In formula (P'),
n, p, q, and r are the same as defined in formula (P2), and X, Y, A, B, and C are the same as defined in formula (P2).

In formula (P2), Y is a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a bifunctional or higher thiol group-containing compound (herein, “organic group (i) ”). In this embodiment, the valence is the number of functional groups (the number of thiol groups). That is, the bifunctional or more thiol group-containing compound contains two or more thiol groups, and the organic group (i) is a structural unit in [ ]n via 2 to 6 thioether groups derived from the thiol group. and [ ] binds to the structural unit in m. The organic group (i) may have a thiol group that does not participate in bonding with the structural units in [ ]n and the structural units in [ ]m, and the polymer P(II) has n+m number (bonds number) can be obtained as a mixture of resins of 2 to 6.
The organic group (i) having 1 to 30 carbon atoms is bifunctional or more, preferably trifunctional or more. Although the upper limit is not particularly limited, it is hexafunctional or less.
The valence of the organic group (i) having 1 to 30 carbon atoms is 2 to 6 valence, preferably 3 to 6 valence, from the viewpoint of the effects of the present invention.

The divalent to hexavalent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P and Si. Examples of the divalent to hexavalent organic group (i) having 1 to 30 carbon atoms include an alkyl group having 2 to 6 thioether groups (-S-* (* is a bond)), an alkenyl group, Examples include alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups and heterocyclic groups.

Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group. , octyl, nonyl, and decyl groups. Alkenyl groups include, for example, allyl groups, pentenyl groups, and vinyl groups.

Alkynyl groups include ethynyl groups.
The alkylidene group includes, for example, a methylidene group and an ethylidene group. Aryl groups include, for example, tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.
Aralkyl groups include, for example, benzyl groups and phenethyl groups.
The alkaryl group includes, for example, a tolyl group and a xylyl group.

Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-pentyloxy, and neopentyloxy groups. , and n-hexyloxy groups.
Heterocyclic groups include, for example, epoxy groups and oxetanyl groups.

Examples of bifunctional or higher thiol group-containing compounds from which Y in formula (P2) can be derived include compounds represented by the following chemical formulas (s-1) to (s-21). That is, the polymer P(II) contains a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a difunctional or higher thiol group-containing compound represented by the following.

The bifunctional or higher thiol group-containing compounds may be used singly or in combination of two or more. Among them, it is preferable to use tri- to hexa-functional (tri- to hexavalent) thiol group-containing compounds having 3 to 6 thiol groups in one molecule from the viewpoint of excellent reactivity with other monomers.
In the present embodiment, the bifunctional or higher thiol group-containing compound is, among the compounds represented by the chemical formulas (s-1) to (s-21), the chemical formulas (s-1) to (s-3), It is more preferable to contain compounds represented by (s-5) and (s-8) to (s-10), and chemical formulas (s-1) to (s-3), (s-5) and (s It is particularly more preferable to contain the compound represented by -9).
The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms is a thioether group (-S-* (* is a bond)) derived from the thiol group of these thiol group-containing compounds. and binds to the structural unit in [ ]n and the structural unit in [ ]m via a thioether group. The organic group (i) may have a thiol group that does not participate in bonding with the structural unit in [ ]n and the structural unit in [ ]m.

When the polymer P(II) of the present embodiment uses a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) as the bifunctional or higher thiol group-containing compound, for example, It can have a structure as represented by the following formula (I).

In formula (I), A, B, C, X, p, q and r have the same definitions as in formula (P2). A, B, C, X, p, q and r contained in the four structural units in [ ] may be the same or different.

In formula (I), the bonding order of A, B and C is not particularly limited, and any of A, B and C may be bonded to a thioether group. Further, in formula (I), four structural units in [ ] are bonded via thioether groups derived from four mercapto groups of the compound represented by chemical formula (s-2). 1 to 3 structural units in [ ] are bonded to thioether groups derived from four mercapto groups, and the remaining thioether groups are bonded to organic groups different from the structural units in [ ]. There may be. In this embodiment, the polymer P can be obtained as a mixture containing at least one compound in which 1 to 4 structures in [ ] are bonded.

The weight average molecular weight Mw of polymer P(II) is, for example, 2,000 to 20,000. The weight average molecular weight Mw of polymer P(I) is preferably 2,500 to 17,500, more preferably 3,000 to 15,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust sensitivity and solubility in an alkaline developer.
Further, the degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P(I) of the present embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and further Preferably, it is 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer P can be made uniform, which is preferable. These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.
Physical properties such as glass transition temperature, softening point, melting point, acid value, double bond equivalent, and alkali dissolution rate of polymer P(II) are the same as those of polymer P(I) described above.

(Method for producing polymer P(II))
A method for producing the polymer P(II) will be described.
Polymer P(II) can be produced (synthesized) by any method. Typically, polymer P(II) can be prepared by the following processes, step bII and step bIII.
Step bI: a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (MA), and a divalent to hexavalent organic having 1 to 30 carbon atoms providing a raw polymer containing group (i);
Step bII: the raw material polymer obtained in step bI, a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound), and/or a hydroxy group and one (meth)acryloyl A compound having a group (monofunctional (meth)acrylic compound) is reacted in the presence of a basic catalyst to obtain a structural unit represented by the formula (NB), a structural unit represented by the formula (AK), 2 to a hexavalent organic group (i) having 1 to 30 carbon atoms, and a structural unit represented by formula (1) and/or a structural unit represented by formula (2), optionally further containing formula (MA ) to prepare a polymer P(II) containing a structural unit represented by ).

If polymer P(II) further comprises structural units of formula (3), step bIII below is carried out.
Step bIII: In step bII, a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (1) and/or a structural unit represented by formula (2) A structural unit and a polymer precursor containing a structural unit represented by formula (MA) (corresponding to polymer P(II) in step bII above) are prepared, and then the polymer precursor is reacted in the presence of a base catalyst, Treatment with water to obtain polymer P(II).

In step bII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, first the polyfunctional (meth)acrylic compound is reacted with the raw material polymer obtained in step bI to obtain It is preferable to react a monofunctional (meth)acrylic compound with the reaction mixture.

Each step will be described below.
(Step bI)
In step bI, a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (MA), and a divalent to hexavalent carbon number of 1 to 30 The step of preparing a raw material polymer containing an organic group (i) includes a monomer represented by the formula (NBm), a monomer represented by the formula (AKm), and a monomer represented by the formula (MAm). The composition can be polymerized (addition polymerization) in the presence of a compound containing a thiol group having a functionality of two or more.

Examples of bifunctional or higher thiol group-containing compounds include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-21). The bifunctional or higher thiol group-containing compounds may be used singly or in combination of two or more.
Specific conditions for step bI are the same as for step aI in the method for producing polymer P(I) of the first embodiment.

(Step bII)
For step bII, the same conditions as for step aII in the method for producing polymer P(I) of the first embodiment can be applied.

(Step bIII)
In step bIII, the same conditions as in step aIII in the method for producing polymer P(I) of the first embodiment can be applied.

[Third Embodiment]
(Polymer P(III))
The polymer in the fifth embodiment of the present invention (herein referred to as "polymer P(III)") comprises a structural unit represented by formula (NB) and a structural unit represented by formula (AK) and a structural unit represented by the formula (MA).

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.

In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

The polymer P(III) is a raw material polymer used in the production of the polymer P(I) in the first embodiment, and is the polymer obtained in the above step aI.

Polymer P(III) has a low softening point of 160° C. or less due to the structural unit represented by formula (AK). The softening point of polymer P(III) is preferably 140° C. or lower, more preferably 130° C. or lower. Moreover, the polymer P(III) has a low melting point of 180° C. or lower due to the inclusion of the structural unit represented by the formula (AK). The melting point of polymer P(III) is preferably 160° C. or lower, more preferably 140° C. or lower.

The weight average molecular weight Mw of polymer P(III) is, for example, 1,000 to 10,000. The weight average molecular weight Mw of polymer P(III) is preferably 1,000 to 7,500, more preferably 1,000 to 5,000. By appropriately adjusting the weight-average molecular weight, it becomes possible to adjust the weight-average molecular weight of the polymer P(I) obtained from the polymer P(III), and as a result, the sensitivity of the polymer P(I) and the alkali developer can be adjusted to the desired degree.
Further, the degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P(III) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, still more preferably 1.0. ~3.0.

[Fourth embodiment]
(Polymer P(IV))
The polymer in the fourth embodiment of the present invention (referred to herein as "polymer P(IV)") has a structure represented by formula (P4). The polymer P (IV) is represented as "Y" in the formula (P4) and is typically a divalent to hexavalent organic group having 1 to 30 carbon atoms derived from a difunctional or higher thiol group-containing compound. Specifically, it has a structure in which a polymer chain composed of structural unit A, structural unit B′ and structural unit C is bonded.

In formula (P4),
m is an integer of 0 to 5, preferably 0 or 1, more preferably 0;
n is an integer of 1-6, preferably 3-6.
m+n is 2-6, preferably 3-6.
p, q and r denote the molar contents of A, B and C respectively, p+q+r=1.
p is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, more preferably 0.35 to 0.60.
q is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, more preferably 0.25 to 0.45.
r is greater than 0, preferably 0.03 to 0.3, more preferably 0.04 to 0.28, particularly preferably 0.05 to 0.25.
p, q or r may be the same or different for every n structural units in [ ].
X is hydrogen or an organic group having 1 to 30 carbon atoms.
Y is a divalent to hexavalent organic group having 1 or more and 30 or less carbon atoms derived from a thiol group-containing compound having a functionality of 2 or more.
A is a structural unit represented by formula (NB).
B' is a structural unit represented by formula (MA).
C represents a structural unit represented by formula (AK).
Multiple A's, B''s, and C's may be the same or different.
D is any structure different from the structure in [ ]n, eg, one or two of A, B', and C above.

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2.

式（ＭＡ）中、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素原子または炭素数１～３の有機基である。

In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

式（ＡＫ）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の少なくとも１つは、炭素数３以上の直鎖状もしくは分枝鎖状のアルキル基であり、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４の残りは、それぞれ独立して、水素原子、または炭素数１～３０の直鎖もしくは分枝鎖のアルキル基である。

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

The polymer P(IV) is a raw material polymer used in the production of the polymer P(II) described above, and is the polymer obtained in the step bI described above.

The weight average molecular weight Mw, polydispersity (weight average molecular weight Mw/number average molecular weight Mn), softening point, and melting point of the polymer P(IV) are the same as those of the polymer P(III) described above.

[Polymer solution]
The polymer solution of this embodiment contains polymer P(I) or polymer P(II) as described above. The polymer solution of the present embodiment may contain at least one selected from polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds along with polymer P(I) or polymer P(II).

(Polyfunctional (meth)acrylic compound)
The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that can be contained in the polymer solution of the present embodiment is the (meth)acrylic compound used in the above step aII or step bII in the production of the polymer P. It may be a reactant or may be added separately.

Examples of the polyfunctional (meth)acrylic compound that can be incorporated into the polymer solution include compounds represented by the following formula (1b-p), compounds represented by the formula (1c-p), and formula (1d -p), but are not limited to these.

The definitions and specific embodiments of k, R, X ¹ , X ¹ ' and X ² in formula (1b-p) are the same as in formula (1b) above. The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in formula (1c-p) are the same as in formula (1c) above.

Y in Formula (1b-p), Formula (1c-p) and Formula (1d-p) is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

Compounds of formula (1b-p), formula (1c-p) and formula (1d-p) in which Y is a hydrogen atom are unreacted monomers (i.e. formulas (1b-p), formulas (1c-p) and compound represented by the formula (1d-p)), or can be added separately.
n in the formula (1dp) is an integer of 2 or more, preferably an integer of 2-5, more preferably an integer of 2-3.

Separately from the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P(I), polymer P(II), polymer P(III) or P(IV), When the polyfunctional (meth)acrylic compound is blended, the blending amount is such that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is polymer P (I ), preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less relative to the peak area of polymer P(II), polymer P(III) or P(IV). can be done.

(Monofunctional (meth)acrylic compound)
Examples of the monofunctional (meth)acrylic compound blended in the polymer solution of the present embodiment include compounds represented by the following formulas (2a-m). In formulas (2a-m), the definitions of X ¹⁰ and R are the same as in formula (2a).

Separately from the unreacted monofunctional (meth)acrylic compound used in the production of polymer P(I), polymer P(II), polymer P(III) or P(IV), When a monofunctional (meth)acrylic compound is blended, the blending amount is such that the peak area derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is the polymer P (I ), preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less relative to the peak area of polymer P(II), polymer P(III) or P(IV). can be done.

The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Specific examples of organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyl lactone, N-methylpyrrolidone and cyclohexanone. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the organic solvent to be used is not particularly limited, but it is used in such an amount that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[Production of polymer solution]
The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material for the photosensitive resin composition described below.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment contains the above polymer P(I), polymer P(II), polymer P(III) or polymer P(IV), and a photopolymerization initiator. That is, the photosensitive resin composition of this embodiment contains the polymer solution of this embodiment described above and a photopolymerization initiator. Each component is explained below.

(Photoinitiator)
The photopolymerization initiator used in the photosensitive resin composition of the present embodiment includes a photoradical polymerization initiator. As the radical photopolymerization initiator, known compounds can be used. methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4- [4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) ) phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin compounds such as benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4- methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; 2-trichloromethyl -5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 4 -oxadiazole, halomethylated oxadiazole compounds such as 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2′-bis(2-chlorophenyl)-4,4′, 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole compounds such as 1,2-octane dione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1 -Oxime ester compounds such as (O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)- titanocene compounds such as phenyl) titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; A photoradical polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.
The radical photopolymerization initiator is used in an amount of, for example, 1 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the polymer P.

The photosensitive resin composition of the present embodiment has high sensitivity in photolithographic processing and excellent alkali solubility by containing the above components. Therefore, the photosensitive resin composition has excellent developability and excellent processability in photolithography.

(coloring agent)
As one aspect, the photosensitive resin composition may contain a colorant. By containing a coloring agent, it can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state imaging device. Various pigments or dyes can be used as colorants.
An organic pigment or an inorganic pigment can be used as the pigment.

Organic pigments include azo-based pigments, phthalocyanine-based pigments, quinacridone-based pigments, perylene-based pigments, perinone-based pigments, isoindolinone-based pigments, isoindoline-based pigments, dioxazine-based pigments, thioindigo-based pigments, anthraquinone-based pigments, and quinophthalone-based pigments. Pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, dye lake pigments, and the like can be used.

Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow, cadmium-based, chrome vermillion, nickel titanium, chrome titanium , yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, navy blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments ( zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used.
When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only one coloring agent, or may contain two or more coloring agents.

Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. Particle size is preferred, and when concealing properties such as paint are required, a large average particle size of 0.5 μm or more is preferred.

The colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application.

When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose and application. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, based on the total components (components excluding the solvent).

(Surfactant)
The photosensitive resin composition of the present embodiment can contain a surfactant, and the surfactant is preferably a nonionic surfactant.

By including a nonionic surfactant, the coating properties of the photosensitive resin composition are improved when a resin film is obtained by applying the composition onto a substrate, and a coating film having a uniform thickness can be obtained. In addition, it is possible to prevent residues and patterns from rising when the coating film is developed.

A nonionic surfactant is, for example, a compound containing a fluorine group (eg, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In the present embodiment, it is more preferable to use a fluorine-based surfactant or a silicone-based surfactant as the nonionic surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorosurfactants include Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477 and F manufactured by DIC Corporation. -554, F-556, and F-557, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, and the like, but are not limited thereto.
When a surfactant is used, the amount of the surfactant to be blended is preferably 0.01 to 10% by weight with respect to 100 parts by mass of the resin.

(solvent)
The photosensitive resin composition can typically contain a solvent. An organic solvent is preferably used as the solvent. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl- n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.
The amount of the solvent used is not particularly limited, but it is used in such an amount that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

(Light shielding agent)
The resin composition of the present embodiment can contain a light shielding agent. The photosensitive resin composition may contain only 1 type of light-shielding agents, and may contain 2 or more types.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and application. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, based on the total components (components excluding the solvent).

(crosslinking agent)
The photosensitive resin composition of this embodiment can contain a cross-linking agent.
The cross-linking agent is not particularly limited as long as it can cross-link the polymer P (chemically bond with the polymer P) by the action of the active chemical species generated from the photopolymerization initiator.
The cross-linking agent may not only chemically bond with the polymer, but may react with each other to form a bond.

The cross-linking agent is, for example, preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and a polyfunctional (meth) acrylic compound having two or more (meth)acryloyl groups in one molecule. is more preferred (but the cross-linking agent does not fall under the aforementioned polymers). It is preferable to use a cross-linking agent having the same type of cross-linking group as the cross-linking group (polymerizable double bond) of the polymer from the viewpoint of uniform curability and further improvement of sensitivity.
Although there is no particular upper limit to the number of functionalities (the number of polymerizable double bonds) per molecule of the cross-linking agent, it is, for example, 8 or less, preferably 6 or less.

Specific examples of cross-linking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, (meth)acrylates, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth) Acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylol Propane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate Acrylates, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate , ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, polyfunctional (meth) acrylates;
Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Polyfunctional vinyl ethers such as adduct dipentaerythritol hexavinyl ether;
2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4 (meth) acrylic acid -vinyloxybutyl, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, ( Vinyl ether group-containing (meth) such as p-vinyloxymethylphenylmethyl meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate acrylic acid esters;
ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;
Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate;
Polyfunctional (meth)acryloyl such as tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate group-containing isocyanurates;
Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;
Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Polyfunctional urethane (meth) acrylates obtained in;
Polyfunctional aromatic vinyls such as divinylbenzene;
etc. can be mentioned.

Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; ) acrylate and hexafunctional (meth)acrylate such as dipentaerythritol hexa(meth)acrylate are preferred.

When the photosensitive resin composition contains a cross-linking agent, the photosensitive resin composition may contain only one cross-linking agent, or two or more cross-linking agents. When the photosensitive resin composition contains a cross-linking agent, the amount thereof may be appropriately set according to the purpose and application. As an example, the amount of the cross-linking agent can be usually about 30 to 70 parts by weight, preferably about 40 to 60 parts by weight, per 100 parts by weight of the photosensitive resin.

(Other additives)
Depending on various purposes and required properties, the photosensitive resin composition may contain fillers, binder resins other than the above polymers, acid generators, heat resistance improvers, development aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, oxidation Ingredients such as inhibitors, matting agents, antifoaming agents, leveling agents, antistatic agents, dispersing agents, slip agents, surface modifiers, thixotropic agents, thixotropic aids, silane coupling agents, polyhydric phenol compounds, etc. may include

[Use]
A patterned film can be obtained by forming a film using the photosensitive resin composition described above, exposing and developing the film to form a pattern. This film is applied to color filters, black matrices, and the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Moreover, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light shielding agent. Then, a liquid crystal display device and a solid-state imaging device having color filters and a black matrix can be manufactured.
A typical procedure for forming a pattern will be described.

(Formation of photosensitive resin film)
For example, a photosensitive resin film is first obtained by applying the above photosensitive resin composition onto an arbitrary substrate and drying it as necessary.

The substrate to which the composition is applied is not particularly limited. Examples thereof include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates.
The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed thereon. It may be surface-treated to improve adhesion.

The method of applying the photosensitive resin composition is not particularly limited. It can be applied by spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating, inkjet method, or the like.

Drying of the photosensitive resin composition coated on the substrate is typically performed by heat treatment using a hot plate, hot air, an oven, or the like. The heating temperature is usually 80-140°C, preferably 90-120°C. The heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

The film thickness of the photosensitive resin film is not particularly limited, and may be appropriately adjusted according to the pattern to be finally obtained. In addition, the film thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, and the like.

(exposure)
Exposure is typically performed by exposing the photosensitive resin film to actinic rays through a suitable photomask.

Actinic rays include, for example, X-rays, electron beams, ultraviolet rays, and visible rays. Light with a wavelength of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp, and particularly preferably i-line. Also, two or more rays may be mixed and used. A contact aligner, mirror projection or stepper is preferred as the exposure device.
The amount of light for exposure may be appropriately adjusted depending on the amount of the photosensitive agent in the photosensitive resin film, and is, for example, about 100 to 500 mJ/cm ² .

After the exposure, the photosensitive resin film may be heated again as necessary (post-exposure heating: Post Exposure Bake). The temperature is, for example, 70-150°C, preferably 90-120°C. Also, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. Heating after exposure accelerates the reaction by radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

(developing)
By developing the exposed photosensitive resin film with a suitable developer, a pattern can be obtained and a patterned substrate can be manufactured.
Since the photosensitive resin film made of the photosensitive resin composition containing the polymer solution of the present embodiment has excellent adhesion to the substrate, peeling of the pattern is suppressed in the development process.

In the development step, development can be carried out using a suitable developer, for example, by a dipping method, a puddle method, a rotary spray method, or the like. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) of the photosensitive resin film is eluted and removed to obtain a pattern.
Usable developer is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used.

Specific examples of alkaline aqueous solutions include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia, (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine and triethanolamine, and (iii) Examples include aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Since the polymer of the present embodiment has adjusted alkali solubility and excellent sensitivity, when using a strongly basic developer such as a TMAH (tetramethylammonium hydroxide) solution, the pattern after exposure and development can be formed as designed. can be in the shape of

Specific examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether.
A water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the developer.

In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, a sodium carbonate aqueous solution, or a potassium hydroxide aqueous solution.
The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.5 to 5% by mass.
Through the above steps, a pattern can be obtained/a patterned substrate can be manufactured, and various treatments may be performed after development.

For example, after development, the pattern and substrate may be washed with a rinse. Examples of rinse liquids include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more.

Alternatively, the obtained pattern may be heated to sufficiently harden it. The heating temperature is typically 150-400°C, preferably 160-300°C, more preferably 200-250°C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a heating oven in which a temperature program can be set, or the like. The atmospheric gas for the heat treatment may be air or an inert gas such as nitrogen or argon. Moreover, you may heat under pressure reduction.
FIG. 1 schematically shows an example of the structure of a liquid crystal display device and/or solid-state imaging device having color filters and/or black matrices.

A black matrix 11 and color filters 12 are formed on the substrate 10 . A protective film 13 and a transparent electrode layer 14 are provided on the black matrix 11 and the color filter 12 .

The substrate 10 is generally made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, or a cyclic olefin polymer. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like, if necessary.
Substrate 10 is preferably composed of glass.
The black matrix 11 is composed of, for example, a cured photosensitive resin composition containing a light shielding agent.

As the color filter 12, there are usually three colors of red, green and blue. The color filter 12 is composed of a cured photosensitive resin composition containing a colorant corresponding to each color.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted.

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

The compounds used in Examples may be indicated by the following abbreviations or trade names.
・MAN: maleic anhydride ・NB: 2-norbornene ・FADB: dibutyl fumarate ・BVE: butyl vinyl ether ・VBR: vinyl butyrate ・HXE: 1-hexene ・OTE: 1-octene ・DCE: 1-decene ・DDCE: 1 -Dodecene ODCE: 1-octadecene MEK: methyl ethyl ketone PEMP: pentaerythritol tetrakis (3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.)
・4-HBA: 4-hydroxybutyl acrylate ・A-TMM-3LM-N: A mixture of the following two compounds, the amount of the left compound in the mixture based on gas chromatography measurement is about 57% (Shin-Nakamura Chemical Co., Ltd. manufactured by the company)

<Synthesis of raw polymer>
(Synthesis of Raw Polymer 1)
602.56 g of a 75% toluene solution of 2-norbornene (451.92 g as 2-norbornene, 4.8 mol), maleic anhydride (MAN, 470.69 g) were placed in a reaction vessel equipped with a stirrer, condenser and dropping funnel. , 4.8 mol) and 2281.74 g of methyl ethyl ketone (MEK) were added, stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, trade name: V-601 , 44.21 g, 0.19 mol) and PEMP (93.82 g, 0.19 mol) dissolved in 193.4 g of MEK was added over 1 hour. After that, the mixture was further reacted at 80° C. for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The resulting white solid was further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120° C. to obtain a polymer having structural units derived from 2-norbornene and structural units derived from maleic anhydride ( 910.1 g of raw polymer 1) was obtained.
As a result of measuring the obtained raw material polymer 1 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was was 1.62.

(Confirmation of thioether structure contained in raw material polymer 1)
^{A 13} C-NMR measurement of PEMP alone represented by the following chemical formula confirmed a peak a derived from carbon a at around 19.0 ppm and a peak b derived from carbon b at around 62.0 ppm.

In the ¹³ C-NMR measurement of raw material polymer 1 synthesized using PEMP, the appearance of peak b derived from carbon b was confirmed near 62.0 ppm. In the GPC measurement of the reaction solution, no PEMP single peak was observed, and no unreacted PEMP remained.

Also, in the ¹³ C-NMR measurement of the starting polymer 1, the peak a derived from carbon a was not confirmed, and instead, the peak c corresponding to the thioether (RSR') appeared around 28 ppm. Since the integrated value of this peak c is approximately twice the integrated value of peak b, the starting polymer 1 has a skeleton having a thioether group as shown below, and the thiol group has disappeared.

The conditions for ¹³ C-NMR measurement are as follows.
(Test conditions) A measurement sample was prepared by adding a measurement solvent to a weighed sample to adjust the concentration, and then pouring a specified amount into a sample tube for NMR measurement.
・Measuring device: JEOL JNM-ECA400 superconducting FT-NMR device ・Resonance frequency: 100.53MHz
・Measurement nuclei: ¹³ C
・Measurement method: NNE measurement (inverse gate decoupling method)
・Pulse width: 3.83 μsec
・Pulse repetition waiting time: 30s
・Number of accumulations: 4096 times ・Measurement temperature: room temperature ・Measurement solvent: DMSO-d ₆ (deuterated dimethyl sulfoxide)
・ Sample concentration: 20% (w / v)
The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the polymer was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the raw material polymer 1.

As a result of elemental analysis, the sulfur content in the starting polymer 1 was found to be 2.4 wt %.

(Synthesis of raw material polymer 2)
112.98 g of a 75% toluene solution of 2-norbornene (equivalent to 2-norbornene, 84.75 g, 0.900 mol), maleic anhydride (MAN, 88.0 mol), were placed in a reaction vessel equipped with a stirrer, condenser and dropping funnel. 25 g, 0.900 mol), 102.73 g (0.450 mol) of dibutyl fumarate, and 179.12 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 70 ° C., dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, trade name: V-601 , 10.36 g, 0.045 mol) and PEMP (32.98 g, 0.0675 mol) dissolved in 76.77 g of MEK was added over 1 hour. Further, the temperature was raised to 80°C, and after the temperature was raised, reaction was carried out at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3016.2 g of methanol to precipitate a white solid. The resulting white solid was further washed with 754.1 g of methanol and then vacuum dried at a temperature of 120° C. to obtain a structural unit derived from 2-norbornene, a structural unit derived from dibutyl fumarate, and maleic anhydride. 154.2 g of a polymer (raw material polymer 2) having a structural unit derived from was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,800, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 54.

[Structural analysis of raw material polymer 2]
At the start of the reaction, the synthesis of the raw material polymer 2 starts with the monomer and PEMP dissolved in a solvent, after which the reaction progresses to produce a polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

(a) Analysis of reaction solution No peak of PEMP alone was observed in the GPC measurement of the reaction solution before reprecipitation purification. That is, it was confirmed that no PEMP remained in the reaction solution. In addition, in GC (gas chromatography) measurement of the reaction solution before reprecipitation purification, the peaks of norbornene alone, dibutyl fumarate alone, and maleic anhydride alone in the reaction solution after the reaction are reduced compared to before the reaction. , norbornene, dibutyl fumarate and maleic anhydride reacted to form a polymer.

(b) Polymer Analysis GPC measurement of the polymer after reprecipitation and purification showed no peaks for PEMP alone, norbornene alone, dibutyl fumarate alone, or maleic anhydride alone. That is, it was confirmed that PEMP, simple norbornene, simple dibutyl fumarate, and simple maleic anhydride did not remain in the polymer.

(Synthesis of Raw Polymer 3)
In a reaction vessel equipped with a stirrer, condenser and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g as 2-norbornene, 0.900 mol), maleic anhydride (MAN, 1110. 32 g, 1.125 mol), 22.54 g (0.225 mol) of butyl vinyl ether (BVE), and 206.89 g of methyl ethyl ketone (MEK) were added, stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, trade name: V-601 , 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 109.99 g MEK was added over 1 hour. Furthermore, it was made to react at 80 degreeC for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3016.2 g of methanol to precipitate a white solid. The resulting white solid was further washed with 754.1 g of methanol and then vacuum dried at a temperature of 120° C. to give a structural unit derived from 2-norbornene, a structural unit derived from butyl vinyl ether, and maleic anhydride. 181.5 g of a polymer (raw material polymer 3) having the derived structural unit was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 4,500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.0. was 33.

The amount of sulfur in the obtained raw material polymer 3 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 3 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of Raw Polymer 4)
In the same manner as the starting polymer 3 except that 25.68 g (0.225 mol) of vinyl butyrate (VBR) was used instead of butyl vinyl ether (BVE), structural units derived from 2-norbornene and butyl vinyl ether 195.1 g of a polymer (raw material polymer 4) having a structural unit derived from maleic anhydride and a structural unit derived from maleic anhydride was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,700, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 89.

The amount of sulfur in the obtained raw material polymer 4 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 4 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of Raw Polymer 5)
In a reaction vessel equipped with a stirrer, condenser and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g as 2-norbornene, 0.900 mol), maleic anhydride (MAN, 110. 32 g, 1.125 mol), 31.56 g (0.225 mol) of 1-decene (DCE), and 569.75 g of methyl ethyl ketone (MEK) were added, stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, trade name: V-601 , 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 48.20 g of MEK was added over 1 hour. Furthermore, it was made to react at 80 degreeC for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3621.5 g of methanol to precipitate a white solid. The resulting white solid was further washed with 905.4 g of methanol and then vacuum dried at a temperature of 120° C. to obtain a structural unit derived from 2-norbornene, a structural unit derived from 1-decene, and maleic anhydride. 180.1 g of a polymer (raw material polymer 5) having a structural unit derived from was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,700, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 77. Regarding raw material polymer 5, the ratio of structures derived from each monomer actually introduced into the raw material polymer calculated by ¹³ C-NMR was norbornene:maleic anhydride:1-decene=42.0%:51.0%:7. 0%, and the amount of PEMP actually introduced into the starting polymer was 2.9 mol% with respect to the total amount of each monomer.

(Confirmation of structure of raw material polymer 5)
Structural units derived from PEMP, structural units derived from 1-decene (structural units of formula (AK)), structural units derived from maleic anhydride (structural units of formula (MA)), and structures derived from norbornene in raw material polymer 5 The amount (molar fraction, mol %) of (structural unit of formula (NB)) was calculated by integral value analysis of ¹³ C-NMR. A ¹³ C-NMR chart is shown in FIG.
The chemical shifts in the ¹³ C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values were measured.
・ k (4C) of PEMP: 62.0 to 64.0 ppm
・ 1-decene terminal (1C): 13.0 to 15.0 ppm
· g (4C) of maleic anhydride ester (2C) + PEMP: 170.0 to 174.7 ppm
· Maleic acid ester (2C) (structure in which maleic anhydride is ring-opened): 174.7 to 178.0 ppm
・ Alkyl chain: 20 to 60 ppm
· DMSO: around 40 ppm · Norbornene (7C) = alkyl chain - DMSO - PEMP (9C, h + i + j) - maleic anhydride (2C) - maleic acid (2C) - decene (9C)
Here, the structural ratio derived from maleic anhydride actually introduced into the raw material polymer was calculated including the structure of maleic acid ring-opened from maleic anhydride in addition to the structural units of the formula (MA).

At the start of the reaction, the synthesis of the raw material polymer 5 starts with the monomer and PEMP dissolved in a solvent, and then the reaction progresses to produce a polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

(a) Analysis of reaction solution No peak of PEMP alone was observed in the GPC measurement of the reaction solution before reprecipitation purification. That is, it was confirmed that no PEMP remained in the reaction solution. In addition, in the GC (gas chromatography) measurement of the reaction solution before reprecipitation purification, the peaks of norbornene alone, 1-decene alone, and maleic anhydride alone in the reaction solution after the reaction are reduced compared to before the reaction. , norbornene, 1-decene and maleic anhydride reacted to form a polymer.
The measurement conditions for the gas chromatography measurement were as follows.
・GC device: GC-2030 (Shimadzu Corporation)
・Carrier gas: _N2
・ Detector: Flame ionization (FID) detector, FID temperature: 300 ° C.
・ Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Co., Ltd.)
・Vaporization chamber temperature: 210°C
・Column flow rate: 0.64 mL/min
・Column heating conditions: 50° C. 5 min hold, 20° C./min up to 300° C., 300° C. 10 min hold

(b) Polymer Analysis GPC measurement of the polymer after reprecipitation and purification showed no peaks for PEMP alone, norbornene alone, 1-decene alone, and maleic anhydride alone. That is, it was confirmed that no PEMP, norbornene monomer, 1-decene monomer, or maleic anhydride monomer remained in the polymer.

The amount of sulfur in the obtained raw material polymer 5 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 5 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of Raw Polymer 6)
In a reaction vessel equipped with a stirrer, condenser and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g as 2-norbornene, 0.900 mol), maleic anhydride (MAN, 110. 32 g, 1.125 mol), 31.56 g (0.225 mol) of 1-decene (DCE), and 217.12 g of methyl ethyl ketone (MEK) were added, stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, trade name: V-601 , 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 115.43 g MEK was added over 1 hour. Furthermore, it was made to react at 80 degreeC for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3621.5 g of methanol to precipitate a white solid. The resulting white solid was further washed with 905.4 g of methanol and then vacuum dried at a temperature of 120° C. to obtain a structural unit derived from 2-norbornene, a structural unit derived from 1-decene, and maleic anhydride. 190.1 g of a polymer (raw material polymer 6) having a structural unit derived from was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,600, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 90.

The amount of sulfur in the obtained raw material polymer 6 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 6 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of Raw Polymer 7)
84.74 g of 75% toluene solution of 2-norbornene (63.55 g in terms of 2-norbornene, 0.675 mol), 63.12 g (0.450 mol) of 1-decene Same as raw polymer 5 Thus, 205.1 g of a polymer (raw material polymer 7) having structural units derived from 2-norbornene, structural units derived from 1-decene, and structural units derived from maleic anhydride was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,000, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 58.
The amount of sulfur in the obtained raw material polymer 7 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 7 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of Raw Polymer 8)
A structural unit derived from 2-norbornene and a structural unit derived from 1-hexene were prepared in the same manner as raw polymer 5 except that 18.94 g (0.225 mol) of 1-hexene was used instead of 1-decene. and a structural unit derived from maleic anhydride (raw polymer 8) was obtained (179.2 g).
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 73.
The amount of sulfur in the raw material polymer 8 obtained was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 8 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of raw material polymer 9)
A structural unit derived from 2-norbornene and a structural unit derived from 1-octene in the same manner as raw polymer 5 except that 25.25 g (0.225 mol) of 1-octene was used instead of 1-decene. and a structural unit derived from maleic anhydride (raw polymer 9) was obtained (185.1 g).
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 74.
The amount of sulfur in the obtained raw material polymer 9 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 9 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of Raw Polymer 10)
A structural unit derived from 2-norbornene and a structural unit derived from 1-dodecene were prepared in the same manner as raw polymer 5 except that 37.87 g (0.225 mol) of 1-dodecene was used instead of 1-decene. and a structural unit derived from maleic anhydride (raw polymer 10) was obtained (192.7 g).
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 98.
The amount of sulfur in the obtained raw material polymer 10 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 10 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

(Synthesis of raw material polymer 11)
A structural unit derived from 2-norbornene and a structural unit derived from 1-octadecene were prepared in the same manner as the starting polymer 6 except that 56.81 g (0.225 mol) of 1-octadecene was used instead of 1-decene. and a structural unit derived from maleic anhydride (raw polymer 11) was obtained (205.7 g).
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 79.
The amount of sulfur in the obtained raw material polymer 11 was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in the raw material polymer 11 was confirmed. Also in the GPC measurement of the reaction solution before dropping methanol, the PEMP-derived peak disappeared, confirming that PEMP was incorporated into the polymer.

For raw material polymers 2 to 11, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC) measurement, and the consumption of each monomer was calculated to obtain the amount of each introduced into the raw material polymer. The ratio of monomers was calculated.
Table 1 below shows the charging ratio of the monomers used in the synthesis of the raw material polymer, the ratio of the monomers introduced into the raw material polymer, the weight average molecular weight (Mw) and other dispersity (Mw/Mn) of the raw material polymer.
The measurement conditions for the gas chromatography measurement are as follows.
・GC device: GC-2030 (Shimadzu Corporation)
・Carrier gas: _N2
・ Detector: Flame ionization (FID) detector, FID temperature: 300 ° C.
・ Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Co., Ltd.)
・Vaporization chamber temperature: 210°C
・Column flow rate: 0.64 mL/min
・Column heating conditions: 50°C 5min hold, 20°C/min up to 300°C, 300°C 10min hold

<Synthesis of Polymer P>
Polymer P was prepared using the following method.

(Preparation Example 1)
A polymer P1 was prepared by ring-opening the MA unit of the raw material polymer 1 with a monofunctional (meth)acrylic compound. Details will be described below.
First, 18.44 g of MEK was added to 10.00 g of raw material polymer 1 (0.052 mol in terms of MA calculated from the charged amount of raw material polymer 1) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added and reacted at a temperature of 70° C. for 6 hours to obtain a reaction solution. was made.
The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. After that, the polymer was purified by the following reprecipitation method.
- Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The resulting reaction product was dried at 40° C. for 12 hours.
As a result, 8.7 g of polymer P1 was obtained in which the maleic anhydride-derived structural unit in raw material polymer 1 was ring-opened with 4-HBA.
The obtained polymer P1 was subjected to GPC measurement to determine the weight average molecular weight and polydispersity of polymer P1. Table 2 shows the results.
Further, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P1. Thereby, it was confirmed that the obtained polymer P1 contained no unreacted monofunctional (meth)acrylic compound.

(Preparation Example 2)
A polymer P2 was prepared by ring-opening the MA unit of the starting polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water. Details will be described below.
First, 99.93 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA calculated from the charged amount of raw material polymer 1) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Then, 3.00 g (0.167 mol) of water was added to the reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours.
The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction and subsequent solvent replacement were performed in the following procedure.
Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and then the same operation was performed once.
- Solvent replacement: The solvent was removed from the resulting reaction mixture at 50°C under reduced pressure using a rotary evaporator. After confirming that the solid content concentration of the polymer solution reached 27±2% by mass as measured by a heat drying moisture meter, the solvent removal operation was discontinued. After that, PGMEA was added so that the solid content concentration was 18% by mass, and mixed until uniform. The solvent is removed at 50° C. under reduced pressure in the same manner, and after adjusting the solid content concentration to 27±2% by mass as measured by a heat drying moisture meter, PGMEA is added so that the solid content concentration becomes 18% by mass. and mixing until uniform was repeated two more times. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until uniform. The above operation removes the solvent used for the reaction and replaces the solvent with PGMEA. After that, it was further purified by the following procedure.
• The polymer was reprecipitated with an excess amount of toluene.
- The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.
- The operation of washing the polymer powder after washing twice with an excessive amount of water was repeated three times.
• The resulting reaction product was dried at 40°C for 12 hours.
As described above, a polymer P2 was prepared by ring-opening the MA unit of the raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water.
GPC measurement was performed on the resulting polymer P2 to determine the weight average molecular weight and polydispersity of polymer P2. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P2. Thus, it was confirmed that the obtained polymer P2 contained neither unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P2 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 3)
Raw materials were prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw polymer 2 (calculated from the composition ratio calculated from GC measurement of raw polymer 2, 0.034 mol in terms of MA) was used instead of raw polymer 1. Polymer P3 was prepared by ring-opening the MA unit of polymer 2 with a monofunctional (meth)acrylic compound.
GPC measurements were performed on the resulting polymer P3 to determine the weight average molecular weight and polydispersity of polymer P3. Table 2 shows the results.
Further, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P3. Thereby, it was confirmed that the obtained polymer P3 contained no unreacted monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P3 has a structure in which structural units derived from maleic anhydride are ring-opened with 4-HBA.

(Preparation Example 4)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 2 (calculated from the composition ratio calculated from GC measurement of raw polymer 2, 0.204 mol in terms of MA) was used instead of raw polymer 1. A polymer P4 was prepared by ring-opening the MA unit of the polymer 2 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P4 to determine the weight average molecular weight and polydispersity of polymer P4. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P4. As a result, it was confirmed that the obtained polymer P4 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P4 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 5)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 3 (calculated from the composition ratio calculated from GC measurement of raw polymer 3, 0.304 mol in terms of MA) was used instead of raw polymer 1. A polymer P5 was prepared by ring-opening the MA unit of the polymer 3 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P5 to determine the weight average molecular weight and polydispersity of polymer P5. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P5. Thus, it was confirmed that the obtained polymer P5 contained neither unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P5 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 6)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 4 (calculated from the composition ratio calculated from GC measurement of raw polymer 4, 0.300 mol in terms of MA) was used instead of raw polymer 1. A polymer P6 was prepared by ring-opening the MA unit of the polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P6 to determine the weight average molecular weight and polydispersity of polymer P6. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P6. As a result, it was confirmed that the obtained polymer P6 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound.
Further, ¹³ C-NMR measurement confirmed that the polymer P6 had a structure in which structural units derived from maleic anhydride were ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 7)
Raw material was prepared in the same manner as in Preparation Example 1 except that 10.00 g of raw material polymer 5 (calculated from the composition ratio calculated from GC measurement of raw material polymer 5, 0.048 mol in terms of MA) was used instead of raw material polymer 1. Polymer P7 was prepared by ring-opening the MA unit of polymer 5 with a monofunctional (meth)acrylic compound.
GPC measurements were performed on the resulting polymer P7 to determine the weight average molecular weight and polydispersity of polymer P7. Table 2 shows the results.
Also, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P7. Thereby, it was confirmed that the obtained polymer P7 contained no unreacted monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P7 has a structure in which structural units derived from maleic anhydride are ring-opened with 4-HBA.
By ¹ H-NMR measurement of the polymer P7, the introduction ratio (molar ratio) of the compound reacted with the raw material polymer in the entire structure was calculated. Table 2 shows the results.

(Preparation Example 8)
A resin mixture (polymer solution P8) containing a polymer P8 obtained by ring-opening the MA unit of the starting polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared. Details will be described below.
First, 99.93 g of MEK was added to 60.00 g of raw polymer 5 (0.290 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 5) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Then, 3.00 g (0.167 mol) of water was added to the reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours.
The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction and subsequent solvent replacement were performed in the following procedure.
- Liquid-liquid extraction: The reaction solution was diluted with MEK, then a water/methanol mixed solvent was added and treated to remove the aqueous phase from the reaction solution, and then the same operation was performed once.
- Solvent replacement: The solvent was removed from the resulting reaction mixture at 50°C under reduced pressure using a rotary evaporator. After confirming that the solid content concentration of the polymer solution reached 27±2% by mass as measured by a heat drying moisture meter, the solvent removal operation was discontinued. After that, PGMEA was added so that the solid content concentration was 18% by mass, and mixed until uniform. The solvent is removed at 50° C. under reduced pressure in the same manner, and after adjusting the solid content concentration to 27±2% by mass as measured by a heat drying moisture meter, PGMEA is added so that the solid content concentration becomes 18% by mass. and mixing until uniform was repeated two more times. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until uniform. The above operation removes the solvent used for the reaction and replaces the solvent with PGMEA.

As described above, the structural units derived from maleic anhydride in raw material polymer 5 are A-TMM-3LM-N, polymer P8 ring-opened with 4-HBA and water, and residual (free) A-TMM-3LM-N and residual (free) 4-HBA (polymer solution P8) was obtained.
The resulting polymer solution P8 was analyzed by gel permeation chromatography to determine the amount of the polymer P8 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound, and the amount of the polymer P8. Weight average molecular weight and polydispersity were measured. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P8 in the gel permeation chromatography (GPC) chart of the resin mixture.
The measurement conditions for the gel permeation chromatography method are as follows.
・As a GPC measurement device, HLC-8320GPC EcoSEC manufactured by Tosoh Corporation was used. The column temperature was set to 40.0° C. and the pump flow rate to 0.350 mL/min.
・Peak position (retention time)
Polymer P8: peak detected before 20 minutes (peak with shorter retention time and higher molecular weight than A-TMM-3LM-N and 4-HBA)
A-TMM-3LM-N: Sum of two peaks at 20.0 to 20.6 minutes and 20.6 to 21.5 minutes 4-HBA: 21.7 to 22.4 minutes Measurement conditions: Differential refractive index detection It was analyzed with a detector (RI detector).

(Preparation Example 9)
A raw polymer was prepared in the same manner as in Preparation Example 8 except that 60.00 g of raw polymer 6 (0.296 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 6) was used instead of raw polymer 5. A resin mixture (polymer solution P9) containing a polymer P9 obtained by ring-opening 6 MA units with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared.

The obtained polymer solution P9 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8, and the polymer P9 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic The amount of compound was determined, as well as the weight average molecular weight and polydispersity of polymer P9. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P9 in the gel permeation chromatography (GPC) chart of the resin mixture.

(Preparation Example 10)
A raw polymer was prepared in the same manner as in Preparation Example 8 except that 60.00 g of raw polymer 7 (0.291 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 7) was used instead of raw polymer 5. A resin mixture (polymer solution P10) containing a polymer P10 obtained by ring-opening 7 MA units with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared.

The obtained polymer solution P10 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8, and the polymer P10 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic The amount of compound was measured, as well as the weight average molecular weight and polydispersity of polymer P10. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P10 in the gel permeation chromatography (GPC) chart of the resin mixture.

(Preparation Example 11)
A raw polymer was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw polymer 8 (0.302 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 8) was used instead of raw polymer 5. A resin mixture (polymer solution P11) containing a polymer P11 obtained by ring-opening 8 MA units with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared.

The obtained polymer solution P11 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8, and the polymer P11 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic The amount of compound was measured, as well as the weight average molecular weight and polydispersity of polymer P11. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P11 in the gel permeation chromatography (GPC) chart of the resin mixture.

(Preparation Example 12)
A raw polymer was prepared in the same manner as in Preparation Example 8 except that 60.00 g of raw polymer 9 (0.298 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 9) was used instead of raw polymer 5. A resin mixture (polymer solution P12) containing a polymer P12 obtained by ring-opening 9 MA units with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared.

The obtained polymer solution P12 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8, and the polymer P12 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic The amount of compound was measured, as well as the weight average molecular weight and polydispersity of polymer P12. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P2 in the gel permeation chromatography (GPC) chart of the resin mixture.

(Preparation Example 13)
A raw polymer was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw polymer 10 (0.290 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 10) was used instead of raw polymer 5. A resin mixture (polymer solution P13) containing polymer P13 obtained by ring-opening 10 MA units with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared.

The obtained polymer solution P13 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8, and the polymer P13 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic The amount of compound was measured, as well as the weight average molecular weight and polydispersity of polymer P13. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P13 in the gel permeation chromatography (GPC) chart of the resin mixture.

(Preparation Example 14)
A raw polymer was prepared in the same manner as in Preparation Example 8 except that 60.00 g of raw polymer 11 (0.298 mol in terms of MA calculated from the composition ratio calculated from GC measurement of raw polymer 11) was used instead of raw polymer 5. A resin mixture (polymer solution P14) containing polymer P14 obtained by ring-opening 11 MA units with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water was prepared.

The obtained polymer solution P14 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8, and the polymer P14 contained in the solution, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic The amount of compound was measured, as well as the weight average molecular weight and polydispersity of polymer P14. Table 2 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P14 in the gel permeation chromatography (GPC) chart of the resin mixture.

(Preparation Example 15)
Raw materials were prepared in the same manner as in Preparation Example 2 except that 60.00 g of raw polymer 5 (calculated from the composition ratio calculated from GC measurement of raw polymer 5, 0.290 mol in terms of MA) was used instead of raw polymer 1. A polymer P15 was prepared by ring-opening the MA unit of the polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P15 to determine the weight average molecular weight and polydispersity of polymer P15. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P15. Thus, it was confirmed that the obtained polymer P15 contained neither unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P15 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 16)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 8 (calculated from the composition ratio calculated from GC measurement of raw polymer 8, 0.302 mol in terms of MA) was used instead of raw polymer 1. A polymer P16 was prepared by ring-opening the MA unit of the polymer 8 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P16 to determine the weight average molecular weight and polydispersity of polymer P16. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P16. Thus, it was confirmed that the obtained polymer P16 contained neither unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound.
¹³ C-NMR measurement confirmed that the polymer P16 had a structure in which structural units derived from maleic anhydride were ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 17)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 9 (calculated from the composition ratio calculated from GC measurement of raw polymer 9, 0.298 mol in terms of MA) was used instead of raw polymer 1. A polymer P17 was prepared by ring-opening the MA unit of the polymer 9 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P17 to determine the weight average molecular weight and polydispersity of polymer P17. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P17. Thus, it was confirmed that the obtained polymer P17 contained neither unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound.
Further, by ¹³ C-NMR measurement, it was confirmed that polymer P17 had a structure in which structural units derived from maleic anhydride were ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 18)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 10 (calculated from the composition ratio calculated from GC measurement of raw polymer 10: 0.290 mol in terms of MA) was used instead of raw polymer 1. A polymer P18 was prepared by ring-opening the MA unit of the polymer 10 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P18 to determine the weight average molecular weight and polydispersity of polymer P18. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P18. As a result, it was confirmed that the obtained polymer P18 contained neither an unreacted polyfunctional (meth)acrylic compound nor a monofunctional (meth)acrylic compound.
¹³ C-NMR measurement confirmed that the polymer P18 had a structure in which structural units derived from maleic anhydride were ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 19)
Raw materials were prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw polymer 11 (calculated from the composition ratio calculated from GC measurement of raw polymer 11: 0.298 mol in terms of MA) was used instead of raw polymer 1. A polymer P15 was prepared by ring-opening the MA unit of the polymer 11 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water.
GPC measurements were performed on the resulting polymer P19 to determine the weight average molecular weight and polydispersity of polymer P195. Table 2 shows the results.
Further, disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P19. Thus, it was confirmed that the obtained polymer P19 contained neither unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound.
¹³ C-NMR measurement confirmed that polymer P19 had a structure in which structural units derived from maleic anhydride were ring-opened with A-TMM-3LM-N, 4-HBA and water.

(Evaluation of the physical properties)
The acid value and double bond equivalent of each polymer P prepared in Preparation Examples 3, 4, 7, 15 to 19 were measured by the methods shown below.

(acid number)
The acid value of the polymer was measured by the following method.
About 50 mg of polymer and about 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was subjected to ¹ H-NMR measurement using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). Based on the integrated value of the 4H peak (around 8.1 ppm) of the phenyl group of the dimethyl terephthalate internal standard measured by ¹ H-NMR, the H peak (around 12.4 ppm) of the carboxy group (—COOH) of the polymer Calculate the amount of carboxyl groups from the integrated value of . Then, the acid value (mgKOH/g) can be calculated from the amount. A larger acid value indicates a larger amount of carboxy groups per unit mass of the polymer.
Table 2 shows the results. When the acid value is 50 gKOH/g or more, it can be considered that the carboxy groups necessary for the polymer to have sufficient developability are present in the polymer.

(double bond equivalent)
The double bond equivalent weight of the polymer was measured by the following method.
¹ H-NMR was measured in the same manner as the acid value measurement method described above. The amount of acryloyl groups in the polymer was determined from the integral ratio of the signal (5.6-5.8 ppm, 3H) derived from the acryloyl group in the spectrum chart obtained and the signal (8.1 ppm, 4H) of the phenyl group of the internal standard substance. (mol / g), and from the integral ratio of the signal derived from the methacryloyl group (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard substance (8.1 ppm, 4H), A methacryloyl group content (mol/g) was calculated. Here, the signal derived from the methacryloyl group at 6.0 to 6.1 ppm was minute and overlapped with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The amount of double bonds (mol/g) is calculated from the total amount of acryloyl groups (mol/g) and methacryloyl groups (mol/g) in the polymer, and the double bond equivalent (g/ mol) was calculated.
Table 2 shows the results. A smaller double bond equivalent value indicates a higher amount of C═C double bonds per unit mass of the polymer.

(Examples 1 to 13, Comparative Examples 1 to 6)
In each example and comparative example, a resin composition was produced and evaluated for the following items.
<Evaluation>
[Alkaline Dissolution Rate of Resin Composition]
Polymers P1 to P6 and P15 to P19 obtained in Preparation Examples 1 to 6 and 15 to 19 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 7 having a solid concentration of 30% by mass. , 15-19 were made.
Next, the resin compositions 1 to 7, 15 to 19 or the resin compositions 8 to 14 consisting of the polymer solutions P8 to P14 obtained in Preparation Examples 8 to 14 are spin-coated on the wafer, the PGMEA is dried, and By pre-baking at a temperature of 100° C. for 2 minutes, a resin film having a thickness of about 2 μm was produced.
This resin film was immersed together with the wafer in a 2% sodium carbonate aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time required for the resin film to dissolve and the interference pattern to disappear, and dividing the film thickness by that time. Table 3 shows the results. If the alkali dissolution rate is 120 nm/s or more, it can be used as a photosensitive material without any problem. can be considered better than

[Softening point of raw material polymer]
The softening points of the starting polymers 1 to 11 were measured by the following method.
First, 0.1 to 1.0 mg of the polymer to be measured (raw polymer 1 to 11) is placed in an aluminum sample pan, and a differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., "EXSTAR TMA/ SS6100") was used to measure the softening point. The measurement mode was compression, the load was 30 mN, and the temperature was raised in the range of 30° C. to 200° C. at a rate of 3° C./min. When the sample softens due to heating, the sample deforms and is detected as a displacement (μm), which is an extension of the straight portion without displacement on the low temperature side, or a tangent to the portion with the lowest displacement speed and a tangent to the portion with the highest displacement speed. was taken as the softening point. As an example, a TMA chart of Raw Polymer 5 is shown in FIG. Table 1 shows the softening point measurement results.
If the softening point of the raw material polymer is 160° C. or lower, it can be said that the softening point is low, if it is 140° C. or lower, it can be said that it is lower, and if it is 130° C. or lower, it can be said that it is particularly low.

[Melting point of raw polymer]
The melting points of the starting polymers 1 to 11 were measured by the following method.
First, 1 to 2 mg of the polymer to be measured (raw polymer 1 to 11) is placed in an aluminum sample pan, and a differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., "STA7200RV") is used in a nitrogen atmosphere. The temperature was raised from 30° C. at a rate of 10° C./min while observing the image. The temperature at which the sample starts to melt was visually confirmed and defined as the melting point.
If the melting point of the raw material polymer is 180° C. or lower, it can be said that the melting point is low, if it is 160° C. or lower, it can be said that it is lower, and if it is 140° C. or lower, it can be said that it is particularly low. Table 1 shows the results.

[Softening point of polymer P]
The softening points of the polymers P1 to P6 and P15 to P19 obtained in Preparation Examples 1 to 6 and 15 to 19 were measured by the following method.
First, 0.1 to 1.0 mg of the polymer to be measured (polymers P1 to P6, P15 to P19) was placed in an aluminum sample pan, and under a nitrogen atmosphere, a differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., " The softening point was measured using an EXSTAR TMA/SS6100"). The measurement mode was compression, the load was 30 mN, and the temperature was raised in the range of 30° C. to 200° C. at a temperature elevation rate of 3° C./min. When the sample softens due to heating, the sample deforms and is detected as a displacement (μm), which is an extension of the straight portion without displacement on the low temperature side, or a tangent to the portion with the lowest displacement speed and a tangent to the portion with the highest displacement speed. was taken as the softening point. Table 2 shows the results.
If the softening point of the polymer P is 110° C. or lower, it can be said that the softening point is low, if it is 100° C. or lower, it can be said that it is lower, and if it is 90° C. or lower, it can be said that it is particularly low.

[Melting point of polymer P]
The melting points of polymers P1-P6 and P15-P19 obtained in Preparation Examples 1-6 and 15-19 were measured by the following method.
First, 1 to 2 mg of the polymer to be measured (polymers P1 to P6, P15 to P19) is placed in an aluminum sample pan, and a differential thermal analyzer (manufactured by Hitachi High-Technologies Corporation, "STA7200RV") is analyzed under a nitrogen atmosphere. The temperature was raised from 30° C. at a rate of 10° C./min while observing the image. The temperature at which the sample starts to melt was visually confirmed and defined as the melting point. Table 2 shows the results.
If the melting point of the polymer P is 140° C. or lower, it can be said that the melting point is low, if it is 130° C. or lower, it can be said that it is lower, and if it is 120° C. or lower, it can be said that it is particularly low.

[Softening point of cured product of photosensitive resin composition]
The softening points of the photosensitive resin compositions prepared from the polymers P1 to P6 and P15 to P19 obtained in Preparation Examples 1 to 6 and 15 to 19, or the polymer solutions P8 to P14 obtained in Preparation Examples 8 to 14 were measured. , was measured by the following method.
First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid concentration was 30% by mass.
Polymers P1-P6, P15-P19 (polymers P1-P6, P15-P19 of Preparation Examples 1-6, 15-19, respectively) or resin mixtures 8-14 (polymer solutions P8-14 of Preparation Examples 8-14, respectively) P14): 100 parts by mass (here, resin mixtures 8 to 14 were weighed so that the total amount of solid content (polymers P8 to P14) and polyfunctional (meth)acrylic compound) was 100 parts by mass. )
- Photopolymerization initiator (manufactured by BASF, Irgacure OXE01): 5 parts by mass The obtained photosensitive resin composition was coated with a Teflon adhesive tape (Nitoflon adhesive tape, No. 903UL (thickness 0.08 mm, width 25 mm, length 10 mm), Nitto Denko Co., Ltd.) was pasted without gaps, and then poured into a container having dimensions of 2 cm x 2 cm and a height of 5 mm, followed by vacuum drying at 40°C for 16 hours to remove the solvent. Thereafter, g+h+i line exposure was performed with a g+h+i line mask aligner (PLA-600F) manufactured by Canon Inc. at an exposure amount of 100 mJ/cm ² . After exposure, the cured product was peeled off from the Teflon adhesive tape to obtain a cured product of the photosensitive resin composition.
0.1 to 1.0 mg of the cured product of the photosensitive resin composition to be measured is placed in an aluminum sample pan and subjected to a differential thermal analysis device (manufactured by Hitachi High-Tech Science Co., Ltd., "EXSTAR TMA / SS6100") under a nitrogen atmosphere. ) was used to measure the softening point. The measurement mode was compression, the load was 30 mN, and the temperature was raised in the range of 30° C. to 200° C. at a temperature elevation rate of 1° C./min. When the sample softens due to heating, the sample deforms and is detected as a displacement (μm), which is an extension of the straight portion without displacement on the low temperature side, or a tangent to the portion with the lowest displacement speed and a tangent to the portion with the highest displacement speed. was taken as the softening point.
Table 3 shows the evaluation results of the softening point of the cured product of the photosensitive resin composition evaluated according to the following criteria.
◯: Softening point lower than 100° C. ×: Softening point 100° C. or higher If the softening point of the cured product of the photosensitive resin composition is 100° C. or lower, it can be said that the softening point is low and the pattern formability is good.

[Sensitivity evaluation 1 of photosensitive resin composition (exposure amount at which residual film ratio is 90% or more/exposure amount at which residual film ratio is 95% or more)]
First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid concentration was 30% by mass.
Polymers P1 to P6, P15 to P19 (polymers P of Preparation Examples 1 to 6 and 15 to 19, respectively) or resin compositions 8 to 14 (polymer solutions P8 to P14 of Preparation Examples 8 to 14, respectively): 100 mass (Here, resin compositions P8 to P14 were weighed so that the total amount of solid content (polymers P8 to P14) and polyfunctional (meth)acrylic compound) was 100 parts by mass. )
· Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass · Photopolymerization initiator (manufactured by BASF, Irgacure OXE01): 5 parts by mass · Adhesion aid (Shin-Etsu Chemical Kogyo Co., Ltd., KBM-403): 1 part by mass Surfactant (DIC Corporation, F-556): 0.5 parts by mass

The resulting photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100° C. for 120 seconds to give a thickness of about 3.0 μm (±0.3 μm). A thin film A was obtained.
This thin film A was exposed to g+h+i rays at an exposure amount of 100 mJ/cm ² using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a photomask having a gradation with a light shielding rate of 1 to 100%.
After the exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (the whole wafer was immersed) to obtain a thin film B exposed and developed at each exposure amount of 1 to 100 mJ/cm ² . .
From the film thicknesses of thin film A and thin film B obtained by the above method, the residual film ratio was calculated from the following formula.
Remaining film ratio (%) = (film thickness of thin film B/film thickness of thin film A at each exposure dose) x 100
The exposure dose at which the residual film ratio becomes 90% or more was measured as the sensitivity of each photosensitive resin composition. Table 3 shows the results. If the exposure amount at which the residual film rate becomes 90% or more is 35 mJ/cm ² or less, it can be used as a photosensitive composition without problems, and if it is 20 mJ/cm ² or less, the sensitivity is considered to be good. 15 mJ/cm ² or less can be considered better, and 10 mJ/cm ² or less can be considered particularly good.
Also, the exposure amount at which the residual film ratio becomes 95% or more was measured as the sensitivity of each photosensitive resin composition. Table 3 shows the results. If the exposure amount at which the residual film rate becomes 95% or more is 50 mJ/cm ² or less, it can be used as a photosensitive composition without problems, and if it is 30 mJ/cm ² or less, the sensitivity is considered to be good. 20 mJ/cm ² or less can be considered better, and 15 mJ/cm ² or less can be considered particularly good.

[Sensitivity evaluation 2 of photosensitive resin composition (remaining film ratio after exposure with low exposure dose)]
(Remaining film rate at an exposure dose of 5 mJ/cm ² )
The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), baked on a hot plate at 100° C. for 120 seconds, and baked to a thickness of 3.0 μm (± A thin film A of 0.3 μm) was obtained.
This thin film A was exposed to g+h+i rays at an exposure amount of 5 mJ/cm ² using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a photomask having a gradation with a light shielding rate of 1 to 100%.
After the exposure, thin film B was obtained by developing the thin film in a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (immersing the wafer together).
From the film thicknesses of thin film A and thin film B obtained by the above method, the residual film ratio was calculated from the following formula.
Remaining film ratio (%) = (film thickness of thin film B/film thickness of thin film A at each exposure dose) x 100
Table 3 shows the results. It can be considered that the higher the residual film ratio at an exposure dose of 5 mJ/cm ² is, the better the sensitivity is because the curing is performed at a lower exposure dose.

(Remaining film rate at an exposure dose of 10 mJ/cm ² )
The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), baked on a hot plate at 100° C. for 120 seconds, and baked to a thickness of 3.0 μm (± A thin film A of 0.3 μm) was obtained.
This thin film A was exposed to g+h+i rays at an exposure amount of 10 mJ/cm ² using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a photomask having a gradation with a light shielding rate of 1 to 100%.
After the exposure, thin film B was obtained by developing the thin film in a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (immersing the wafer together).
From the film thicknesses of thin film A and thin film B obtained by the above method, the residual film ratio was calculated from the following formula.
Remaining film ratio (%) = (film thickness of thin film B/film thickness of thin film A at each exposure dose) x 100
Table 3 shows the results. It can be considered that the higher the residual film ratio at an exposure dose of 10 mJ/cm ² is, the better the sensitivity is because the film is cured at a lower exposure dose.

[Alkali dissolution rate of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)]
The photosensitive resin composition prepared in Sensitivity Evaluation 1 was spin-coated on a wafer, the PGMEA was dried, and pre-baked at 100° C. for 2 minutes to prepare a resin film having a thickness of about 2 μm.
This resin film was immersed together with the wafer in a 2% sodium carbonate aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time required for the resin film to dissolve and the interference pattern to disappear, and dividing the film thickness by that time. Table 3 shows the results. If the alkali dissolution rate is 480 nm/s or more, it can be used as a photosensitive material without problems, if it is 700 nm/s or more, it can be considered to have good developability, and if it is 900 nm/s or more, can be considered particularly good.

[Yellow Index]
The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on Eagle XG glass (manufactured by Corning, thickness 0.5 mm), and baked on a hot plate at 100° C. for 120 seconds to give about 3. A thin film of 0 μm thickness (±0.1 μm) was obtained.
This thin film was exposed to g+h+i rays at an exposure dose of 100 mJ/cm ² using a g+h+i ray mask aligner (PLA-600F) manufactured by Canon Inc.
After the exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (the whole wafer was immersed) to obtain an exposed and developed thin film with an exposure dose of 100 mJ/cm ² .
The thin film was heat treated at 230° C. for 30 minutes in air. After cooling the thin film at room temperature under air, the thin film was again heat-treated at 230° C. for 30 minutes under air. The same operation was repeated, and the heat treatment was performed three times in total for 30 minutes in the air.
The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement points using a color difference meter CR-5 (manufactured by Konica Minolta), and the average value was taken as the YI value. The measurement type was transmission measurement, and uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm) was used for 100% calibration. Table 3 shows the results. If the yellow index is 1.40 or less, it can be considered that the heat discoloration resistance is good, if it is 1.20 or less, it can be considered that the heat discoloration resistance is better, and 1.10 or less If it is 1.00 or less, it can be considered that the heat discoloration resistance is even better, and it can be considered that it is particularly good.

Table 3 shows the results of developability evaluation and sensitivity evaluation.

By comparing Raw Polymers 5 to 11 with Raw Polymer 1, Raw Polymers 5 to 11 containing a structural unit derived from a long-chain alkene had significantly lower softening points and melting points than Raw Polymer 1.
A comparison of the starting polymers 5, 8 to 11 revealed that the longer the chain length of the long-chain alkene-derived structure introduced into the polymer, the lower the softening point and melting point.
Polymers P7 and P15 to P19 containing structural units derived from long-chain alkenes had a softening point of 110° C. or lower and a melting point of 140° C. or lower, indicating low softening points and low melting points.
The photosensitive resin compositions containing the polymers of Examples 1 to 13 have well-balanced alkali solubility, sensitivity and heat discoloration resistance, and the cured products of the photosensitive resin compositions prepared from the polymers of Examples 1 to 13 are The softening point was lower than 100°C. The polymer of Comparative Example 1 has a low softening point and a low melting point, and the cured product of the photosensitive resin composition prepared from the polymer of Comparative Example 1 has a softening point lower than 100°C, but the sensitivity of the photosensitive resin composition is insufficient. Was. The polymer of Comparative Example 2 had a high softening point and a high melting point, and the softening point of the cured product of the photosensitive resin composition prepared from the polymer of Comparative Example 2 was 100° C. or higher. The polymers of Comparative Examples 3 and 4 and their starting polymers have low softening points and melting points, and the softening points of the cured photosensitive resin compositions prepared from the polymers of Comparative Examples 3 and 4 are lower than 100°C. , the alkali solubility of the polymer and the photosensitive resin composition was insufficient. The polymers of Comparative Examples 5 and 6 and their starting polymers have low softening points and melting points, and the softening points of the cured photosensitive resin compositions prepared from the polymers of Comparative Examples 5 and 6 are lower than 100°C. However, the heat discoloration resistance of the photosensitive resin composition was insufficient. The photosensitive resin compositions prepared from Examples 2 to 13, which contain a structural unit derived from a long-chain alkene and contain a polymer having a structure ring-opened with a polyfunctional (meth)acrylic compound, have particularly excellent sensitivity. rice field. The photosensitive resin compositions prepared from Examples 2 to 8 containing free polyfunctional/monofunctional (meth)acrylic compounds in the polymer solution had a high film retention rate at an exposure dose of 5 mJ/cm ² , and more particularly sensitivity. was excellent.

<Production of color filter>
Colored photosensitive resin compositions were prepared by adding an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichiseika Kogyo Co., Ltd., green) to the photosensitive resin compositions prepared in Examples 1 to 13.
A green color filter could be formed by forming a film of this on a substrate, and performing exposure, alkali development, and the like.
Further, by using NX-053 (blue), NX-032 (red), etc. manufactured by the same company as the pigment dispersion instead of NX-061, a blue or red color filter could be formed.

<Preparation of black matrix>
A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichi Seika Kogyo Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 13.
A black matrix was formed by forming a film of this on a substrate, and subjecting it to exposure, alkali development, and the like.

10 substrate 11 black matrix 12 color filter 13 protective film 14 transparent electrode layer

Claims (26)

a structural unit represented by the formula (NB);
a structural unit represented by the formula (AK);
at least one structural unit selected from structural units represented by formula (1) and structural units represented by formula (2);
A polymer comprising

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms,

In formula (1), R ^p is a group having two or more (meth)acryloyl groups, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (2), R ^s is a group having one (meth)acryloyl group, and R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.
polymer. A polymer according to claim 1, wherein
further comprising a structural unit represented by formula (3),

A polymer in which R ²¹ and R ²² in formula (3) are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. 3. A polymer according to claim 1 or 2,
further comprising a structural unit represented by the formula (MA),

A polymer in which R ²¹ and R ²² in formula (MA) are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. A polymer according to any one of claims 1 to 3,
The polymer contains a structural unit represented by the formula (1),
R ^p in the formula (1) is at least one selected from the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d). ,

In formula (1b),
k is 2 or 3;
R is a hydrogen atom or a methyl group, multiple R may be the same or different,
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -ZX- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms ), and multiple X ¹ may be the same or different,
X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, Z' is -O- or -COO-),
X ² is a k+1 valent organic group having 1 to 12 carbon atoms,

In formula (1c),
k, R, X ¹ and X ² are respectively synonymous with R, k, X ¹ and X ² in formula (1b); X ¹ may be the same or different,
X ³ is a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁶ is a divalent organic group having 1 to 6 carbon atoms,

In formula (1d),
n is an integer from 2 to 5,
R is independently a hydrogen atom or a methyl group;
polymer. A polymer according to any one of claims 1 to 4,
The polymer contains a structural unit represented by the formula (2),
R ^s in the formula (2) is a group represented by formula (2a),

In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.
polymer. A polymer according to any one of claims 1 to 5,
One of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the formula (AK) is a linear or branched alkyl group having 3 or more carbon atoms, and the remaining three are hydrogen atoms is a polymer. A polymer according to any one of claims 1 to 6,
The polymer, wherein the linear or branched alkyl group having 3 or more carbon atoms is a linear alkyl group having 3 or more carbon atoms. A polymer according to any one of claims 1 to 7,
A polymer having a weight average molecular weight of 2,000 or more and 30,000 or less. 9. A polymer according to any one of claims 1 to 8,
A polymer having a softening point of 110° C. or lower. A polymer having a structure represented by formula (P2),

In formula (P2),
m is an integer from 0 to 5,
n is an integer from 1 to 6,
m+n is 2 to 6;
p, q and r denote the molar contents of A, B and C respectively, p+q+r=1, p is greater than 0, q is greater than 0, r is 0 or greater, p, q or r may be the same or different for each structural unit in n [ ],
X is hydrogen or an organic group having 1 to 30 carbon atoms,
Y is a divalent to hexavalent organic group having 1 or more and 30 or less carbon atoms derived from a compound containing a thiol group having two or more functions,
A represents a structural unit represented by formula (NB),
B contains at least one structural unit selected from structural units represented by formula (1) and structural units represented by formula (2),
C represents a structural unit represented by formula (AK),
A plurality of A's, B's, and C's may be the same or different,
D represents a structure different from the structure in [ ]n,

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (1), R ^p is a group having two or more (meth)acryloyl groups, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (2), R ^s is a group having one (meth)acryloyl group, R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms,
polymer. 11. The polymer of claim 10, comprising
The B further comprises a structural unit represented by formula (MA),

A polymer in which R ²¹ and R ²² in formula (MA) are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. 12. A polymer according to claim 10 or 11,
The polymer contains a structural unit represented by the formula (1),
R ^p in the formula (1) is at least one selected from the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d). ,

In formula (1b),
k is 2 or 3;
R is a hydrogen atom or a methyl group, multiple R may be the same or different,
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -ZX- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms ), and multiple X ¹ may be the same or different,
X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, Z' is -O- or -COO-),
X ² is a k+1 valent organic group having 1 to 12 carbon atoms,

In formula (1c),
k, R, X ¹ and X ² are respectively synonymous with R, k, X ¹ and X ² in formula (1b); X ¹ may be the same or different,
X ³ is a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁶ is a divalent organic group having 1 to 6 carbon atoms,

In formula (1d),
n is an integer from 2 to 5,
R is independently a hydrogen atom or a methyl group;
polymer. 13. A polymer according to any one of claims 10-12,
The polymer contains a structural unit represented by the formula (2),
R ^s in the formula (2) is a group represented by formula (2a),

In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.
polymer. 14. A polymer according to any one of claims 10-13,
One of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the formula (AK) is a linear or branched alkyl group having 6 to 30 carbon atoms, and the remaining three are each independently , a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. 15. A polymer according to any one of claims 10-14,
One of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the formula (AK) is a linear or branched alkyl group having 6 to 30 carbon atoms, and the remaining three are hydrogen atoms. Yes, polymer. 16. A polymer according to any one of claims 10-15,
A polymer having a weight average molecular weight of 2,000 or more and 20,000 or less. 17. A polymer according to any one of claims 10-16,
A polymer having a softening point of 110° C. or less. A polymer solution comprising a polymer according to any one of claims 1-17. 19. A polymer solution according to claim 18,
A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof. 20. A polymer solution according to claim 18 or 19,
A polymer solution used to form a color filter or black matrix. a polymer according to any one of claims 1 to 17;
and a photoradical polymerization initiator,
A photosensitive resin composition. A cured product formed from the photosensitive resin composition according to claim 21 . a structural unit represented by the formula (NB);
a structural unit represented by the formula (AK);
A polymer comprising a structural unit represented by the formula (MA),

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms,

In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms;
polymer. A polymer having a structure represented by formula (P4),

In formula (P4),
m is an integer from 0 to 5,
n is an integer from 1 to 6,
m+n is 2 to 6;
p, q and r denote the molar contents of A, B and C respectively, p+q+r=1, p is greater than 0, q is greater than 0, r is 0 or greater, p, q or r may be the same or different for each structural unit in n [ ],
X is hydrogen or an organic group having 1 to 30 carbon atoms,
Y is a divalent to hexavalent organic group having 1 or more and 30 or less carbon atoms derived from a compound containing a thiol group having two or more functions,
A represents a structural unit represented by formula (NB),
B' represents a structural unit represented by the formula (MA),
C represents a structural unit represented by formula (AK),
A plurality of A's, B's, and C's may be the same or different,
D represents a structure different from the structure in [ ]n,

In formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, a ₁ is 0, 1 or 2,

In formula (MA), R ²¹ and R ²² are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms,

In formula (AK), at least one of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a linear or branched alkyl group having 3 or more carbon atoms, and R ¹¹ , R ¹² and R ¹³ and the rest of R ¹⁴ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms,
polymer. 25. A polymer according to claim 23 or 24,
A polymer having a weight average molecular weight of 1,000 or more and 10,000 or less. 26. A polymer according to any of claims 23-25,
A polymer having a softening point of 160° C. or lower.

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