JP2022085872A - Polymer, polymer solution, photosensitive resin composition, and cured product - Google Patents

Abstract

To provide a polymer having high sensitivity and high alkali solubility.SOLUTION: A polymer has a structure represented by formula (P). (In the formula (P), m denotes an integer of 0-5, n is an integer of 1-6, m+n is 2-6, p, q and r each represent molar contents of A, B and C, with p+q+r=1, where p is greater than 0, q is greater than 0, r is equal to or greater than 0, and p, q and r may be the same or different for each of n constitutional units, X is hydrogen or a C1-30 organic group, Y is a divalent to hexavalent, C1-30 organic group induced from a di-functional or multi-functional thiol group-containing compound, A is an indene monomer-derived constitutional unit, B includes a specific constitutional unit having a (meth)acryloyl group, C denotes a divalent constitutional unit induced from a copolymerizable compound having a double bond, and D denotes a different structure from the structure within []n).SELECTED DRAWING: None

Description

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 or a solid-state image sensor usually includes a color filter or a black matrix. The color filter and the black matrix have a structure in which a structure such as a coloring pattern or a protective film is formed on the substrate. Among these structures, as a method for forming a colored pattern or a protective film, a method of forming by photolithography using a photosensitive resin composition is the mainstream. Various studies have been made on the photosensitive resin composition, for example, in Patent Document 1, an alkali having an acidic group and two or more different polymerizable unsaturated groups in at least a side chain. A photosensitive resin composition containing a soluble resin, a polymerizable compound, and a photopolymerization initiator is described. Further, in the 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 the methacrylic acid / allyl methacrylate / glycidyl adduct.

International Publication No. 2012/147706

As the photosensitive resin composition for forming a color filter or a black matrix, a resin having a property of being cured by causing a polymerization reaction by light is used. The color filter and the black matrix are produced by patterning the photosensitive resin composition by exposure and development and then curing the photosensitive resin composition. In the photosensitive resin composition, "high sensitivity" seems to be a general problem, but with the complication and widespread use of display devices and image pickup devices, a higher level of high sensitivity is required. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the higher the productivity can be improved. Further, the photosensitive resin composition is required to have excellent processability in a development process using an alkaline developer. Further, the cured product of the photosensitive resin composition is required to have high transparency.

By improving the polymer used in the photosensitive resin composition and the formulation of the composition, the present inventors have good sensitivity, high alkali solubility, and reduced yellowing. We have found that a cured product can be obtained, and have reached the present invention.

According to the present invention, a polymer having a structure represented by the formula (P) is provided.

（式（Ｐ）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（ＩＮ）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、式（２）で表される構造単位、および式（３）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、二重結合を有する共重合性化合物から誘導される２価の構造単位を表し、
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す。

(In equation (P)
m is an integer from 0 to 5 and
n is an integer of 1 to 6 and
m + n is 2 to 6,
p, q and r indicate the molar content of A, B and C, respectively, p + q + r = 1, p is greater than 0, q is greater than 0, r is greater than or equal to 0, 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 or more and 30 or less carbon atoms.
Y is an organic group having 2 to 6 valences having 1 or more and 30 or less carbon atoms derived from a bifunctional or higher functional thiol group-containing compound.
A represents a structural unit represented by the formula (IN).
B includes at least one structural unit selected from the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3).
C represents a divalent structural unit derived from a copolymerizable compound having a double bond.
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.

（式（ＩＮ）において、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または炭素数１～３０の有機基である。）

(In the formula (IN), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.)

（式（１）において、Ｒ^ｐは、２つ以上の（メタ）アクリロイル基を含む基を表す。）

(In formula (1), R ^p represents a group containing two or more (meth) acryloyl groups.)

（式（２）において、Ｒ^ｓは、１つの（メタ）アクリロイル基を含む基を表す。）

(In formula (2), R ^s represents a group containing one (meth) acryloyl group.)

（式（３）において、
Ｚは、１以上の（メタ）アクリロイル基を含む基であり、
Ｑは、水素原子、または置換もしくは未置換の炭素数１～６のアルキル基であり、
Ｘは、酸素原子、置換もしくは未置換の炭素数１～４のアルキレン基を表し、
Ｑが前記アルキル基であり、Ｘが前記アルキレン基である場合、ＱとＸが縮合して環式基を形成してもよい。））

(In equation (3)
Z is a group containing one or more (meth) acryloyl groups.
Q is a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
X represents an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. )))

Further, according to the present invention, a polymer solution containing the above polymer is provided.

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

Further, according to the present invention, a cured product of the photosensitive resin composition is provided.

According to the present invention, for use in a photosensitive resin composition having good sensitivity, high alkali solubility, excellent developability, reduced yellowing, and thus high heat-resistant discoloration. Polymers as resin materials are provided.

It is a figure (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and / or a solid-state image sensor.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate. All drawings are for illustration purposes only. The shape and dimensional ratio of each member in the drawing do not necessarily correspond to the actual article. In the present specification, the notation "a to b" in the description of the numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less".

In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "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) acrylic" herein represents a concept that includes both acrylic and methacrylic. The same applies to similar notations such as "(meth) acrylate".
In particular, the "(meth) acryloyl group" in the present specification means an acryloyl group represented by -C (= O) -CH = CH ₂ and -C (= O) -C (CH ₃ ) = CH ₂ . Represents a concept including a methacryloyl group represented by.

[Polymer P]
(First embodiment)
The polymer of the present embodiment (referred to as “polymer P” in the present specification) has a structure represented by the following general formula (P). The polymer P is a 2- to hexavalent organic group having 1 to 30 carbon atoms derived from a bifunctional or higher thiol group-containing compound represented by “Y” in the formula, and typically has a structural unit A and a structure. It has a structure in which polymer chains composed of the unit B are bonded.

一般式（Ｐ）において、
ｍは、好ましくは、０または１であり、より好ましくは、０である。
ｎは、１～６の整数であり、好ましくは、３～６である。
ただし、ｎ＋ｍは、２～６であり、好ましくは、３～６である。
ｐは０より大きく、好ましくは０．２５～０．７５である。
ｑは０より大きく、好ましくは０．２５～０．７５である。
ｒは０以上であり、好ましくは０～０．５、より好ましくは０～０．３、特に好ましくは０～０．１である。
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い。
Ｘは、水素または炭素数１以上３０以下の有機基である。
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（ｉ）であり、チオール基から誘導されるチオエーテル基を介して［ ］ｎ内の構造単位および［ ］ｍ内の構造単位と結合する。
Ａは、式（ＩＮ）で表される構造単位を表す。
Ｂは、式（１）で表される構造単位、式（２）で表される構造単位、および式（３）で表される構造単位から選択される少なくとも１つの構造単位を含む。
Ｃは、二重結合を有する共重合性化合物から誘導される２価の構造単位を含む。
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い。
なお、一般式（Ｐ）において、Ａ、ＢおよびＣの結合順序は特に限定されず、Ａ、ＢおよびＣのいずれがＹと結合していてもよい。
Ｄは、［ ］ｎ内の構造とは異なる構造を表し、Ｄは、Ａ、Ｂ、Ｃのいずれかを含んでもよい。

In the general formula (P)
m is preferably 0 or 1, and more preferably 0.
n is an integer of 1 to 6, preferably 3 to 6.
However, n + m is 2 to 6, preferably 3 to 6.
p is greater than 0, preferably 0.25 to 0.75.
q is greater than 0, preferably 0.25 to 0.75.
r is 0 or more, preferably 0 to 0.5, more preferably 0 to 0.3, and particularly preferably 0 to 0.1.
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 or more and 30 or less carbon atoms.
Y is an organic group (i) having 2 to 6 valences of 1 to 30 carbon atoms derived from a bifunctional or higher functional thiol group-containing compound, and is contained in [] n via a thioether group derived from the thiol group. Combines with the structural units of and the structural units within [] m.
A represents a structural unit represented by the formula (IN).
B includes at least one structural unit selected from the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3).
C comprises a divalent structural unit derived from a copolymer having a double bond.
A plurality of A's, B's, and C's may be the same or different.
In the general formula (P), the binding order of A, B, and C is not particularly limited, and any of A, B, and C may be bound to Y.
D represents a structure different from the structure in [] n, and D may include any of A, B, and C.

式（ＩＮ）において、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または炭素数１～３０の有機基である。

In formula (IN), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.

式（１）において、Ｒ^ｐは、２つ以上の（メタ）アクリロイル基を含む基を表す。好ましくは、Ｒ^ｐは、２～９の（メタ）アクリロイル基を含む基であり、より好ましくは、３～６の（メタ）アクリロイル基を含む基である。（メタ）アクリロイル基の数を最適にすることで、得られるポリマーＰのフォトリソグラフィー法における感度を高めることができる。また感度と現像性とをより高度なバランスで両立することができ、さらに耐熱性を改善することができる。

In formula (1), R ^p represents a group containing two or more (meth) acryloyl groups. Preferably, R ^p is a group containing 2 to 9 (meth) acryloyl groups, and more preferably a group containing 3 to 6 (meth) acryloyl groups. By optimizing the number of (meth) acryloyl groups, the sensitivity of the obtained polymer P in the photolithography method can be increased. In addition, sensitivity and developability can be achieved at a higher balance, and heat resistance can be further improved.

式（２）において、Ｒ^ｓは、１つの（メタ）アクリロイル基を含む基を表す。

In formula (2), R ^s represents a group containing one (meth) acryloyl group.

式（３）において、
Ｚは、１以上の（メタ）アクリロイル基を含む基である。
Ｑは、水素原子、または置換もしくは未置換の炭素数１～６のアルキル基である。このアルキル基としては、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基を挙げることができる。置換された炭素数１～６のアルキル基の置換基としては、ハロゲン原子、水酸基、カルボキシル基、アミノ基、シアノ基、メルカプト基等を挙げることができる。
Ｘは、酸素原子、置換もしくは未置換の炭素数１～４のアルキレン基を表す。Ｘを構成するアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基を挙げることができる。置換された炭素数１～４のアルレン基の置換基としては、ハロゲン原子、水酸基、カルボキシル基、アミノ基、シアノ基、メルカプト基等を挙げることができる。
Ｑが前記アルキル基であり、Ｘが前記アルキレン基である場合、Ｑのアルキル基とＸのアルキレン基の何れかの炭素原子とが結合して環を形成してもよい。環構造としては、シクロプロパン環、シクロブタン環、シクロペンタン環、シクロヘキサン環、デカリン環、ベンゼン環、ナフタレン環等を挙げることができる。
式（３）において、Ｘが炭素数１～４のアルキレンであり、かつＺが（メタ）アクリロイルオキシ基である態様、またはＸが酸素原子であり、かつＺが（メタ）アクリロイル基である態様が好ましく用いられる。

In equation (3)
Z is a group containing one or more (meth) acryloyl groups.
Q is a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Examples of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group and the like.
X represents an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituted allene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group and the like.
When Q is the alkyl group and X is the alkylene group, the alkyl group of Q and the carbon atom of any of the alkylene groups of X may be bonded to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, a naphthalene ring and the like.
In formula (3), X is an alkylene having 1 to 4 carbon atoms and Z is a (meth) acryloyloxy group, or X is an oxygen atom and Z is a (meth) acryloyl group. Is preferably used.

The polymer P of the present embodiment is typical of an organic group having 2 to 6 valences having 1 or more and 30 or less carbon atoms derived from a bifunctional or higher functional thiol group-containing compound represented by “Y” in the formula (P). Has a structure in which a polymer chain composed of structural unit A and structural unit B is bonded. By having the thioether group, the polymer P has excellent sensitivity in the photolithography method and has higher alkali solubility, and thus can provide a cured resin product having better developability.

The polymer P of the present embodiment also has, as the structural unit B, a structural unit represented by the general formula (1), a structural unit represented by the general formula (2), and a structural unit represented by the general formula (3). Includes at least one of. In other words, the polymer P comprises a structural unit having at least one (meth) acryloyl group as an essential component. As a result, the photosensitive resin composition containing the polymer P has excellent sensitivity when subjected to a photolithography method. It is considered that this is because the curing reaction (polymerization reaction) is promoted by the (meth) acryloyl group contained in the structural units represented by the general formulas (1) to (3).

Further, the polymer P contains a structural unit derived from indene represented by the general formula (IN) as the structural unit A. This structural unit (IN) is chemically robust. Therefore, the polymer P containing this as a structural unit has a small weight loss and is stable when subjected to heat treatment. Therefore, the photosensitive resin composition containing the polymer P can be suitably used for producing a film or a filter for use in a liquid crystal display device or a solid-state image sensor that requires heat resistance.

In one embodiment, the polymer P may contain the structural unit represented by the formula (4) in addition to the structural unit represented by the above formulas (1) to (3) as the structural unit B. By including the structural unit represented by the formula (4), the polymer P has high alkali solubility. As a result, the photosensitive resin composition containing such a polymer P has excellent developability when subjected to a photolithography treatment using an alkaline aqueous solution as a developing solution.

In one embodiment, the polymer P may contain a structural unit C derived from a monomer polymerizable with indene and maleic anhydride. Structural unit C is, for example, a substituted or unsubstituted structural unit derived from norbornene, styrene, maleimide, or norbornadiene. Examples of the substituent that these monomers can have include an alkyl group and an aryl group. More specifically, examples of the substituted maleimide include cyclohexylmaleimide and phenylmaleimide. Examples of the substituted styrene include methylstyrene and vinyltoluene.

Above all, the structural unit C is preferably a structural unit represented by the general formula (11) (a divalent structural unit derived from substituted or unsubstituted norbornen) and a structural unit represented by the general formula (12) (12). A divalent structural unit derived from a substituted or unsubstituted maleimide), a structural unit represented by the general formula (13) (a divalent structural unit derived from a substituted or unsubstituted styrene), or a general formula (a divalent structural unit). A structural unit represented by 14) (a divalent structural unit derived from a substituted or unsubstituted norbornadiene) is included.

In the general formula (11), R ¹ to R ⁴ independently represent a hydrogen atom, an alkyl group or an aryl group, and a ₁ is 0 or 1. In the general formula (12), R ³ represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (13), R ⁴ to R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (14), R ⁷ to R ¹⁰ independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

In the structural unit represented by the general formula (IN) constituting the polymer P, the organic group having 1 to 30 carbon atoms which can constitute R ¹ and R ² is a substituted or unsubstituted, linear or branched chain. Examples thereof include an alkyl having 1 to 30 carbon atoms, and more specifically, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group, a heterocyclic group and a carboxyl group. The group etc. can be mentioned.

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

Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group and the like.
Examples of the alkynyl group include an ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.

Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaline group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group and a neopentyloxy group. , N-hexyloxy group and the like.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

In the structural unit represented by the general formula (IN), hydrogen or an alkyl group is preferable as R ¹ and R ² , and hydrogen is more preferable.
The hydrogen atoms in the organic groups having 1 to 30 carbon atoms of R ¹ and R ² may be substituted with arbitrary atomic groups. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, an alkyl fluoride group or the like may be selected as the organic group having 1 to 30 carbon atoms of R ¹ and R ² .

The proportion of the structural unit represented by the general formula (IN) in the total structural unit of the polymer P is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%. be.

In the structural unit represented by the general formula (1) that can constitute the polymer P, R ^p is a group containing two or more (meth) acryloyl groups, preferably 2 to 6 (meth) acryloyl groups. It is a group containing, and more preferably a group containing 3 to 5 (meth) acryloyl groups. By optimizing the number of (meth) acryloyl groups contained in R ^p , the sensitivity of the polymer P containing them in the exposure treatment can be further increased. In addition, it becomes easier to achieve a higher degree of compatibility between the sensitivity of the polymer P and the alkali solubility. Furthermore, the heat resistance of the polymer P can be improved.

R ^p in the general formula (1) is preferably a group represented by the general formula (1b), a group represented by the general formula (1c), or a group represented by the general formula (1d). Includes at least one selected from. With such a group, it tends to be easy to obtain the above-mentioned various effects.

In equation (1b),
k is 2 or 3
R is a hydrogen atom or a methyl group, and multiple Rs 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 —Z—X— (Z is —O— or —OCO—, and X is an alkylene group having 1 to 6 carbon atoms. ), And multiple ^X1s 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, and 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 because of further improvement in sensitivity (easiness of polymerization) and the like.
Although k may be 2 or 3, it is preferably 3 from the viewpoint of further improving the availability of raw materials and the 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, and further preferably −CH. _2- (Methylene group).

When X ¹ is a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), X has 1 to 6 carbon atoms. The alkylene group may be linear 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 further preferably _{−CH2 -} CH2-(. Ethylene group) or -CH ₂ -CH (CH ₃ )-.

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

Examples of the k + 1-valent organic group having 1 to 12 carbon atoms of X ² include any group obtained by removing k + 1 hydrogen atoms from any organic compound. The "arbitrary organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and 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. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon.
In another aspect, X ² may be a group comprising a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure, a group containing a heterocyclic structure (for example, an isocyanuric acid structure), and the like.

In equation (1c),
k, R, X ¹ and X ² are synonymous with R, k, X ¹ and X ² in the equation (1b), respectively, and a plurality of Rs may be the same as or different from each other, and a plurality of Rs may be different from each other. X ^1s may be the same or different from each other
X3 is a divalent organic group having 1 to ⁶ carbon atoms.
X ⁴ and X ⁵ are independently single-bonded or divalent organic groups having 1 to 6 carbon atoms, respectively.
X ⁶ is a divalent organic group having 1 to 6 carbon atoms.

Specific embodiments, preferred embodiments, and the like of R, k, X ¹ and X ² are the same as those described in the general formula (1b).
Examples of the divalent organic group having 1 to ⁶ carbon atoms of X3 and X6 include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to ⁶ carbon atoms. Can be done. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon.
Examples of the divalent organic group having 1 to ⁶ carbon atoms of X4 and ^X5 include a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

In formula (1d), n is an integer of 2 to 5, preferably 2 or 3.
The specific embodiment and the preferred embodiment of R are the same as those described in the general formula (1b).

When the polymer P contains the structural units represented by the general formula (1), the ratio of the structural units represented by the general formula (1) to the total structural units of the polymer P is preferably 3 to 40 mol%. , More preferably 3 to 30 mol%.

In the structural unit represented by the general formula (2) that can constitute the polymer ^P , RS is a group containing only one (meth) acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while an attempt is made to improve the developability. In some cases, curing tends to be insufficient, so that the polymer P preferably contains one or both of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). As a result, both sensitivity and developability can be achieved in a good balance.

^RS is, for example, a group represented by the following formula (2a).

In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.
The total number of carbon atoms of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.
The total number of carbon atoms of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
As the divalent organic group of 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.

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

The divalent organic group (eg, alkylene group) of X ¹⁰ may be substituted with any substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group and the like.
Further, the divalent organic group of X ¹⁰ may be any group other than the alkylene group. For example, it may be a divalent group composed of 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 contains the structural unit represented by the general formula (2), the ratio of the structural unit represented by the general formula (2) to the total structural unit of the polymer P is preferably 5 to 40 mol%. More preferably, it is 10 to 30 mol%.

Further, when the polymer P contains both the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), it is represented by the general formula (1) in the polymer P. The total content of the structural unit and the structural unit represented by the general formula (2) is preferably 5 to 60 mol%, more preferably 10 to 50 mol% based on all the structural units constituting the polymer P. , More preferably 10-40 mol%.

When the polymer P contains the structural units represented by the general formula (3), the ratio of the structural units represented by the general formula (3) to the total structural units of the polymer P is preferably 0.25 to 17. Mol%, more preferably. It is 0.5 to 12 mol%.

In the general formula (P), X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms. The organic group having 1 or more and 30 or less carbon atoms is the same as the organic group having 1 or more and 30 or less carbon atoms constituting R ¹ and R ² in the above formula (IN).

In the general formula (P), Y is an organic group (i) having 2 to 6 valences having 1 or more and 30 or less carbon atoms derived from a bifunctional or higher thiol group-containing compound. In this embodiment, the number of functional groups is the number of thiol groups. That is, the thiol group-containing compound contains two or more thiol groups, and the organic group (i) is a structural unit within [] n and [] n via 1 to 6 thioether groups derived from the thiol group. ] Combines with structural units within m. The organic group (i) may have a thiol group that does not participate in the bond with the structural unit in [] n and the structural unit in [] m, and the polymer P may have a number of n + m (number of bonds). Can be obtained as a mixture of the respective resins of 2 to 6.
The organic group (i) having 1 or more and 30 or less carbon atoms is bifunctional or higher, preferably trifunctional or higher. The upper limit is not particularly limited, but is 6 functional or less.
The valence of the organic group (i) having 1 or more and 30 or less carbon atoms is 2 to 6 valences, preferably 2 to 6 valences, from the viewpoint of the effect of the present invention.

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

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group and a heptyl group. , Octyl group, nonyl group, and decyl group. Examples of the alkenyl group include an allyl group, a pentaenyl group, and a vinyl group.

Examples of the alkynyl group include an ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaline group include a tolyl group and a xylyl group.

Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group and a neopentyloxy group. , And n-hexyloxy groups.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

The polymer P is represented by the structural unit represented by the formula (5) and the formula (6) as a structural unit containing any one or two of the above general formulas (1), (2) and (3). Can include at least one selected from the structural units represented by the formula (8), the structural units represented by the formula (8), and the structural units represented by the formula (9). By including such a structural unit, the polymer P may have high alkali solubility. In the formulas (5), (6), (8), and (9), R ^p , R ^s , Q, X, and Z are synonymous with those in the formulas (1) to (3).

When the polymer P contains the structural units represented by the general formula (5), the ratio of the structural units represented by the general formula (5) to the total structural units of the polymer P is preferably 0.5 to 25 mol. %, More preferably 1-18 mol%.

When the polymer P contains the structural units represented by the general formula (6), the ratio of the structural units represented by the general formula (6) to the total structural units of the polymer P is preferably 3 to 35 mol%. More preferably, it is 5 to 25 mol%.

When the polymer P contains the structural units represented by the general formula (8), the ratio of the structural units represented by the general formula (8) to the total structural units of the polymer P is preferably 0.25 to 17 mol. %, More preferably 0.5-12 mol%.

When the polymer P contains the structural units represented by the general formula (9), the ratio of the structural units represented by the general formula (9) to the total structural units of the polymer P is preferably 0.5 to 35 mol. %, More preferably 2 to 25 mol%.

In one embodiment, the polymer P may comprise a structural unit represented by formula (10). By including the structural unit represented by the formula (10), the polymer P has excellent alkali solubility. As a result, the photosensitive resin composition containing the polymer P has an excellent balance between sensitivity and developability even when subjected to a photolithography process using a strong basic developer.

When the polymer P contains the structural units represented by the general formula (10), the ratio of the structural units represented by the general formula (10) to the total structural units of the polymer P is preferably 1 to 15 mol%. More preferably, it is 2 to 10 mol%.

In one embodiment, the polymer P may comprise a structural unit represented by formula (MA). The structural unit represented by the general formula (MA) is ring-opened with an alkaline developer to generate two carboxyl groups. Therefore, the polymer P containing such a structural unit has excellent developability. When the polymer P contains a structural unit represented by the general formula (MA), the structural unit represented by the general formula (MA) in all the structural units of the polymer P is preferably 1 to 35 mol%. More preferably, it is 2 to 30 mol%.

In the general formula (P), the divalent to hexavalent organic group represented by Y is derived from a bifunctional or higher functional thiol group-containing compound. Examples of the bifunctional or higher thiol group-containing compound capable of inducing Y include compounds represented by the following chemical formulas (s-1) to (s-21).

As the bifunctional or higher functional thiol group-containing compound, one kind may be used alone, or two or more kinds may be used in combination. Above all, it is preferable to use a 3- to 6-functional (3 to 6-valent) thiol group-containing compound having 3 to 6 thiol groups in one molecule because the reactivity with other monomers is excellent.
In the present embodiment, the bifunctional or higher functional thiol group-containing compound has the chemical formulas (s-1) to (s-3), among the compounds represented by the chemical formulas (s-1) to (s-21). It is more preferable to contain the compounds represented by (s-5) and (s-8) to (s-10), and the chemical formulas (s-1) to (s-3), (s-5) and (s) are more preferable. It is particularly preferable to include the compound represented by -9).
Y, which is the organic group (i) having 1 to 6 valences of 1 to 30 carbon atoms, is a thioether group derived from the thiol group of these thiol group-containing compounds (-S- * (* is a bond)). Combines with structural units in [] n and / or structural units in [] m via. The organic group (i) may have a thiol group that does not participate in the bond with the structural unit in [] n and the structural unit in [] m.

When Y in the polymer P of the present embodiment is an organic group derived from a tetrafunctional (tetravalent) thiol group-containing compound represented by the above chemical formula (s-2), the polymer P may be, for example, It may have a structure as represented by the following general formula (I).

The structure of the general formula (I) corresponds to the case where m is 0 and n is 4 in the general formula (P). In the general formula (I), A, B, C, X, p, q and r are synonymous with the general formula (P). A, B, C, X, p, q and r contained in the structural units in the four [] may be the same or different.

In the general 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 the thioether group. Further, in the general formula (I), an example in which the compound represented by the chemical formula (s-2) is bonded to the structural unit in four [] via a thioether group derived from the four mercapto groups. As shown by, a structure in which 1 to 3 structural units in [] are bonded to a thioether group derived from four mercapto groups, and an organic group different from the structural unit in [] is bonded to the remaining thioether groups. It may be. In the present 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 the polymer P is, for example, 5,000 to 80,000, preferably 6,000 to 75,000, more preferably 7,000 to 70,000, still more preferably 8,000 to 60, It is 000. By appropriately adjusting the weight average molecular weight, the sensitivity and the solubility in an alkaline developer can be adjusted.

The dispersity of the polymer P (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3. It is 0. By appropriately adjusting the dispersity, 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 is preferably 150 to 250 ° C, more preferably 170 to 230 ° C. The polymer P has a relatively high glass transition temperature mainly by containing a structural unit represented by the general formula (IN). This is preferable in that a pattern formed on a substrate can be stably present in the manufacture of a liquid crystal display device or a solid-state image sensor. The glass transition temperature can be determined by, for example, differential thermal analysis (DTA).

The acid value of the polymer P is 70 mgKOH / g or more and 150 mgKOH / g or less, preferably 80 mgKOH / g or more and 140 mgKOH / g or less. The double bond equivalent of the polymer P is 100 g / mol or more and 700 g / mol or less, preferably 200 g / mol or more and 600 g / mol or less, and more preferably 200 g / mol or more and 430 g / mol or less.
When the acid value of the polymer P is 70 mgKOH / g or more, good developability can be obtained. Further, when the double bond equivalent is 700 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P can be increased.

If the acid value of the polymer P is too high, the exposed portion is likely to dissolve during development with an alkaline developer, the amount of exposure required for photocuring increases, and the pattern shape becomes insufficient. There is a concern about it. Therefore, in the present embodiment, the upper limit of the acid value is set to 150 mgKOH / g.
Further, if the double bond equivalent of the polymer P is too small (that is, the density of the double bonds in the polymer is too large), it becomes difficult to dissolve the unexposed part and the low-exposed part during development with an alkaline developer. There is a tendency, and a residual film tends to be generated during development. Further, if the double bond equivalent is too small, the molecular weight is excessively increased due to cross-linking, and there is a concern that the solubility is excessively lowered. Therefore, in the present embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

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

The acid value and double bond equivalent of the polymer P can be determined by spectral measurement or the like. For example, it can be obtained by the following procedure (more specifically, refer to the examples).
(1) From the ¹ H-NMR chart of the polymer, the area (integrated value) of the peak corresponding to the hydrogen atom of the carboxy group and the hydrogen atom in the vicinity of the polymerizable carbon-carbon double bond is obtained.
(2) For the area obtained in (1), the amount of carboxy group and the amount of carbon-carbon double bond are obtained from the area of the peak derived from the standard substance.
(3) The amount of the carboxy group obtained in (2) is converted into an acid value (mgKOH / g). Further, 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 are the ratio of the structural units introduced into the polymer P, particularly the polymerizable property of the (meth) acryloyl group contained in the structural units represented by the formulas (1) to (3). By properly designing the number of carbon-carbon double bonds, it can be adjusted to the desired value.

The content (ratio) of each structural unit contained in the polymer P of the present embodiment is the amount of raw material charged (molar amount) at the time of polymer synthesis, the amount of raw material remaining after synthesis, and the peak area of various spectra (for example,). ¹ It can be estimated / calculated from (peak area of 1 H-NMR) and the like.

(Second embodiment)
In the second embodiment, the polymer P is obtained by polymerizing a monomer composition containing an inden monomer represented by the following formula (INm) and maleic anhydride in the presence of a bifunctional or higher thiol group-containing compound. , A raw material polymer is prepared, and then the raw material polymer can be reacted with a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound in the presence of a basic catalyst to obtain a polymer. In formula (INm), R ¹ and R ² are synonymous with those in formula (IN).

The polymer P obtained by the above method is derived from the structural unit represented by the above formula (IN) derived from the inden monomer, maleic anhydride and a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound. The structural unit represented by the above formula (5) and / or the structural unit represented by the formula (6) is included.

(Third embodiment)
In the third embodiment, the polymer P is obtained by polymerizing a monomer composition containing the monomer represented by the above formula (INm) and maleic anhydride by polymerizing in the presence of a bifunctional or higher thiol group-containing compound. A raw material polymer is prepared, and then the raw material polymer is reacted with a polyfunctional (meth) acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to prepare a polymer precursor, and then this It can be a polymer obtained by treating the polymer precursor with water in the presence of a basic catalyst.

The polymer P obtained by the above method is derived from the structural unit represented by the above formula (IN) derived from the inden monomer, maleic anhydride and a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound. The structural unit represented by the above formula (5) and / or the structural unit represented by the formula (6) and the structure represented by the above formula (10) derived from the reaction between maleic anhydride and water. Includes units.

(Fourth Embodiment)
In the fourth embodiment, the polymer P is obtained by polymerizing a monomer composition containing the monomer represented by the above formula (INm) and maleic anhydride by polymerizing in the presence of a bifunctional or higher thiol group-containing compound. A raw material polymer is prepared, and then the raw material polymer is reacted with a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound in the presence of a basic catalyst to prepare a polymer precursor. The polymer precursor can then be a polymer obtained by reacting with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst.

The polymer P obtained by the above method is derived from the structural unit represented by the above formula (IN) derived from the inden monomer, maleic anhydride and a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound. The structural unit represented by the above formula (5) and / or the structural unit represented by the formula (6), and the maleic anhydride and the polyfunctional (meth) acrylic compound and / or the monofunctional (meth) acrylic compound. It contains a structural unit represented by the above formula (7) and / or a structural unit represented by the above formula (8) derived from the epoxy group-containing (meth) acrylic compound.

[Manufacturing method of polymer P]
The method for producing the polymer P of the present embodiment will be described by exemplifying the method for producing the polymer P in the second, third and fourth embodiments.

(Method for producing polymer P according to the second embodiment)
The polymer P of the second embodiment containing the structural unit represented by the above formula (5) and / or the structural unit represented by the above formula (6) is a polymer P.
Step (I): The structural unit represented by the general formula (IN), the structural unit represented by the general formula (MA), and the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms. Step (II): The raw material polymer obtained in step (I) and a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter, "polyfunctional (meth)". ) Acrylic compound ”) and / or a compound having a hydroxyl group and one (meth) acryloyl group (hereinafter referred to as“ monofunctional (meth) acrylic compound ”) are reacted in the presence of a basic catalyst. The structural unit represented by the general formula (IN), the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms, and the structural unit represented by the general formula (5) and / or general. It can be produced by a step of preparing a polymer P containing a structural unit represented by the formula (6), and optionally further containing a structural unit represented by the general formula (MA).

When both the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound are used in the step (II), the polyfunctional (meth) acrylic compound is first reacted with the raw material polymer, and the resulting reaction mixture is combined with the polyfunctional (meth) acrylic compound. It is preferable to react with a monofunctional (meth) acrylic compound.

(Method for producing polymer P according to the third embodiment)
The polymer P of the third embodiment, which comprises the structural unit represented by the above formula (5) and / or the structural unit represented by the above formula (6), and the structural unit represented by the above formula (10). ,
Step (I): The structural unit represented by the general formula (IN), the structural unit represented by the general formula (MA), and the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms. Step (II): The raw material polymer obtained in step (I) and a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter, "polyfunctional (meth)". ) Acrylic compound ”) and / or a compound having a hydroxyl group and one (meth) acryloyl group (hereinafter referred to as“ monofunctional (meth) acrylic compound ”) are reacted in the presence of a basic catalyst. The structural unit represented by the general formula (IN), the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms, the structural unit represented by the general formula (5), and / or the general formula. A step of preparing a polymer precursor containing the structural unit represented by (6) and the structural unit represented by the general formula (MA).
Step (IIIa): By treating the polymer precursor obtained in Step (II) with water in the presence of a base catalyst, the structural unit represented by the general formula (IN) has 1 to 6 valent carbon atoms. The organic group (i) of 1 or more and 30 or less, the structural unit represented by the general formula (5) and / or the structural unit represented by the general formula (6), and the structural unit represented by the formula (10) are included, and in some cases more general. It can be produced by the step of preparing the polymer P containing the structural unit represented by the formula (MA).

When both the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound are used in the step (II), the polyfunctional (meth) acrylic compound is first reacted with the raw material polymer, and the resulting reaction mixture is combined with the polyfunctional (meth) acrylic compound. It is preferable to react with a monofunctional (meth) acrylic compound.

(Method for producing polymer P according to the fourth embodiment)
The structural unit represented by the above formula (5) and / or the structural unit represented by the above formula (6), and the structural unit represented by the above formula (8) and / or represented by the above formula (9). The polymer P of the fourth embodiment including the structural unit is
Step (I): The structural unit represented by the general formula (IN), the structural unit represented by the general formula (MA), and the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms. The process of preparing the raw material polymer, including
Step (II): The raw material polymer obtained in Step (I), a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as "polyfunctional (meth) acrylic compound"), and /. Alternatively, a compound having a hydroxyl group and one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylic compound”) is reacted in the presence of a basic catalyst and represented by the general formula (IN). The organic group (i) having 1 to 6 valences of 1 to 30 carbon atoms, the structural unit represented by the general formula (5) and / or the structural unit represented by the general formula (6). A step of preparing a polymer precursor containing a structural unit represented by the general formula (MA), and step (IIIb): the polymer precursor obtained in step (II) is contained in an epoxy group in the presence of a catalyst. (Meta) A structural unit represented by the general formula (IN) after reacting with an acrylic compound, and the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms is represented by the general formula (5). Structural unit and / or structural unit represented by the general formula (6), structural unit represented by the general formula (7) and / or structural unit represented by the general formula (8), and in some cases, the general formula (MA). It can be produced by the step of preparing the polymer P containing the structural unit represented by.

When both the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound are used in the step (II), the polyfunctional (meth) acrylic compound is first reacted with the raw material polymer, and the resulting reaction mixture is combined with the polyfunctional (meth) acrylic compound. It is preferable to react with a monofunctional (meth) acrylic compound.

Hereinafter, each step will be described.
(Step (I))
In the step (I), the structural unit represented by the general formula (IN), the structural unit represented by the general formula (MA), and the organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms. In the step of preparing the raw material polymer containing the above, a monomer composition containing an inden monomer represented by the general formula (INm) and maleic anhydride is polymerized in the presence of the bifunctional or higher functional group-containing compound. It can be carried out by (addition polymerization). The definitions of R ¹ and R ² of the general formula (INm) are the same as those of the general formula (IN). The same applies to the preferred embodiment.

The monomer composition may contain other monomers in addition to the above-mentioned monomers. The other monomer is not particularly limited as long as it is a copolymerizable compound having a double bond, and examples thereof include substituted or unsubstituted norbornene, maleimide, styrene, acenaphtylene, norbornadiene, dihydrofuran, and terpene compounds (for example). , Pinen, limonene, etc.), linear alkene (eg, pentene, etc.), cyclic alkene (cyclohexene, etc.), cyclododecatorien, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.) Etc.), coumarin, (meth) acrylate compounds (eg, methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ether (eg, 2-hydroxyethyl vinyl ether, etc.) and the like. In step (I), the monomer represented by the general formula (INm), maleic anhydride, and if necessary, other monomers are polymerized in the presence of the bifunctional or higher functional thiol group-containing compound. (Addition polymerization) can be performed.

Examples of the bifunctional or higher functional thiol group-containing compound include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-21). As the bifunctional or higher functional thiol group-containing compound, one kind may be used alone, or two or more kinds may be used in combination.

The method of polymerization is not limited, but radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, or the like can be used.
Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile) (ABCN). Can be mentioned.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), methyl ethyl ketone peroxide (MEKP) and the like.
As the polymerization initiator, only one kind may be used, or two or more kinds may be used in combination.

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

In the synthesis of the raw material polymer, the monomer represented by the formula (INm), maleic anhydride and the polymerization initiator are dissolved in a solvent and charged into a reaction vessel, and then heated to obtain the bifunctional or higher functional thiol group-containing compound. It is carried out by advancing the addition polymerization while dropping. The heating temperature is, for example, 50 to 80 ° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the formula (INm) to maleic anhydride when charged in the reaction vessel is preferably 0.5: 1 to 1: 0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1: 1.
Further, from the viewpoint of controlling the thioether group content in the raw material polymer and the molecular weight of the raw material polymer, the total molar amount of the monomer represented by the formula (INm) and maleic anhydride charged when charged in the reaction vessel is increased. The amount of the bifunctional or higher thiol group-containing compound charged is preferably 0.5 to 10 mol%, particularly preferably 1 to 8 mol%, and further preferably 2 to 6 mol%. ..
By such a step, a "raw material polymer" can be obtained.
The raw material polymer may be any of a random copolymer, an alternate copolymer, a block copolymer, a periodic copolymer and the like. It is typically a random copolymer or an alternating copolymer. In addition, maleic anhydride is generally known as a monomer having strong alternating copolymerizability.

After synthesizing the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiator may be performed.
Specifically, the organic phase containing the synthesized raw material polymer and the low molecular weight component is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, this solution is mixed with a poor solvent such as methanol to precipitate the monomer. By filtering this precipitate and drying it, the purity of the raw material polymer can be increased.

(Step (II))
The formula contained in the raw material polymer is obtained by reacting the raw material polymer obtained in the step (I) with the polyfunctional (meth) acrylic compound and / or the monofunctional (meth) acrylic compound in the presence of a basic catalyst. A part of the structural unit represented by (MA) is opened, and the structural unit represented by the formula (5) and / or the structural unit represented by the formula (6) is formed, and the general formula (IN) is formed. The structural unit represented by the above organic group (i) having 1 to 6 valent carbon atoms of 1 or more and 30 or less, and the structural unit represented by the general formula (5) and / or represented by the general formula (6). A polymer P containing a structural unit and optionally a structural unit represented by the formula (MA) is obtained.

More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. 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), and tetrahydrofuran (THF) can be used. However, various organic solvents used in the synthesis of organic compounds and polymers can be used.

To obtain the polymer P containing both the structural unit represented by the general formula (IN), the structural unit represented by the general formula (5), and the structural unit represented by the general formula (5), then, the above Add a polyfunctional (meth) acrylic compound to the solution of. In addition, a basic catalyst is added. Then, the solutions are appropriately mixed to form a uniform solution, in which at least the structural unit of the general formula (IN) and the structural unit of the general formula (5) have 1 to 1 to the organic group (i) having 1 or more and 30 or less carbon atoms. A polymer containing a structure bonded via 6 thioether groups is obtained (step (II-i)).

Examples of the polyfunctional (meth) acrylic compound that can be used here include a compound represented by the formula (1 bm), a compound represented by the formula (1 cm), and a compound represented by the formula (1 dm). The compounds to be used are mentioned. The definitions and specific embodiments of k, R, X1, X1'and X2 in the formula (1b-m) are the same as those in the above formula (1b). Further, the definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in the formula (1c-m) are the same as those in the above formula (1c). N and R in the formula (1dm) are the same as those in the above formula (1d).

Next, by reacting the polymer obtained in step (II-i) with a monofunctional (meth) acrylic compound in the presence of a basic catalyst, at least the structural unit of the general formula (IN), the general formula (5). ) And the structural unit of the general formula (6) are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups to obtain a polymer. Yes (step (II-ii)).

As the basic catalyst, an amine compound or a nitrogen-containing heterocyclic compound known in the field of organic synthesis can be appropriately used. For example, an amine compound such as triethylamine, pyridine, or 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 raw material polymer. It should be noted that if an excessive amount of the basic catalyst is used, the amount of acid required for neutralization increases, which may complicate purification.

By heating the above solution at preferably 60 to 80 ° C. for about 3 to 9 hours, ring-opening of the structural unit of the general formula (MA) contained in the raw material polymer / formation of the structural unit of the general formula (5). Is done.

For example, by adding a monofunctional (meth) acrylic compound having a hydroxy group to the reaction system during the above heating, the structural unit represented by the above-mentioned general formula (6) is added to the polymer P. Can be introduced.

From the viewpoint of steric hindrance of the reaction, the monofunctional (meth) acrylic compound having a hydroxy group tends to react more easily with the raw material polymer than the polyfunctional (meth) acrylic compound having a hydroxy group. Therefore, when the structural unit represented by the above-mentioned general formula (6) is introduced into the polymer P, the monofunctional (meth) acrylic compound having a hydroxy group is not charged into the reaction system from the beginning, and the reaction system is not charged. It is preferable to add to the inside.
Examples of the monofunctional (meth) acrylic compound having a hydroxy group include compounds represented by the following general formula (2am).
In the general formula (2am), the definitions of X ¹⁰ and R are the same as those in the general formula (2a).

Specific examples of the compound represented by the general formula (2am) include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, and 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. be able to.

The structural unit represented by the formula (IN), the organic group (i) having 1 to 6 valences of 1 to 30 carbon atoms, and the structural unit represented by the formula (1) and the formula (2). When obtaining a polymer containing any one of the structural units, only one of the steps (II-i) and the step (II-ii) may be carried out after the step (I).
(Step (IIIa))
When the step (IIIa) is carried out, a step of treating the polymer obtained in the step (II) with water in the presence of a basic catalyst is used. By the step (IIIa), the structural unit represented by the general formula (MA) contained in the polymer obtained in the step (II) is opened, and the structural unit represented by the general formula (10) is formed. The structural unit represented by the general formula (IN), the structural unit represented by the general formula (5) and / or the structural unit represented by the general formula (6), and the structural unit represented by the general formula (10). The polymer P containing the above can be produced. When a part of the structural unit represented by the general formula (MA) is opened and a part of the structural unit of the general formula (MA) remains without opening the ring, the polymer P is expressed by the general formula (IN). , The structural unit of the general formula (5) and / or the structural unit of the general formula (6), the organic group (i) having 1 to 6 valences of 1 to 30 carbon atoms, and the structural unit of the general formula (310). , Includes structural units represented by the general formula (MA).

Examples of the basic catalyst used in the step (IIIa) include amine compounds such as triethylamine, pyridine and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

In the step (IIIa), water is added to the reaction system containing the polymer precursor obtained in the step (II), and the obtained reaction solution is preferably used at 60 to 80 ° C. for about 0.25 to 6 hours. By heating, the structural unit of the formula (MA) contained in this polymer is opened, and the structural unit represented by the formula (10) is produced. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (II) can be used as it is. Therefore, step (IIIa) is preferably carried out by adding water to the reaction mixture obtained in step (II) in situ without any post-treatment.

The polymer P 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 can also be appropriately performed in order to remove unnecessary components other than the desired polymer.

First, in the above, the reaction solution diluted with an organic solvent and added with an acid (for example, formic acid) is vigorously stirred in a separating 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. In this way, an organic solution of the polymer is obtained.

The obtained organic solution containing the polymer P is purified by a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of the polymer P is added to an excess amount of toluene or water to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is washed with toluene or water several times.
Further, in order to remove formic acid and the basic catalyst, the 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 after washing with ion-exchanged water at, for example, 30 to 60 ° C. for 16 hours or more.
In the liquid-liquid extraction method, water is added to the obtained organic solution of polymer P, and the mixture is vigorously stirred with a separating 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 removing the water times, and the mixture is vigorously stirred 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. In this way, an organic solution of the polymer is obtained. If necessary, further steps of water addition and aqueous phase removal may be performed.
The obtained polymer organic solution is heated under reduced pressure by a rotary evaporator to concentrate, and then the final solvent (PGMEA, etc.) is added and diluted repeatedly to obtain a polymer P solution dissolved in the final solvent. Can be done.

In addition, the polymer solution may contain a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound used in synthesizing the polymer P. 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 5-50% of the peak area of the polymer P. The amount is preferably 10 to 35%, and the peak area derived from the monofunctional (meth) acrylic compound is 5 to 50% with respect to the peak area of the polymer P, particularly 10 The amount is preferably about 35%. Thereby, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

(Step (IIIb))
In step (IIIa), the polymer precursor obtained in step (II) is reacted with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst to contain the carboxyl group of the polymer precursor and the epoxy group (meth). ) The reaction of the acrylic compound with the epoxy group forms a structural unit represented by the general formula (8) and / or a structural unit represented by the general formula (9), which is represented by the general formula (IN). The organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms, the structural unit represented by the general formula (5) and / or the structural unit represented by the general formula (6), and the general. A polymer P containing a structural unit represented by the formula (8) and / or a structural unit represented by the general formula (9), and optionally a structural unit represented by the general formula (MA) is produced.

The step (IIIb) is preferably carried out by adding an epoxy group-containing (meth) acrylic compound to the reaction system containing the polymer precursor obtained in the step (II).

The reaction between the polymer precursor and the epoxy group-containing (meth) acrylic compound proceeds in the presence of a basic catalyst. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (II) can be used as it is. Therefore, in step (IIIb), the polymer precursor is isolated and purified from the reaction mixture containing the polymer precursor obtained in step (II), or the basic catalyst contained in the mixture is neutralized. Instead, it is preferably carried out in situ by adding an epoxy group-containing (meth) acrylic compound to the reaction mixture containing the polymer precursor obtained in step (II).

Specifically, the reaction solution obtained by adding an epoxy group-containing (meth) acrylic compound to the reaction mixture containing the polymer precursor is preferably heated at 60 to 80 ° C. for about 1 to 9 hours. The structure represented by the general formula (8) by the reaction between the carboxyl group of the polymer precursor (carboxyl group in the formula (5) and / or the formula (6)) and the epoxy group of the epoxy group-containing (meth) acrylic compound. Units and / or structural units represented by the general formula (9) are formed to produce the polymer P.

Examples of the epoxy group-containing (meth) acrylic compound include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethylacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and acrylic acid. Examples include glycidyl and the like, and one or more selected from these can be used.

The amount of the epoxy group-containing (meth) acrylic compound added is preferably 0.1 to 3.0 mol with respect to 1 mol of the carboxyl group of the polymer precursor.

After the step (IIIb), it is preferable to appropriately perform the following steps in order to remove unnecessary components other than the desired polymer P.

First, in the above, the reaction solution diluted with an organic solvent and added with an acid (for example, formic acid, citric acid, etc.) is vigorously stirred in a separating 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. In this way, an organic solution of polymer P is obtained.

An excess amount of toluene is added to the obtained organic solution of the polymer P to reprecipitate the polymer P. In addition, the polymer powder obtained by reprecipitation is washed with toluene several times (for example, twice).
Further, in order to remove the acid and the basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (for example, three times).
The polymer (A) of the present embodiment having high purity can be obtained by drying the polymer powder after washing with ion-exchanged water at, for example, 30 to 60 ° C. for 16 hours or more.

[Polymer solution]
The polymer solution of this embodiment contains the above-mentioned polymer P.
The polymer solution of the present embodiment, together with the polymer (A), is at least one selected from a polyfunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and a compound having a thiol group and an alkoxy group or an oligomer thereof. May include.

(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 may be an unreacted product of the (meth) acrylic compound used in the production of the polymer P. However, it may be added separately.

Examples of the polyfunctional (meth) acrylic compound that can be blended in the polymer solution include a compound represented by the following general formula (1bp), a compound represented by the general formula (1cp), and a general compound. Examples thereof include compounds represented by the formula (1d-p), but the present invention is not limited thereto.

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

Y in the general formula (1bp), the general formula (1c-p) and the general formula (1d-p) is a hydrogen atom or a (meth) acryloyl group, or a combination thereof.

The compounds in which Y is a hydrogen atom in the general formula (1bp), the general formula (1c-p) and the general formula (1d-p) are unreacted monomers (that is, the general formula (1bp), the general formula (1bp). It may be 1 c-p) or a compound represented by the general formula (1 d-p)), and may be added separately.
In the general formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

When the polyfunctional (meth) acrylic compound is blended in the polymer solution of the present embodiment separately from the unreacted product of the polyfunctional (meth) acrylic compound used in the production of the polymer P, the blending amount thereof is the polymer. The peak area derived from the polyfunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart of the solution is preferably 10% or less, more preferably 5% or less, still more preferably 5% or less, based on the peak area of the polymer P. It can be blended in an amount of 2% or less.

(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 formula (2am). In the formula (2am), the definitions of X ¹⁰ and R are the same as those in the formula (2a).

When the monofunctional (meth) acrylic compound is blended in the polymer solution of the present embodiment separately from the unreacted product of the monofunctional (meth) acrylic compound used in the production of the polymer P, the blending amount thereof is the polymer. The peak area derived from the monofunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart of the solution is preferably 10% or less, more preferably 5% or less, still more preferably 5% or less, based on the peak area of the polymer P. It can be blended in an amount of 2% or less.

(A compound having a thiol group and an alkoxy group or an oligomer thereof (compound (B)))
A compound having a thiol group and an alkoxy group or an oligomer thereof (referred to as "Compound (B)" in the present specification) which can be blended in the polymer solution of the present embodiment may have a thiol group and an alkoxy group. For example, known compounds can be used as long as the effects of the present invention are exhibited.

By containing the compound (B) or an oligomer thereof, the polymer solution of the present embodiment can provide a cured resin product having excellent adhesion to a substrate or the like. The substrate is not particularly limited, and examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate, as described later.

In the present embodiment, the alkoxy group contained in the compound (B) is preferably an alkoxy group having 1 to 3 carbon atoms from the viewpoint of the effect of the present invention, and is selected from O, N, S, P and Si. It is also preferable to have a structure in which a thiol group and an alkoxy group are bonded to an organic chain which may contain one or more atoms.
Specifically, the compound (B) preferably contains a compound represented by the following general formula (a).

In the general formula (a), R independently represent an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two Rs are alkoxy groups having 1 to 3 carbon atoms.
L represents an m + n valent organic chain which may contain one or more atoms selected from O, N, S, P and Si.

In the present embodiment, the L m + n-valent organic chain is derived from a linear or branched alkylene group (m + n: 2) having 1 to 10 carbon atoms and a linear or branched alkane having 1 to 20 carbon atoms. Examples include m + n-valent groups and m + n-valent groups derived from substituted or unsubstituted siloxanes.

X represents a single bond or a divalent organic group which may contain a carbonyl group, a (thio) ester group or a (thio) amide group.
In the present embodiment, X is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms.
Q represents a single bond or a divalent organic group which may contain a carbonyl group or a (thio) ester group or a (thio) amide group.
In the present embodiment, Q is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms.
m: n (molar ratio) is 1: 1 to 1: 8, and m + n is 2 to 20.
The weight average molecular weight of the compound is 100 to 2000.

Examples of the compound (B) include 3-mercaptopropylmethyldimethoxysilane (KBM-802, manufactured by Shinetsu Silicone Co., Ltd.), 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shinetsu Silicone Co., Ltd.), and (3-mercaptopropyl) tri. Examples thereof include ethoxysilane, a siloxane chain-containing polyfunctional silane coupling agent (KR-519, manufactured by Shinetsu Silicone Co., Ltd.), and an organic chain-containing polyfunctional silane coupling agent having the following structural units.

In the above general formula, a: b (molar ratio) is 2: 1 to 4: 1. The weight average molecular weight is 1000-1500. * Is a bond. Examples of the compound include X-12-1154 (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.
Further, the compound (B) or an oligomer thereof may be used alone or in combination of two or more.

In the polymer solution of the present embodiment, the compound (B) is 0.25 to 20% by mass, preferably 1.0 to 15% by mass, based on the polymer P from the viewpoint of the effect of the present invention. More preferably, it is blended in an amount of 2.0 to 12% by mass.

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 a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent and the like can be used.

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

[Manufacturing of polymer solution]
The polymer solution of the present 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-mentioned polymer P and a photopolymerization initiator. That is, the photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution of the present embodiment and a photopolymerization initiator. Each component will be described below.

(Photopolymerization initiator)
Examples of the photopolymerization initiator used in the photosensitive resin composition of the present embodiment include a photoradical polymerization initiator. Known compounds can be used as the photoradical polymerization initiator, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-. Methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methylpropionyl) benzyl] Phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2, -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] Alkylphenone compounds such as -1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 2-carboxybenzophenone; benzoinmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-based compounds such as benzoin isobutylate; thioxanthone-based compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; 2- (4- (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-ethoxycarbokynylnaphthyl) -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 -Halomethylated oxadiazole compounds such as oxadiazol, 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) Biimidazole compounds such as -4,4', 5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxim)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and other oxime ester compounds; bis (η5) -2,4-Cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) Titanosen compounds such as titanium; p-dimethylaminobenzoic acid, p. -A benzoic acid ester-based compound such as diethylaminobenzoic acid; an acridin-based compound such as 9-phenylacridin; and the like can be mentioned. The photoradical polymerization initiator may be used alone or in combination of two or more.
The photoradical polymerization initiator is used, for example, in an amount of 1 to 20 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polymer.

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

(Colorant)
In one aspect, the photosensitive resin composition may contain a colorant. By containing a colorant, it can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used.
As the pigment, an organic pigment or an inorganic pigment can be used.

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

Inorganic pigments include white / extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium-based, chrome vermillion, nickel titanium, chrome titanium). , Yellow iron oxide, red iron oxide, zinc chromate, lead tan, ultramarine, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), bright material 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 and the like can be used.
When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one colorant or two or more colorants.

A colorant (particularly a pigment) having an appropriate average particle size can be used depending on the purpose and application, but a small average of 0.1 μm or less is particularly required when transparency such as a color filter is required. When the particle size is preferable and other concealing properties such as paint are required, a large average particle size of 0.5 μm or more is preferable.

The colorant may be surface-treated such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, and wax coating, 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, but from the viewpoint of achieving both the coloring concentration and the dispersion stability of the colorant, the photosensitive resin composition is non-volatile. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 50% by mass with respect to the entire component (component excluding the solvent).

(Surfactant)
The photosensitive resin composition of the present embodiment may contain a surfactant, and the nonionic surfactant is preferable as the surfactant.

By containing the nonionic surfactant, the coatability when the photosensitive resin composition is applied onto the substrate to obtain a resin film is improved, and a coated film having a uniform thickness can be obtained. In addition, it is possible to prevent residues and pattern floating when developing the coating film.

The nonionic surfactant is, for example, a compound containing a fluorine group (for example, 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 nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of the fluorine-based surfactant include Megafuck 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, FC4432, etc. manufactured by Sumitomo 3M Ltd., but are not limited thereto.
When a surfactant is used, the blending amount of the surfactant 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 a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent and the like can be used.

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

(Shading agent)
The resin composition of the present embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one kind of light-shielding agent, or may contain two or more kinds of light-shielding agents.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and application, but from the viewpoint of achieving both light-shielding performance and dispersion stability of the light-shielding agent, the photosensitive resin composition is non-volatile. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 50% by mass with respect to the entire component (component excluding the solvent).

(Crosslinking agent)
The photosensitive resin composition of the present embodiment may contain a cross-linking agent.
The cross-linking agent is not particularly limited as long as it can cross-link the polymer by the action of the active chemical species generated from the photopolymerization initiator (those that can chemically bond with the polymer).
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, 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. (However, the cross-linking agent does not correspond to the above-mentioned polymer). It is preferable to use a cross-linking agent having the same kind of cross-linking group as the cross-linking group (polymerizable double bond) of the polymer in terms of uniform curability and further improvement of sensitivity.
The upper limit of the functional number (the number of polymerizable double bonds) per molecule of the cross-linking agent is not particularly limited, but is, for example, 8 or less, preferably 6 or less.

Specific examples of the cross-linking agent 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, and hexanediol di. (Meta) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol Falkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) Acrylate, glycerintri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropanetri (meth) acrylate, ethylene oxide-added ditrimethylol Propanetetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropanetri (meth) acrylate, propylene oxide-added dimethylolpropanetetra (meth) Acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added trimethylolpropane tetra (meth) acrylate , Ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, and other 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, trimetylol propanetrivinyl ether, ditri Methylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylol propanetrivinyl ether, ethylene oxide-added ditrimethylol propanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide. Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether;
2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylic acid, 1-methyl-2-vinyloxyethyl (meth) acrylic acid, 2-vinyloxypropyl (meth) acrylic acid, 4 (meth) acrylic acid -Vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyloxyhexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, ( Contains vinyl ether groups (meth) such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 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 Falkylene oxide diallyl ether, trimethyl propanetriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl 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) acrylic acid;
Polyfunctional (meth) acryloyl such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate, etc. Group-containing isocyanates;
Polyfunctional allyl group-containing isocyanates 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;
And so on.

Among them, trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, and tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dimethylolpropane tetra (meth) acrylate. ) Hexofunctional (meth) acrylates such as acrylates and dipentaerythritol hexa (meth) acrylates are preferred.

When the photosensitive resin composition contains a cross-linking agent, the photosensitive resin composition may contain only one kind of cross-linking agent, or may contain two or more kinds of 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 mass, preferably about 40 to 60 parts by mass with respect to 100 parts by mass of the photosensitive resin.

(Other additives)
The photosensitive resin composition may be a filler, a binder resin other than the above-mentioned polymers, an acid generator, a heat resistance improver, a development aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, or an oxidation, depending on various purposes and required properties. Ingredients such as inhibitors, matting agents, defoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, rocking agents, rocking aids, silane coupling agents, polyhydric phenol compounds, etc. May include.

[Use]
A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition and 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. Further, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Then, it is possible to manufacture a liquid crystal display device or a solid-state image sensor provided with a color filter and a black matrix.
A typical procedure for forming a pattern will be described.

(Formation of photosensitive resin film)
For example, the above-mentioned photosensitive resin composition is applied onto an arbitrary substrate and dried if necessary to first obtain a photosensitive resin film.

The substrate on which the composition is applied is not particularly limited. For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper-clad laminate, and the like can be mentioned.
The substrate may be an unprocessed substrate or a substrate on which electrodes and elements are formed on the surface. It may be surface-treated to improve the adhesiveness.

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

Drying of the photosensitive resin composition applied on the substrate is typically performed by heat treatment with a hot plate, hot air, an oven or the like. The heating temperature is usually 80 to 140 ° C, preferably 90 to 120 ° C. The heating time is usually about 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, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by adjusting the content of the solvent in the photosensitive resin composition, the coating method, and the like.

(exposure)
The exposure is typically performed by irradiating the photosensitive resin film with an active ray through a suitable photomask.

Examples of the active ray include X-rays, electron beams, ultraviolet rays, visible rays and the like. In terms of wavelength, light having 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 i-line is particularly preferable. Further, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferable.
The amount of light for exposure may be appropriately adjusted depending on the amount of the photosensitive agent in the photosensitive resin film and the like, and is, for example, about 100 to 500 mJ / cm ² .

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

(developing)
By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained and a substrate having the pattern 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 developing process.

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

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

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

In the present embodiment, it is preferable to use an alkaline aqueous solution as a developer, and it is more preferable to use a 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.
By the above steps, a pattern can be obtained / a substrate having the pattern can be manufactured, but various processes may be performed after the development.

For example, after development, the pattern and substrate may be washed with a rinse solution. Examples of the rinsing solution 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.

Further, the obtained pattern may be heated to be sufficiently cured. 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, in the range of 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature-increasing oven in which a temperature program can be set, or the like. The atmospheric gas for heat treatment may be air or an inert gas such as nitrogen or argon. Further, it may be heated under reduced pressure.
FIG. 1 schematically shows an example of the structure of a liquid crystal display device and / or a solid-state image sensor provided with a color filter and / or a black matrix.

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

The substrate 10 is usually made of a material that allows light to pass through, and is made of, for example, a polymer of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin, or the like, in addition to glass. The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical solution treatment, or the like, if necessary.
The substrate 10 is preferably made of glass.
The black matrix 11 is composed of, for example, a cured product of a photosensitive resin composition containing a light-shielding agent.

The color filter 12 usually has three colors of red, green, and blue. The color filter 12 is composed of a cured product of a 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 the above can be adopted.
Hereinafter, examples of further embodiments of the present invention will be added.

（式（ＩＮｍ）において、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または炭素数１～３０の有機基である。） [1] A step of polymerizing a monomer composition containing a monomer represented by the formula (INm) and maleic anhydride in the presence of a bifunctional or higher thiol group-containing compound to prepare a raw material polymer.
A method for producing a polymer, comprising a step of reacting the raw material polymer with a polyfunctional (meth) acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to obtain a polymer.

(In the formula (INm), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.)

（式（ＩＮｍ）において、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または炭素数１～３０の有機基である。） [2] A step of polymerizing a monomer composition containing a monomer represented by the formula (INm) and maleic anhydride in the presence of a bifunctional or higher thiol group-containing compound to prepare a raw material polymer.
A step of reacting the raw material polymer with a polyfunctional (meth) acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to prepare a polymer precursor.
A method for producing a polymer, which comprises a step of obtaining a polymer by treating the polymer precursor with water in the presence of a basic catalyst.

(In the formula (INm), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.)

（式（ＩＮｍ）において、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または炭素数１～３０の有機基である。） [3] A step of polymerizing a monomer composition containing a monomer represented by the formula (INm) and maleic anhydride in the presence of a bifunctional or higher thiol group-containing compound to prepare a raw material polymer.
A step of reacting the raw material polymer with a polyfunctional (meth) acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to prepare a polymer precursor.
A method for producing a polymer, which comprises a step of reacting the polymer precursor with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst to obtain a polymer.

(In the formula (INm), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.)

[4] The compound according to any one of [1] to [3], wherein the bifunctional or higher functional thiol group-containing compound is at least one compound selected from the formulas (s-1) to (s-21). How to make a polymer.

[5] A polymer solution containing the polymer obtained by the method for producing a polymer according to any one of [1] to [4].

[6] The polymer solution according to [5], further comprising at least one selected from a polyfunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, a compound having a thiol group and an alkoxy group, or an oligomer thereof. ..

[7] The polymer solution according to [5] or [6], which is used for forming a color filter or a black matrix.

[8] A photosensitive resin composition comprising the polymer solution according to [5] or [6] and a photopolymerization initiator.

[9] A cured product of the photosensitive resin composition according to [8].

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The compounds used in the examples may be indicated by the following abbreviations or trade names.
-MA: maleic anhydride-IN: indene-MEK: methyl ethyl ketone-PEMP: pentaerythritol tetrakis (3-mercaptopropionate), thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemistry Co., Ltd.)
NB: 2-norbornene-4-HBA: 4-hydroxybutyl acrylate-A-TMM-3LM-N: A mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatograph measurement is about 57%. (Made by Shin-Nakamura Chemical Industry Co., Ltd.)

-GMA: glycidyl methacrylate-KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd.)

<Synthesis of raw material polymer>
(Synthesis of raw material polymer 1)
122.4 g (1.05 mol) of inden, 1376.7 g of methyl ethyl ketone and dimethyl 2,2'-azobis (2-methylpropionate) 9 in an appropriately sized reaction vessel equipped with a stirrer and a condenser. .70 g (0.042 mol) was weighed and added, and the mixture was stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., 103.2 g (1.05 mol) of maleic anhydride is dissolved in MEK741.30 g, and nitrogen is used. A solution from which dissolved oxygen in the system had been removed by bubbling was added over 3 hours. Then, by further heating at 80 ° C. for 4 hours, maleic anhydride and indene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 2047.94 g of methanol to precipitate a white solid. The obtained white solid is further washed with 2047.94 g of methanol and then vacuum dried at a temperature of 120 ° C. to provide a polymer having a structural unit derived from inden and a structural unit derived from maleic anhydride (raw material polymer). 1) 320.1 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 9248, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.31. there were.

(Synthesis of raw material polymer 2)
122.4 g (1.05 mol) of inden, 131.0 g of methyl ethyl ketone and dimethyl 2,2'-azobis (2-methylpropionate) 3 in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Weighed in .73 g (0.016 mol) and added, stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, it was heated, and when the internal temperature reached 55 ° C., 103.2 g (1.05 mol) of maleic anhydride and pentaerythritol tetrakis (3-mercaptopro). Pionate) (PEMP, 20.58 g, 0.042 mol) was dissolved in MEK 131.02 g, and a solution from which dissolved oxygen in the system had been removed by nitrogen bubbling was added over 3 hours. Then, by further heating at 55 ° C. for 3 hours, maleic anhydride and indene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 2047.94 g of methanol to precipitate a white solid. The obtained white solid is further washed with 2047.94 g of methanol and then vacuum dried at a temperature of 120 ° C. to provide a polymer having a structural unit derived from inden and a structural unit derived from maleic anhydride (raw material polymer). 2) 315.0 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 8284, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.41. there were.

[Structural analysis of raw material polymer 2]
At the start of the reaction, the synthesis of the raw material polymer 2 is started with the monomer and PEMP dissolved in the solvent, and then the reaction proceeds to form the polymer. Analysis of each of the reaction solution and the obtained polymer gave 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 inden alone and maleic anhydride alone in the reaction solution after the reaction were reduced compared to before the reaction, and inden and male anhydride were reduced. It was confirmed that the acid reacted to form a polymer.
The measurement conditions for gas chromatography measurement were as follows.
-GC equipment: GC-2030 (Shimadzu Corporation)
・ Carrier gas: N2
-Detector: Hydrogen 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 ℃
-Column flow rate: 0.64 mL / min
-Column temperature rise conditions: 50 ° C 5 min hold, 20 ° C / min temperature rise to 300 ° C, 300 ° C 10 min hold

(B) Polymer analysis In the GPC measurement of the polymer after reprecipitation and purification, no peaks of PEMP alone, inden alone, and maleic anhydride alone were observed. That is, it was confirmed that PEMP, elemental indene and maleic anhydride did not remain in the polymer.
The amount of sulfur in the obtained raw material polymer 2 was confirmed by flask combustion and elemental analysis by an ion chromatographic method, and it was confirmed that the sulfur element was present in the raw material polymer 2. Further, in the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained. Therefore, it was confirmed that PEMP was incorporated into the raw material polymer 2.

The elemental analysis method is as follows.
-Test item Flask combustion-Quantification of total sulfur by ion chromatography-Test method Flask combustion-Ion chromatography (1) Completely burn about 50 mg of a sample in a sealed flask replaced with oxygen.
(2) The generated gas is collected in a hydrogen peroxide absorbing solution in a flask to which a pre-added gas is added, and the volume is adjusted to 50 ml as the test solution.
(3) A test solution and a standard solution are introduced into an ion chromatographic analyzer, the concentration of sulfate ion is determined by the calibration curve method, and the amount of sulfur contained in the sample is calculated.
-Device used Dionex ICS-3000 type ion chromatograph

[Confirmation of thioether structure contained in raw material polymer 2]
By ¹³ C-NMR measurement of PEMP alone represented by the following chemical formula, the peak a derived from carbon a was confirmed to be around 19.0 ppm, and the peak b derived from carbon b was confirmed to be around 62.0 ppm.

In the ¹³ C-NMR measurement of the raw material polymer 2 synthesized using PEMP, the appearance of the peak b derived from carbon b was confirmed at around 62.0 ppm. In the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained. Therefore, it was confirmed that PEMP was incorporated into the raw material polymer 2.

Further, in the ¹³ C-NMR measurement of the raw material polymer 2, the peak a derived from carbon a was not confirmed, and instead, the peak c corresponding to the thioether (RSR') appeared in the vicinity of 28 ppm. Since the integrated value of the peak c is about twice the integrated value of the peak b, the raw material polymer 2 has a skeleton having a thioether group as described below, and the thiol group has disappeared. It is considered that the polymer of the example synthesized by using the raw material polymer 2 also has a similar skeleton.

¹³ The conditions for C-NMR measurement are as follows.
(Test conditions) The measurement sample was prepared by adding a measurement solvent to the 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 nucleus: ¹³ C
-Measurement method: NNE measurement (inverse gate decoupling method)
-Pulse width: 3.83 μsec
・ Pulse repetition waiting time: 30s
・ Number of integrations: 4096 times ・ Measurement temperature: Room temperature ・ Measurement solvent: DMSO-d ₆ (deuterated dimethyl sulfoxide)
-Sample concentration: 20% (w / v)

¹³ The amount of PEMP incorporated in the raw material polymer 2 was 2.2 mol% with respect to the total amount of indene and maleic anhydride in the raw material polymer 2 calculated from the C-NMR measurement based on the following calculation method. there were.

[Calculation method of the amount (mol%) of PEMP in the raw material polymer 2]
First, the amount of PEMP introduced into the raw material polymer 2 is calculated from the peak integral value of 60 ppm to 64 ppm corresponding to the peak b (4C minutes) of PEMP.
Next, by subtracting the peak integral value (integral value of PEMP peak b = integral value of PEMP peak d) corresponding to the peak bd (4C minutes) of PEMP covered by the peak from the peak integral value of 170 ppm-175 ppm, the following The amount of MA in the raw material polymer 2 corresponding to the peak e (2C minutes) of maleic anhydride (MA) is calculated.

Then, the amount of IN in the raw material polymer 2 is calculated from the peak integral value of 125 ppm-142 ppm corresponding to the aromatic ring (6C minutes) of the indene (IN).
Based on the above, the amount (mol%) of PEMP incorporated in the raw material polymer 2 with respect to the total amount of indene and maleic anhydride in the raw material polymer 2 is calculated as "(amount of PEMP in the raw material polymer 2) ÷ ((raw material). Calculated from (amount of MA in polymer 2) + (amount of IN in raw material polymer 2)) ".

(Synthesis of raw material polymer 3)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, a 75% toluene solution of 2-norbornene 602.56 g (2-norbornene equivalent 451.92 g, 4.8 mol), maleic anhydride (MAN, 470.69 g). 4.8 mol) and 2281.74 g of methyl ethyl ketone (MEK) were added, and the mixture was stirred and dissolved. Next, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 80 ° C., dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., 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 were added over 1 hour. Then, the reaction was further 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 3686.4 g of methanol to precipitate a white solid. The obtained white solid is further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120 ° C. to provide a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (a polymer having a structural unit derived from maleic anhydride. Raw material polymer 4) 910.1 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3500, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.62. there were.
[Confirmation of thioether structure contained in raw material polymer 3]
In the ¹³ C-NMR measurement of the raw material polymer 3 synthesized using PEMP, the appearance of the peak b derived from carbon b was confirmed at around 62.0 ppm. In the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained. Therefore, it was confirmed that PEP was incorporated into the raw material polymer 3.

Further, in the ¹³ C-NMR measurement of the raw material polymer 3, the peak a derived from carbon a was not confirmed, and instead, the peak c corresponding to the thioether (RSR') appeared in the vicinity of 28 ppm. Since the integrated value of the peak c is about twice the integrated value of the peak b, the raw material polymer 3 has a skeleton having a thioether group as described below, and the thiol group has disappeared. It is considered that the polymer of the comparative example synthesized by using the raw material polymer 3 also has a similar skeleton.

The amount of sulfur in the obtained polymer was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that the sulfur element was present in the polymer. In addition, it was confirmed that the peak derived from PEMP disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that PEMP was incorporated into the polymer.

As a result of elemental analysis, the sulfur content in the raw material polymer 3 was 2.4 wt%.

<Preparation of polymer P (polymer solution)>
In each preparation example, polymer P was prepared. Table 1 shows the components used in the preparation examples and the amount of each component charged in terms of maleic anhydride (MA), and the amount of each structural unit (molar fraction, mol%) is analyzed by ¹ H-NMR integrated value. It was calculated and shown in terms of maleic anhydride (MA).

(Preparation Example 1)
The MA unit of the raw material polymer 1 was ring-opened with a monofunctional (meth) acrylic compound to prepare a polymer P1. The details will be described below.
First, 18.44 g of MEK was added to 10.00 g (MA equivalent 0.047 mol) of the raw material polymer to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, then 3.00 g (0.030 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 6 hours to prepare a reaction solution. Was produced.
The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, 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 excess amount of water was repeated twice. The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 9.1 g of polymer P1 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer 1 with 4-HBA was obtained.
GPC measurement was carried out on the obtained polymer P1 to measure the weight average molecular weight and the degree of polydispersity of the polymer P1. The results are shown in Table 1.
In addition, the disappearance of the peak of the monofunctional (meth) acrylic compound used was confirmed by GPC measurement of the polymer P1. As a result, it was confirmed that the obtained polymer P1 did not contain an unreacted monofunctional (meth) acrylic compound.

(Preparation Example 2)
The polymer P2 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer 2 with 4-HBA in the same manner as in Preparation Example 1 except that the raw material polymer 1 of Preparation Example 1 was changed to the raw material polymer 2. 7.5 g was obtained.
GPC measurement was carried out on the obtained polymer P2 to measure the weight average molecular weight and the degree of polydispersity of the polymer P2. The results are shown in Table 1.
In addition, GPC measurement of the polymer P2 confirmed the disappearance of the peak of the monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P2 did not contain an unreacted monofunctional (meth) acrylic compound.

(Preparation Example 3)
A resin mixture containing a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound and a polymer P3 ring-opened with water was prepared from the MA unit of the raw material polymer 1. The details will be described below.
First, 99.71 g of MEK was added to 160.00 g of the raw material polymer (0.280 mol in MA conversion) to prepare a solution. Then, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was 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, without post-treatment, the obtained reaction solution was added with 3.00 g (0.167 mol) of water and reacted at 70 ° C. for 2 hours. The obtained reaction solution was diluted with MEK and treated with an aqueous solution of formic acid and an aqueous solution of citric acid to remove the aqueous phase from the reaction solution. Further, liquid-liquid extraction and then solvent substitution were carried out according to 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 substitution: The obtained reaction mixture was subjected to solvent removal at 50 ° C. under reduced pressure by a rotary evaporator. It was confirmed that the solid content concentration of the polymer solution was 27 ± 2% by mass as measured by a heat-drying moisture meter, and the solvent removal operation was interrupted. Then, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was mixed until uniform. In the same operation, remove the solvent under reduced pressure at 50 ° C., adjust the solid content concentration to 27 ± 2% by mass by measurement with a heat-drying moisture meter, and then PGMEA so that the solid content concentration becomes 18% by mass. Was added, and the operation of mixing until uniform was repeated twice more. Then, the solvent was removed or PGMEA was added so that the solid content concentration became 30 ± 3% by mass, and the operation was performed to stir until uniform. By the above operation, the solvent used for the reaction is removed, and the solvent is replaced with PGMEA.
As described above, the structural units derived from maleic anhydride in the raw material polymer 1 were ring-opened with A-TMM-3LM-N, 4-HBA and water, and the residual (free) A-TMM-3LM-N. And a polymer solution 3 containing residual (free) 4-HBA was obtained.
The obtained polymer solution 3 was analyzed by a gel permeation chromatography method, and the amount of the polymer P3, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the polymer P3 were analyzed. Weight average molecular weight and polydispersity were measured. The results are shown in Table 1. 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 P3 in the gel permeation chromatography (GPC) chart of the resin mixture.
The measurement conditions of the gel permeation chromatography method are as follows.
-As the GPC measuring device, HLC-8320GPC EcoSEC manufactured by Tosoh Corporation was used. The column temperature was set to 40.0 ° C. and the pump flow rate was set to 0.350 mL / min.
・ Peak position (holding time)
-Polymer P3: 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: Total of 2peaks of 20.0 to 20.6 minutes and 20.6 to 21.5 minutes-4-HBA: 21.7 to 22.4 minutes-Measurement condition: Differential refractometer Analysis was performed with a rate detector (RI detector).

(Preparation Example 4)
In the same manner as in Preparation Example 3 except that the raw material polymer 1 of Preparation Example 3 was changed to the raw material polymer 2.
The structural units derived from maleic anhydride in the raw material polymer 2 were ring-opened polymer P4 with A-TMM-3LM-N, 4-HBA and water, and residual (free) A-TMM-3LM-N and residual (free). Free) Polymer solution 4 containing 4-HBA was obtained.
The obtained polymer solution 4 is analyzed by a gel permeation chromatography method, and the amount of the polymer P4, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the polymer P4 Weight average molecular weight and polydispersity were measured. The results are shown in Table 1. 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 P4 in the gel permeation chromatography (GPC) chart of the resin mixture.
The measurement conditions of the gel permeation chromatography method are as follows.
-As the GPC measuring device, HLC-8320GPC EcoSEC manufactured by Tosoh Corporation was used. The column temperature was set to 40.0 ° C. and the pump flow rate was set to 0.350 mL / min.
・ Peak position (holding time)
-Polymer P4: 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: Total of 2peaks of 20.0 to 20.6 minutes and 20.6 to 21.5 minutes-4-HBA: 21.7 to 22.4 minutes-Measurement condition: Differential refractometer Analysis was performed with a rate detector (RI detector).

(Preparation Example 5)
The additives shown in Table 1 were mixed with the polymer solution 4 obtained in Preparation Example 4 in an amount shown in "Additive amount" in Table 1 to prepare a polymer solution 5. Here, the amount of the additive was mixed by weight% with respect to the solid content (polymer P4, polyfunctional (meth) acrylic compound) in the polymer solution 4.

(Preparation Example 6)
The MA unit of the raw material polymer 1 is ring-opened with a trifunctional (meth) acrylic compound (A-TMM-3LM-N) and a monofunctional (meth) acrylic compound (4-HBA), and then an epoxy group-containing (meth) acrylic. The polymer P6 obtained by reacting with compound (GMA) was prepared. The details will be described below.
First, 102.63 g of MEK was added to 160 g of the raw material polymer (0.280 mol in terms of MA) to prepare a solution. Then, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 27.01 g (0.187 mol) of 4-HBA was added, and the mixture was reacted at a temperature of 70 ° C. for 4 hours. After that, 13.31 g (0.094 mol) of GMA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was 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 excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, the structural unit derived from maleic anhydride in the raw material polymer 1 was ring-opened with A-TMM-3LM-N and 4-HBA to obtain 32.0 g of the polymer P6 reacted with GMA.

By GPC measurement of the polymer P6, the disappearance of the peaks of the polyfunctional (meth) acrylic compound, the monofunctional (meth) acrylic compound, and the epoxy group-containing (meth) acrylic compound used was confirmed. As a result, it was confirmed that the obtained polymer P6 does not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, and an unreacted epoxy group-containing (meth) acrylic compound. ..

(Preparation Example 7)
Similar to Preparation Example 6 except that the raw material polymer 1 of Preparation Example 6 was changed to the raw material polymer 2, the structural units derived from maleic anhydride in the raw material polymer 2 were A-TMM-3LM-N and 4-HBA. The ring was opened with GMA to obtain 25.1 g of the polymer P7 reacted with GMA.

By GPC measurement of the polymer P7, the disappearance of the peaks of the polyfunctional (meth) acrylic compound, the monofunctional (meth) acrylic compound, and the epoxy group-containing (meth) acrylic compound used was confirmed. As a result, it was confirmed that the obtained polymer P7 does not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, and an unreacted epoxy group-containing (meth) acrylic compound. ..

(Preparation Example 8)
In the same manner as in Preparation Example 1 except that the raw material polymer 1 of Preparation Example 1 was changed to 10 g (MA equivalent 0.052 mol) of the raw material polymer 3, the structural unit derived from maleic anhydride in the raw material polymer 3 was 4-. 8.7 g of polymer P8 ring-opened with HBA was obtained.
GPC measurement was performed on the obtained polymer P8 to measure the weight average molecular weight and the degree of polydispersity of the polymer P8. The results are shown in Table 1.
In addition, GPC measurement of the polymer P8 confirmed the disappearance of the peak of the monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P8 did not contain an unreacted monofunctional (meth) acrylic compound.

(Preparation Example 9)
(Polymer synthesis)
The MA unit of the raw material polymer 3 was ring-opened with a monofunctional (meth) acrylic compound (HEMA) and then reacted with an epoxy group-containing (meth) acrylic compound (GMA) to prepare a polymer P9. The details will be described below.
First, MEK 111.43 g was added to 360 g (MA equivalent 0.312 mol) of the raw material polymer to prepare a solution. Then, 25.38 g (0.195 mol) of HEMA was added to this lysate, then 6.00 g (0.059 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 6 hours. After that, 13.31 g (0.094 mol) of GMA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess of water.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of water was repeated twice.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with HEMA to obtain 35.1 g of the polymer P9 reacted with GMA.
By GPC measurement of the polymer P9, the disappearance of the peak of the monofunctional (meth) acrylic compound used and the peak of the epoxy group-containing (meth) acrylic compound was confirmed. As a result, it was confirmed that the obtained polymer P9 contained neither an unreacted (meth) acrylic compound nor an epoxy group-containing (meth) acrylic compound.

(Preparation Example 10)
Polymer P10 was prepared by ring-opening the MA unit of the raw material polymer 2 with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water. The details will be described below.
First, 99.71 g of MEK was added to 60.00 g (MA equivalent 0.280 mol) of the raw material polymer to prepare a solution. Then, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was 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, without post-treatment, the obtained reaction solution was added with 3.00 g (0.167 mol) of water and reacted at 70 ° C. for 2 hours.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was 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 excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As a result, 32.4 g of the polymer P10 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer 2 with A-TMM-3LM-N, 4-HBA, and water was obtained.
GPC measurement of the polymer P10 confirmed the disappearance of the peaks of the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P10 contained neither an unreacted (meth) acrylic compound nor a hydroxyl group-free (meth) acrylic compound.

(Evaluation of the physical properties)
The acid value and double bond equivalent of the polymers P synthesized in Examples and Comparative Examples were measured by the methods shown below.

(Acid value)
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 measured by ¹ H-NMR using a nuclear magnetic resonance spectroscope JNM-AL300 (manufactured by JEOL Ltd.). ¹ H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer based on the integrated value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, which is the standard in 1 H-NMR measurement. The amount of carboxyl group is obtained from the integrated value of. Then, the acid value (mgKOH / g) can be calculated from the amount. The larger the acid value, the larger the amount of carboxyl groups per unit mass of the polymer.
The results are shown in Table 1. When the acid value is 70 gKOH / g or more, it can be considered that the carboxy group necessary for the polymer to have sufficient developability is present in the polymer.

(Double bond equivalent)
The double bond equivalent of the polymer was measured by the following method.
¹ H-NMR measurement was carried out in the same manner as in the above acid value measuring method. From the integral ratio of the signal derived from the acryloyl group (5.6-5.8 ppm, 3H) of the obtained spectrum chart and the signal of the phenyl group of the internal standard substance (8.1 ppm, 4H), the amount of acryloyl group in the polymer (Mol / g) is calculated, 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), in the polymer. The amount of methacryloyl group (mol / g) was calculated. Here, since the signal derived from the methacryloyl group of 6.0-6.1 ppm is minute and overlaps with the signal of the acryloyl group, it was calculated as the signal of the acryloyl group. The double bond amount (mol / g) is calculated from the total of the acryloyl group amount (mol / g) and the methacryloyl group (mol / g) in the calculated polymer, and the double bond equivalent (g / g) is calculated from the double bond amount. mol) was calculated.
The results are shown in Table 1. The smaller the value of the double bond equivalent, the larger the amount of C = C double bonds per unit mass of polymer.

(Examples 1 to 5, Comparative Examples 1 to 5)
The following items were evaluated in each Example and Comparative Example.
<Evaluation>
[Alkaline dissolution rate of polymer solution]
The polymers P1, P2, and P6 to 10 obtained in Preparation Examples 1, 2, 6 to 10 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid content concentration of 30% by mass.
Then, the above solution or the polymer solutions 3 to 5 obtained in Preparation Examples 3 to 5 are spin-coated on the wafer, PGMEA is dried, and prebaked at a temperature of 100 ° C. for 2 minutes to obtain a resin having a film thickness of about 2 μm. A film was made.
This resin film was immersed in a 2% sodium carbonate aqueous solution having a temperature of 23 ° C. for each wafer, and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern disappearing, and dividing the film thickness by that time. The results are shown in Table 2. If the alkali dissolution rate is 100 nm / s or more, it can be used as a photosensitive material without any problem. In particular, if it is 200 nm / s or more, it can be considered to be particularly good.

[Sensitivity evaluation 1 of the photosensitive resin composition (exposure amount at which the residual film ratio is 95% or more)]
First, a photosensitive resin composition in which the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) was obtained so that the total solid content concentration was 30% by mass.
Polymers P1, P2, P6 to 10 (polymers P1, P2, P6 to 10 of Preparation Examples 1, 2, 6 to 10) or polymer solutions 3 to 5 (polymer solutions 3 to 5 obtained in Preparation Examples 3 to 5). ): 100 parts by mass (Here, for the polymer solutions 3 to 5, the total amount of the solid content (polymer P3 or P4 and the polyfunctional (meth) acrylic compound, and if an additive is contained, the total including the additive). Weighed so that the amount) is 100 parts by mass.)
・ Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass ・ Photopolymerization initiator (manufactured by BASF, Ingacure OXE01): 5 parts by mass ・ Adhesion aid (Shin-Etsu Chemical Co., Ltd.) KBM-403) manufactured by Kogyo Co., Ltd.: 1 part by mass ・ Surfactant (F-556 manufactured by DIC Corporation): 0.5 part by mass

The obtained photosensitive resin composition was rotationally coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100 ° C. for 120 seconds to a thickness of about 3.0 μm (± 0.3 μm). Thin film A was obtained.
The thin film A was exposed to g + h + i lines at an exposure amount of 100 mJ / cm ² with a Canon g + h + i line mask aligner (PLA-501F) via a photomask having a gradation with a shading rate of 1 to 100%.
After the exposure, the thin film was developed (immersed together with the wafer) at 23 ° C. for 60 seconds with a 2.0 mass% sodium carbonate aqueous solution 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 the thin films A and B obtained by the above method, the residual film ratio was calculated from the following formula.
Remaining film ratio (%) = (thin film thickness of thin film B / film thickness of thin film Af at each exposure amount) × 100
The exposure amount at which the residual film ratio was 95% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 1. It can be considered that the sensitivity is good when the exposure amount at which the residual film ratio is 95% or more is 20 mJ / cm ² or less, and the sensitivity is particularly good when the exposure amount is 15 mJ / cm ² or less.

[Sensitivity evaluation 2 of resin composition (residual film ratio after exposure at low exposure amount)]
(Residual film ratio at an exposure of 5 mJ / cm ² )
The photosensitive resin composition prepared in the above sensitivity evaluation 1 was rotationally coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), baked on a hot plate at 100 ° C. for 120 seconds, and heated to a thickness of 3.0 μm (±). A thin film A of 0.3 μm) was obtained.
The thin film A was exposed to g + h + i lines at an exposure amount of 5 mJ / cm ² with a Canon g + h + i line mask aligner (PLA-501F) via a photomask having a gradation with a shading rate of 1 to 100%.
After the exposure, the thin film was developed (immersed together with the wafer) at 23 ° C. for 60 seconds with a 2.0 mass% sodium carbonate aqueous solution to obtain a thin film B.
From the film thicknesses of the thin films A and 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 amount) × 100

(Residual film ratio at an exposure of 10 mJ / cm ² )
The photosensitive resin composition prepared in the above sensitivity evaluation 1 was rotationally coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), baked on a hot plate at 100 ° C. for 120 seconds, and heated to a thickness of 3.0 μm (±). A thin film A of 0.3 μm) was obtained.
The thin film A was exposed to g + h + i lines at an exposure amount of 10 mJ / cm ² with a Canon g + h + i line mask aligner (PLA-501F) via a photomask having a gradation with a shading rate of 1 to 100%.
After the exposure, the thin film was developed (immersed together with the wafer) at 23 ° C. for 60 seconds with a 2.0 mass% sodium carbonate aqueous solution to obtain a thin film B.
From the film thicknesses of the thin films A and 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 amount) × 100
If the residual film ratio at an exposure amount of 10 mJ / cm ² is 50% or more, it can be used as a photosensitive material without any problem.

[Alkaline dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)]
The photosensitive resin composition prepared in the above sensitivity evaluation 1 is spin-coated on a wafer with the above solution, dried PGMEA, and prebaked at a temperature of 100 ° C. for 2 minutes to form a resin film having a film thickness of about 2 μm. Made.
This resin film was immersed in a 2% sodium carbonate aqueous solution having a temperature of 23 ° C. for each wafer, and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern disappearing, and dividing the film thickness by that time. The results are shown in Table 1. If the alkali dissolution rate is 200 nm / s or more, it can be used as a photosensitive material without any problem, if it is 300 nm / s or more, it can be considered that the developability is good, and if it is 500 nm / s or more, it can be developed. It can be considered that the sex is particularly good.

[Yellow index]
The photosensitive resin composition prepared in the above sensitivity evaluation 1 was rotationally coated on Eagle XG glass (manufactured by Corning Inc., thickness 0.5 mm), baked at 100 ° C. for 120 seconds on a hot plate, and about 3. A thin film having a thickness of 0 μm (± 0.1 μm) was obtained.
This thin film was exposed to g + h + i lines with an exposure amount of 100 mJ / cm ² using a g + h + i line mask aligner (PLA-600F) manufactured by Canon Inc.
After the exposure, the thin film was developed (immersed together with the wafer) at 23 ° C. for 60 seconds with a 2.0 mass% sodium carbonate aqueous solution to obtain a thin film exposed and developed at an exposure amount of 100 mJ / cm ² .
The thin film was heat treated in air at 230 ° C. for 30 minutes. After cooling the thin film under room temperature air, the thin film was heat-treated again at 230 ° C. for 30 minutes by aeration. The same operation was repeated, and the heat treatment was performed in air for 30 minutes a total of 3 times.
The yellow index (YI) of the thin film obtained by the above method was measured three times using a color difference meter CR-5 (manufactured by Konica Minolta) at different measurement points, and the average value was taken as the YI value. The measurement type used was transmission measurement, and 100% calibration used uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm). The results are shown in Table 1. The lower the yellow index, the better the heat-resistant discoloration. If it is 2.0 or less, it can be used as a photosensitive resin for black matrix production without any problem, and if it is 1.50 or less, the heat-resistant discoloration is considered to be good. Can be done.

Table 2 shows the results of the developability evaluation and the sensitivity evaluation.

The photosensitive resin composition of the example had a good alkali dissolution rate, and was therefore excellent in developability. In the photosensitive resin composition of the example, the exposure amount at which the residual film ratio is 95% or more is 20 mJ / cm ² or less, in other words, it is cured at a low exposure amount, and it can be said that the sensitivity is high. Therefore, the photosensitive resin composition of the example has a good balance of high developability, high sensitivity, and low yellow index.

<Making color filters>
A colored photosensitive resin composition was prepared by further adding an appropriate amount of a pigment dispersion liquid NX-061 (manufactured by Dainichiseika Kogyo Co., Ltd., green) to the photosensitive resin compositions prepared in Examples 1 to 5.
A green color filter could be formed by forming a film on the substrate and performing exposure, alkaline development, and the like.
Further, as the pigment dispersion liquid, NX-053 (blue), NX-032 (red) and the like manufactured by the same company could be used instead of NX-061 to form a blue or red color filter.

<Making a black matrix>
A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Kogyo Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 5.
A black matrix could be formed by forming a film on a substrate and performing exposure, alkaline development, and the like.

10 Substrate 11 Black matrix 12 Color filter 13 Protective film 14 Transparent electrode layer

Claims (14)

A polymer having a structure represented by the formula (P).

(In equation (P)
m is an integer from 0 to 5 and
n is an integer of 1 to 6 and
m + n is 2 to 6,
p, q and r indicate the molar content of A, B and C, respectively, p + q + r = 1, p is greater than 0, q is greater than 0, r is greater than or equal to 0, 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 or more and 30 or less carbon atoms.
Y is an organic group having 2 to 6 valences having 1 or more and 30 or less carbon atoms derived from a bifunctional or higher functional thiol group-containing compound.
A represents a structural unit represented by the formula (IN).
B includes at least one structural unit selected from the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3).
C represents a divalent structural unit derived from a copolymerizable compound having a double bond.
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 the formula (IN), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.)

(In formula (1), R ^p represents a group containing two or more (meth) acryloyl groups.)

(In formula (2), R ^s represents a group containing one (meth) acryloyl group.)

(In equation (3)
Z is a group containing one or more (meth) acryloyl groups.
Q is a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
X represents an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. ))) The polymer according to claim 1, wherein B further comprises a structural unit represented by the formula (4).

B is selected from the structural unit represented by the formula (5), the structural unit represented by the formula (6), the structural unit represented by the formula (8), and the structural unit represented by the formula (9). The polymer according to claim 1 or 2, wherein the polymer comprises at least one thereof.

(In equations (5), (6), (8), and (9), R ^p , R ^s , Q, X, and Z are synonymous with those in the above equations (1) to (3). ) The polymer according to any one of claims 1 to 3, wherein B further comprises a structural unit represented by the formula (10).

The polymer according to any one of claims 1 to 4, wherein the B further comprises a structural unit represented by the formula (MA).

R ^p in the structural unit represented by the formula (1) is selected from a group represented by the formula (1b), a group represented by the formula (1c), and a group represented by the formula (1d). The polymer according to any one of claims 1 to 5, which is at least one.

(In equation (1b),
k is 2 or 3
R is a hydrogen atom or a methyl group, and multiple Rs 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 -LM- (L is -O- or -OCO-, and M is an alkylene group having 1 to 6 carbon atoms. ), And multiple ^X1s 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 -L'-M'-(L'is an alkylene group having 1 to 6 carbon atoms, and M'is -O- or -COO-),
X ² is a k + 1 valent organic group having 1 to 12 carbon atoms. )

(In equation (1c),
k, R, X ¹ and X ² are synonymous with R, k, X ¹ and X ² in the equation (1b), respectively, and a plurality of Rs may be the same as or different from each other, and a plurality of Rs may be different from each other. X ^1s may be the same or different from each other
X3 is a divalent organic group having 1 to ⁶ carbon atoms.
X ⁴ and X ⁵ are independently single-bonded or divalent organic groups having 1 to 6 carbon atoms, respectively.
X ⁶ is a divalent organic group having 1 to 6 carbon atoms. )

(In equation (1d),
n is an integer of 2 to 5,
R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. ) The polymer according to any one of claims 1 to 6, wherein R ^s in the structural unit represented by the formula (2) is a group represented by the formula (2a).

(In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.) The polymer according to any one of claims 1 to 7, wherein the C comprises two sections of structural units derived from at least one compound selected from the substituted or unsubstituted norbornene, styrene, maleimide, and norbornadiene. .. The polymer according to any one of claims 1 to 8, which has a weight average molecular weight of 5,000 or more and 80,000 or less. A polymer solution comprising the polymer according to any one of claims 1 to 9. The polymer solution according to claim 10, further comprising at least one selected from a polyfunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and a compound having a thiol group and an alkoxy group or an oligomer thereof. The polymer solution according to claim 10 or 11, which is used for forming a color filter or a black matrix. With the polymer solution according to claim 10 or 11.
A photosensitive resin composition comprising a photopolymerization initiator. The cured product of the photosensitive resin composition according to claim 13.

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