JP7006837B2 - Polymer manufacturing method - Google Patents

Description

The present invention relates to a polymer and a resin composition containing the same. More specifically, the present invention relates to polymers used as materials for photosensitive resin compositions used in the manufacture of films, color filters, black matrices, display devices and image pickup devices, and resin compositions containing them.

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. 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.

The present inventors have improved the polymer used in the photosensitive resin composition and the formulation of the composition to 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 monomer composition containing a monomer represented by the following general formula (NBm) and maleic anhydride is polymerized in the presence of a bifunctional or higher thiol group-containing compound to obtain a polymer precursor . The process of obtaining and
The polymer precursor is reacted with a compound having a hydroxyl group and two or more (meth) acryloyl groups and / or a compound having a hydroxyl group and one (meth) acryloyl group in the presence of a basic catalyst. , A method for producing a polymer is provided, which comprises a step of obtaining the polymer.

（一般式（ＮＢｍ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２である。）

(In the general formula (NBm), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. .)

（一般式（Ｐ'）中、
ｍは、０～５の整数であり、
ｎは、１～６の整数であり、
ｎ＋ｍは、１～６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以上であるり、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１～６価の炭素数１以上３０以下の有機基であり、
Ａは、一般式（ＮＢ）で表される構造単位を含み、
Ｂは、一般式（１）で表される構造単位、および一般式（２）で表される構造単位から選択される少なくとも１つの構造単位を含み、
Ｃは、二重結合を有する共重合性化合物から誘導される２価の構造単位を含み、
複数存在するＡ同士、Ｂ同士またはＣ同士は同一でも異なっていてもよく、
Ｑは、Ａ、ＢおよびＣと同一または異なる有機基を含む。）

（一般式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２である。）

（一般式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基である。）

（一般式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基である。））Further, according to the present invention, a polymer having a structure represented by the formula (P') is provided.

(In the general formula (P'),
m is an integer from 0 to 5 and
n is an integer of 1 to 6 and
n + m is 1 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 a 1- to hexavalent organic group having 1 to 6 carbon atoms and 30 or less carbon atoms derived from a bifunctional or higher functional thiol group-containing compound.
A includes a structural unit represented by the general formula (NB).
B comprises at least one structural unit selected from the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).
C comprises a divalent structural unit derived from a copolymer having a double bond.
A plurality of A's, B's, or C's may be the same or different.
Q contains the same or different organic groups as A, B and C. )

(In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. .)

(In the general formula (1), R ^p is a group having two or more (meth) acryloyl groups.)

(In the general formula (2), R ^s is a group having one (meth) acryloyl group.))

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

According to the present invention, there is provided a polymer as a resin material for use in a photosensitive resin composition having good sensitivity, high alkali solubility, and thus excellent developability and reduced yellowing. Will be done.

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)
The polymer of the present embodiment (hereinafter referred to as "polymer P") is a compound composed of a monomer represented by the following general formula (NBm) and maleic anhydride and a bifunctional or higher functional thiol group-containing compound. The polymer precursor obtained by polymerization in the presence of a compound having a hydroxyl group and two or more (meth) acryloyl groups in the presence of a basic catalyst, and / or a hydroxyl group and one (meth) acryloyl. It is a polymer obtained by reacting with a compound having a group.

（一般式（ＮＢｍ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ_１は０、１または２である。）

(In the general formula (NBm), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. .)

The polymer P of the present embodiment obtained by the above method has a thioether group. Since the polymer P has a thioether group, it has excellent sensitivity in the photolithography method, has higher alkali solubility, and thus has better developability, and resin curing with reduced yellowing and excellent transparency. Can provide things. Further, the polymer P of the present embodiment obtained by the above method has a structural unit derived from a norbornene monomer represented by the formula (NBm). Structural units derived from norbornene monomers are 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.

Polymer P has a (meth) acryloyl group in addition to the thioether group. The polymer P may be, for example, a resin having a thioether group and a monofunctional (meth) acryloyl group, a resin having a thioether group and a polyfunctional (meth) acryloyl group, a thioether group and a monofunctional (meth) acryloyl group and a polyfunctional (meth) acryloyl group. It can be a resin having a meta) acryloyl group.

The polymer P is preferably a resin having a thioether group and a polyfunctional (meth) acryloyl group from the viewpoint of the effect of the present invention.

More specifically, the polymer P of the present embodiment has a (meth) acrylic resin having a biphenyl skeleton and having one or more thioether groups, and a (meth) acrylic resin having a bisphenol skeleton and having one or more thioether groups. , A (meth) acrylic resin having a bisphenol skeleton containing a fluorene group and having one or more thioether groups, a (meth) acrylic resin having a linear alkylene skeleton and having one or more thioether groups, maleic anhydride and norbornene-based monomers polymerized. It can be a (meth) acrylic resin that has a skeletal structure and has one or more thioether groups.

The (meth) acrylic resin having a thioether group includes not only a polymer of an acrylic acid ester or a methacrylic acid ester, but also a resin having a (meth) acryloyl group added to the side chain of the skeleton.

The polymer P in which one or more thioether groups are introduced into the structure can be obtained by a method of synthesizing the polymer in the presence of a thiol compound, a method of separately reacting the thiol compound after synthesizing the polymer, or the like. Can be done. As the thiol compound used for producing the polymer P of the present embodiment, conventionally known compounds can be used as long as the effects of the present invention can be obtained.

The polymer P of the present embodiment is preferably a thioether group-containing (meth) acrylic resin having a structural unit derived from maleic anhydride (hereinafter, thioether group-containing (meth) acrylic resin (hereinafter, thioether group-containing (meth) acrylic resin), preferably from the viewpoint of the effect of the present invention. It is preferable to include a)). Hereinafter, the thioether group-containing (meth) acrylic resin (a) used as the polymer P of the present embodiment will be described.

<Thioether group-containing (meth) acrylic resin (a)>
The thioether group-containing (meth) acrylic resin (a) of the present embodiment has a structure represented by the following general formula (P'). The structural unit A and the structural unit B in the general formula (P') typically constitute the main chain of the thioether group-containing (meth) acrylic resin (a).

一般式（Ｐ'）中、
ｍは、０～５の整数であり、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、１～６であり、好ましくは、３～６である。
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１～６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、一般式（ＮＢ）で表される構造単位を含む。
Ｂは、一般式（１）で表される構造単位、および一般式（２）で表される構造単位から選択される少なくとも１つの構造単位を含む。
Ｃは、二重結合を有する共重合性化合物より誘導される構造単位を含む。
複数存在するＡ同士、Ｂ同士またはＣ同士は同一で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。
Ｑは、Ａ、ＢおよびＣと同一または異なる任意の有機基を含む。

In the general formula (P'),
m is an integer of 0 to 5, preferably 0 or 1, and more preferably 0.
n is an integer of 1 to 6, preferably 3 to 6.
However, n + m is 1 to 6, preferably 3 to 6.
p, q and r indicate the molar contents of A, B and C, respectively, and p + q + r = 1.
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 1 to 6 valences having 1 to 6 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 includes a structural unit represented by the general formula (NB).
B includes a structural unit represented by the general formula (1) and at least one structural unit selected from the structural units represented by the general formula (2).
C comprises a structural unit derived from a copolymerizable compound having a double bond.
A plurality of A's, B's, or 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.
Q comprises any organic group that is the same as or different from A, B and C.

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

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

式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基である。

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

式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基である。

In formula (2), ^Rs is a group having one (meth) acryloyl group.

式（Ｐ）において、
ｎ、ならびにｐ、ｑおよびｒは、一般式（Ｐ'）における定義と同じであり、Ｘ、Ｙ、Ａ、ＢおよびＣは、一般式（Ｐ'）における定義と同じである。In one embodiment, the thioether group-containing (meth) acrylic resin (a) of the present embodiment has a general formula (P) in which m is 0 in the structure represented by the general formula (P'). It has the structure represented.

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

The thioether group-containing (meth) acrylic resin (a) of the present embodiment contains, as the structural unit B, a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2). In other words, the structural unit B includes 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, the photosensitive resin composition containing the thioether group-containing (meth) acrylic resin (a) 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 unit represented by the general formula (1) or the general formula (2). Further, the thioether group-containing (meth) acrylic resin (a) contains a structural unit represented by the general formula (NB) as the structural unit A. This structural unit (NB) is chemically robust. Therefore, the thioether group-containing (meth) acrylic resin (a) 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 thioether group-containing (meth) acrylic resin (a) is suitably used for producing films and filters for use in liquid crystal display devices and solid-state image pickup devices that require heat resistance. be able to.

In a preferred embodiment, the thioether group-containing (meth) acrylic resin (a) contains a structural unit represented by the general formula (1) as an essential configuration. Since the structural unit represented by the general formula (1) has at least two (meth) acryloyl groups, the (meth) acrylic resin (a) containing this has high sensitivity in the photolithography process.

In one embodiment, the thioether group-containing (meth) acrylic resin (a) is represented by the general formula (3) in addition to the structural unit represented by the formula (1) or the formula (2) as the structural unit B. It may include structural units. By including the structural unit represented by the general formula (3), the thioether group-containing (meth) acrylic resin (a) has high alkali solubility. As a result, the photosensitive resin composition containing the thioether group-containing (meth) acrylic resin (a) has excellent developability when subjected to a photolithography treatment using an alkaline aqueous solution as a developing solution.

In one embodiment, the thioether group-containing (meth) acrylic resin (a) is represented by the general formula (MA) in addition to the structural unit represented by the formula (1) or the formula (2) as the structural unit B. It may include structural units. The structural unit represented by the general formula (MA) is ring-opened with an alkaline developer to generate two carboxyl groups. Therefore, the thioether group-containing (meth) acrylic resin (a) containing the structural unit has excellent developability. When the thioether group-containing (meth) acrylic resin (a) contains the structural unit represented by the general formula (MA), the general formula (MA) in all the structural units of the thioether group-containing (meth) acrylic resin (a). ) Is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

In one embodiment, the thioether group-containing (meth) acrylic resin (a) may comprise structural unit C derived from a monomer polymerizable with the general formula (NBm) and maleic anhydride. The structural unit C is, for example, substituted or unsubstituted, inden, maleimide, styrene, acenaphtylene, norbornadiene, dihydrofuran, terpene compound (eg, pinen, limonene, etc.), linear alkene (eg, pentene, etc.), cyclic alkene (eg, pentene, etc.). For example, cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth) acrylic acid compounds (eg, methyl methacrylate, etc.) It is a structural unit derived from methyl acrylate), vinyl acetate, vinyl ether (for example, 2-hydroxyethyl vinyl ether, etc.). Examples of the substituent that these monomers can have include an alkyl group and an aryl group. More specifically, examples of the substituted indene include methyl indene and the like. Examples of the substituted maleimide include cyclohexylmaleimide and phenylmaleimide. Examples of the substituted styrene include methylstyrene and vinyltoluene.

Of these, the structural unit C is preferably a structural unit represented by the general formula (4) (a divalent structural unit derived from a substituted or unsubstituted inden) or a structural unit represented by the general formula (5). A divalent structural unit derived from a substituted or unsubstituted maleimide), a structural unit represented by the general formula (6) (a divalent structural unit derived from a substituted or unsubstituted styrene), or a general formula (a divalent structural unit). 7) Includes a structural unit (a divalent structural unit derived from a substituted or unsubstituted norbornadiene) represented by.

In the general formula (4), R ¹ and R ² independently represent a hydrogen atom, an alkyl group or an aryl group, respectively. In the general formula (5), R ³ represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (6), R ⁴ to R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (7), 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 (NB) constituting the thioether group-containing (meth) acrylic resin (a), the organic group having 1 to 30 carbon atoms capable of constituting R ¹ to R ⁴ is substituted or absent. Substituent, linear or branched alkyl having 1 to 30 carbon atoms can be mentioned, and more specifically, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group and a cycloalkyl group. , An alkoxy group, a heterocyclic group, a carboxyl group and the like.

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 (NB), hydrogen or an alkyl group is preferable as ^R1 , ^R2 , R3 and ^{R4 ,} and hydrogen is more preferable.
The hydrogen atom in the organic group having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ may be substituted with an arbitrary atomic group. 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 , R ² , R ³ and R ⁴ .
In the structural unit represented by the general formula (NB), a ₁ is preferably 0 or 1, more preferably 0.

The proportion of the structural unit represented by the general formula (NB) in the total structural units of the thioether group-containing (meth) acrylic resin (a) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%. More preferably, it is 40 to 60 mol%.

In one embodiment, the thioether group-containing (meth) acrylic resin (a) is a structural unit represented by the general formula (1), in other words, two or more (meth) acryloyl groups (-C (= O) -CH. = Having one or both of the structural unit containing CH ₂ ) and the structural unit represented by the general formula (2) increases the sensitivity of the thioether group-containing (meth) acrylic resin (a) in the exposure treatment. It is preferable because it can be improved.

In the structural unit represented by the general formula (1) that can constitute the thioether group-containing (meth) acrylic resin (a), R ^p is a group containing two or more (meth) acryloyl groups, and is preferably (). It is a group containing 2 to 6 (meth) acryloyl groups, and more preferably a group containing 3 to 5 (meth) acryloyl groups. By optimizing the number of (meth) acryloyl groups contained in ^Rp , the sensitivity of the thioether group-containing (meth) acrylic resin (a) containing these groups 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 thioether group-containing (meth) acrylic resin (a) and the alkali solubility. Further, the heat resistance of the thioether group-containing (meth) acrylic resin (a) 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 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 thioether group-containing (meth) acrylic resin (a) contains the structural unit represented by the general formula (1), the general formula (1) in all the structural units of the thioether group-containing (meth) acrylic resin (a). ) 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 thioether group-containing (meth) acrylic resin (a), ^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, the curing tends to be insufficient, so that the thioether group-containing (meth) acrylic resin (a) is a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). It is preferable to include either or both, whereby 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 thioether group-containing (meth) acrylic resin (a) contains the structural unit represented by the general formula (2), the general formula (2) in all the structural units of the thioether group-containing (meth) acrylic resin (a). The ratio of the structural unit represented by is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

Further, when the thioether group-containing (meth) acrylic resin (a) contains both the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), the thioether group-containing (meth) acrylic resin (meth) is contained. ) The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the acrylic resin (a) is the thioether group-containing (meth) acrylic resin (a). ) Is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 10 to 40 mol% based on all the structural units constituting the above.

The content (ratio) of each structural unit contained in the thioether group-containing (meth) acrylic resin (a) is the amount of the raw material charged (molar amount) used when synthesizing the polymer, and the raw material remaining after the synthesis. It can be estimated / calculated from the quantity, the presence of peaks in various spectra (for example, IR spectrum, ¹ H-NMR spectrum, ¹³ C-NMR spectrum), peak area, and the like.

In the thioether group-containing (meth) acrylic resin (a) represented by 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 above-mentioned organic group having 1 or more and 30 or less carbon atoms constituting R ¹ to R ⁴ .

In the thioether group-containing (meth) acrylic resin (a) represented by the general formula (P'), Y is a 1- to hexavalent carbon number of 1 to 30 derived from a bifunctional or higher thiol group-containing compound. It is an organic group (i). 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. ] Combine 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 may have a thioether group-containing (meth) acrylic resin (a). Can be obtained as a mixture of the respective resins having a number of n + m (number of bonds) of 1 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 to 30 carbon atoms is 1 to 6 valences, preferably 2 to 6 valences, and more preferably 3 to 6 valences from the viewpoint of the effect of the present invention.

The 1- to hexavalent organic group (i) 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 organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms include an alkyl group and an alkenyl group having 1 to 6 thioether groups (-S- * (* is a bond)). Examples thereof include an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group and a 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.

Examples of the bifunctional or higher functional thiol group-containing compound include compounds represented by the following chemical formulas (s-1) to (s-20).

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.
The organic group (i) having 1 to 6 valences having 1 or more and 30 or less carbon atoms has a thioether group (-S- * (* is a bond)) derived from the thiol group of these thiol group-containing compounds as a terminal. It has and binds to structural units in [] n and structural units in [] m via thioether groups. 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.

The thioether group-containing (meth) acrylic resin (a) of the present embodiment is a tetrafunctional (tetravalent) thiol group-containing compound represented by the chemical formula (s-2) as the bifunctional or higher functional thiol group-containing compound. When used, for example, it can have a structure represented by the following general formula (I).

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 of binding to four structural units in [] via a thioether group derived from four mercapto groups of the compound represented by the chemical formula (s-2). 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 thioether group-containing (meth) acrylic resin (a) 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 thioether group-containing (meth) acrylic resin (a) is, for example, 1,000 to 15,000, preferably 1,500 to 12,000, and more preferably 2,000 to 10,000. , More preferably 3,000 to 8,000. By appropriately adjusting the weight average molecular weight, the sensitivity and the solubility in an alkaline developer can be adjusted.

The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the thioether group-containing (meth) acrylic resin (a) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0. More preferably, it is 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the thioether group-containing (meth) acrylic resin (a) 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 thioether group-containing (meth) acrylic resin (a) is preferably 150 to 250 ° C, more preferably 170 to 230 ° C. The thioether group-containing (meth) acrylic resin (a) has a relatively high glass transition temperature mainly because it contains a structural unit represented by the general formula (NB). 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 content (ratio) of each structural unit contained in the thioether group-containing (meth) acrylic resin (a) of the present embodiment is the amount of raw material charged (molar amount) at the time of polymer synthesis and the amount of raw material remaining after synthesis. , Can be estimated / calculated from the peak area of various spectra (for example, the peak area of ¹ H-NMR).

<Manufacturing method of thioether group-containing (meth) acrylic resin (a)>
The method for producing the above-mentioned thioether group-containing (meth) acrylic resin (a) will be described.
The thioether group-containing (meth) acrylic resin (a) can be produced (synthesized) by any method. The thioether group-containing (meth) acrylic resin (a) is, for example,
Step (I): The structural unit represented by the general formula (NB), 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): A 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 monomer ”) and / or a compound having a hydroxyl group and one (meth) acryloyl group (hereinafter referred to as“ monofunctional (meth) acrylic monomer ”) is reacted in the presence of a basic catalyst. The structural unit represented by the general formula (NB), 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 (1) and / or general. It can be produced by a step of preparing a thioether group-containing (meth) acrylic resin (a) containing a structural unit represented by the formula (2) and, in some cases, further containing a structural unit represented by the general formula (MA).

When the thioether group-containing (meth) acrylic resin (a) further contains the structural unit represented by the general formula (3), in the step (II), the structural unit represented by the general formula (NB), the general formula ( A polymer containing the structural unit represented by 1) and / or the structural unit represented by the general formula (2) and the structural unit represented by the general formula (MA) is prepared, and then the polymer is subjected to a base catalyst. In the presence of, the step of treating with water is carried out (step (III)).

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

(Step (I))
In the step (I), the structural unit represented by the general formula (NB), 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 a monomer represented by the general formula (NBm) and maleic anhydride is polymerized in the presence of the bifunctional or higher functional group-containing compound (thiol group). It can be carried out by performing addition polymerization). The definitions of R ¹ , R ² , R ³ and R ⁴ and a ₁ of the general formula (NBm) are the same as those of the general formula (NB). The same applies to the preferred embodiment.

Examples of the monomer represented by the formula (NBm) include norbornene, bicyclo [2.2.1] -hept-2-ene (conventional name: 2-norbornene), 5-methyl-2-norbornene, and 5-ethyl. -2-Norbornene, 5-Butyl-2-Norbornene, 5-Hexil-2-Norbornene, 5-Decil-2-Norbornene, 5-Allyl-2-Norbornene, 5- (2-Propenyl) -2-Norbornene, 5 -(1-Methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene Examples thereof include methyl-2-carboxylate and 5-norbornene-2,3-dicarboxylic acid anhydride. At the time of polymerization, the monomer represented by the formula (NBm) may be used alone or in combination of two or more.

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 a known compound can be used, and the monomer represented by the general formula (NBm) and maleic anhydride can be polymerized. Other monomers include substituted or unsubstituted inden, maleimide, styrene, acenaphtylene, norbornadiene, dihydrofuran, terpene compounds (eg, pinen, limonene, etc.), linear alkene (eg, pentene, etc.), cyclic alkene (cyclohexene, etc.). Etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth) acrylate compounds (eg, methyl methacrylate, methyl acrylate, etc.) ), Vinyl acetate, vinyl ether (for example, 2-hydroxyethyl vinyl ether, etc.) and the like. In the step (I), the monomer represented by the general formula (NBm), 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-20). 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 (NBm), 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 (NBm) 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 (NBm) 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 step (I) with a polyfunctional (meth) acrylic monomer and / or a monofunctional (meth) acrylic monomer in the presence of a basic catalyst. A part of the structural unit represented by (MA) is opened to form a structural unit represented by the formula (1) and / or a structural unit represented by the formula (2), and the general formula (NB) is formed. The structural unit represented by the above organic group (i) having 1 to 6 valent carbon atoms of 1 to 30 and the structural unit represented by the general formula (1) and / or represented by the general formula (2). A thioether group-containing (meth) acrylic resin (a) containing a structural unit and optionally a structural unit represented by the formula (MA) can be 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.

When obtaining a polymer containing both the structural unit represented by the general formula (NB) and the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), the above-mentioned next Add the polyfunctional (meth) acrylic monomer to the solution. 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 (NB) and the structural unit of the general formula (1) 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 monomer 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). Examples of the compound to be used. The definitions and specific embodiments of k, R, X ¹ , X ^1'and X ² 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 monomer in the presence of a basic catalyst, at least the structural unit of the general formula (NB), the general formula (1). ) And the structural unit of the general formula (2) 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 (1). Is done.

In addition, for example, by adding a monofunctional (meth) acrylic compound having a hydroxy group to the reaction system during the above heating, the above-mentioned general formula is added to the thioether group-containing (meth) acrylic resin (a). The structural unit represented by (3) can be generated.

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 (3) is generated in the thioether group-containing (meth) acrylic resin (a), the monofunctional (meth) acrylic compound having a hydroxy group is reacted from the beginning. It is preferable not to put it in the system but to add it to the reaction system.
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 (NB), 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 (III))
When the step (III) 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 (III), 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 (3) is formed. The structural unit represented by the general formula (NB), the structural unit represented by the general formula (1) and / or the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3). A thioether group-containing (meth) acrylic resin (a) 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, a thioether group-containing (meth) acrylic resin (meth) acrylic resin ( a) is the general formula (NB), the general formula (1) and / or the general formula (2), the organic group (i) having 1 to 6 valences having 1 to 30 carbon atoms, and the general formula (3). In addition to the structural unit, the structural unit represented by the general formula (MA) is included.

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

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

The thioether group-containing (meth) acrylic resin (a) of the present embodiment can be obtained by the above steps, but from the viewpoint of the effect of the present invention, further to remove unnecessary components other than the desired polymer, the following It is also possible to carry out the above steps as appropriate.

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 of the thioether group-containing (meth) acrylic resin (a) is purified by a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of the thioether group-containing (meth) acrylic resin (a) 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 organic solution of the thioether group-containing (meth) acrylic resin (a) obtained, 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 organic solution of the obtained polymer is heated under reduced pressure by a rotary evaporator to concentrate, and then the final solvent (PGMEA, etc.) is added and diluted repeatedly to contain the thioether group dissolved in the final solvent (meth). A polymer solution of the acrylic resin (a) can be obtained.

Further, the polymer solution may contain a monofunctional (meth) acrylic compound used for synthesizing the thioether group-containing (meth) acrylic resin (a). When the polymer solution contains a monofunctional (meth) acrylic compound, the peak area derived from the monofunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart is that of the thioether group-containing (meth) acrylic resin (a). By setting the amount to be 5 to 50% with respect to the peak area, particularly 10 to 35%, it is possible to achieve both good alkali solubility and sensitivity of the obtained photosensitive resin composition.

(Resin composition)
The resin composition of the present embodiment contains the above-mentioned polymer P. In a preferred embodiment, the resin composition of the present embodiment contains the thioether group-containing (meth) acrylic resin (a) in the above-mentioned resin composition of the present embodiment. Further, the resin composition of the present embodiment may contain various components depending on its use.
Each component will be described below.
When the resin composition of the present embodiment is used as a photosensitive resin composition, it contains the above-mentioned thioether group-containing (meth) acrylic resin (a) and a photosensitive agent. Hereinafter, the resin composition containing the photosensitive agent is referred to as a photosensitive resin composition.

Examples of the photosensitive agent used to impart photosensitivity to the 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-methylpropane-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) Oxym ester compounds such as oxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime); bis (η5-). 2,4-Cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium-based compounds such as titanium; p-dimethylaminobenzoic acid, p- Examples thereof include benzoic acid ester compounds such as diethylaminobenzoic acid; and acridin compounds such as 9-phenylacridin; and the like. 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 1000 parts by mass of the polymer P.

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. Further, since the yellowing of the photosensitive resin composition is suppressed, the article obtained by curing the photosensitive resin composition has transparency.

The photosensitive resin composition of the present embodiment may contain a compound having two or more (meth) acryloyl groups (polyfunctional (meth) acrylic compound). By including such a compound, the alkali solubility of the photosensitive resin composition is improved, the yellowing of the photosensitive resin composition is reduced, and a cured product having excellent transparency can be obtained. ..

Examples of the polyfunctional (meth) acrylic compound that may be used in the photosensitive resin composition of the present embodiment include a compound represented by the following formula (1bp) and a formula (1cp). Examples include, but are not limited to, compounds represented by the formula (1d-p). The definitions and specific embodiments of k, R, X ¹ , X ^1'and X ² in the formula (1bp) 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-p) are the same as those in the above formula (1c). N and R in the formula (1d-p) are the same as those in the above formula (1d). Y in formula (1bp), formula (1c-p) and formula (1d-p) is a hydrogen atom or (meth) acryloyl group, or a combination thereof.

The photosensitive resin composition of the present embodiment may contain a compound having one (meth) acryloyl group (monofunctional (meth) acrylic compound). The inclusion of the monofunctional (meth) acrylic compound improves the alkali solubility of the resulting resin composition and further reduces yellowing.

Examples of the monofunctional (meth) acrylic compound that may be used in the photosensitive resin composition 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).

Specific examples of the compound represented by the 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. Can be done.

When the polyfunctional (meth) acrylic compound is blended in the photosensitive resin composition of the present embodiment, the polyfunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart of the photosensitive resin composition is used. The derived peak area is preferably blended in an amount of 5 to 100% with respect to the peak area of the polymer P, more preferably blended in an amount of 10 to 90%, and blended in an amount of 15 to 80%. It is even more preferable that the mixture is blended in such an amount. The photosensitive resin composition obtained by blending the polyfunctional (meth) acrylic compound in the above range has excellent alkali solubility.

When the photosensitive resin composition of the present embodiment contains a monofunctional (meth) acrylic compound, the amount thereof is the monofunctional (meth) in the gel permeation chromatography (GPC) chart of the photosensitive resin composition. The peak area derived from the acrylic compound is preferably blended in an amount of 5 to 50% with respect to the peak area of the polymer P, and more preferably blended in an amount of 10 to 35%. The photosensitive resin composition obtained by blending the monofunctional (meth) acrylic compound in the above range has excellent alkali solubility.

When a polyfunctional (meth) acrylic compound and / or a monofunctional (meth) acrylic compound is blended in the photosensitive resin composition of the present embodiment, these (meth) acrylic compounds are resins having a (meth) acrylic group. It may be a monomer remaining when the compound is synthesized, or it may be added separately to the resin composition.

The photosensitive resin composition of the present embodiment may also contain a thiol group-containing compound. As the thiol group-containing compound, the thiol group-containing compound can be used. The photosensitive resin composition containing a thiol group-containing compound can be prepared by separately adding a thiol group-containing compound after synthesizing the thioether group-containing (meth) acrylic resin (a), or the above-mentioned mercapto group introduction reaction. A reaction solution containing an unreacted thiol group-containing compound remaining later can also be used. As a result, yellowing of the photosensitive resin composition is suppressed, and heat-resistant discoloration is improved. It is preferable to blend a compound having two or more thiol groups in order to improve the heat-resistant discoloration of the obtained photosensitive resin composition. Above all, it is more preferable to blend a polyfunctional thiol group-containing compound having 3 to 6 thiol groups in order to improve heat-resistant discoloration. The thiol group-containing compound may be primary or secondary. Further, the thiol group-containing compound may be used alone or in combination of two or more.

When the thiol group-containing compound is blended in the photosensitive resin composition of the present embodiment, the amount thereof is 0.25 to 20% by mass, preferably 0.5 to 15% by mass, based on the polymer P. It is more preferably 1 to 12% by mass. By using the thiol group-containing compound in an amount in the above range, the heat-resistant discoloration property can be improved while maintaining the sensitivity of the photosensitive resin composition.

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 chromate 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).

In one aspect, the photosensitive resin composition may contain a light-shielding agent. By containing a light-shielding agent, it can be preferably used as a material for forming a black matrix of a liquid crystal display device or a solid-state image sensor.
As the light-shielding agent, a known light-shielding agent can be used without particular limitation. For example, a black pigment such as carbon black, bone black, graphite, iron black, or titanium black can be used as a light-shielding agent.

When the photosensitive resin composition contains a light-shielding agent, the photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agent.
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).

The photosensitive resin composition typically contains a solvent. As the solvent, an organic solvent is preferably used. 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), and 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.

In one aspect, the photosensitive resin composition can 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 the following.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, 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 trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tetra (meth) acrylate, ethylene oxide Additional pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra. (Meta) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropanetri (meth) acrylate, ε-caprolactone-added dimethylolpropanetetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra Polyfunctional (meth) acrylates such as (meth) acrylates and ε-caprolactone-added dipentaerythritol hexa (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 isocyanurates.
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.

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 polymer P.

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. Inhibitors, matting agents, defoaming agents, leveling agents, surfactants, antistatic agents, dispersants, slip agents, surface modifiers, rocking agents, rocking aids, silane coupling agents, polyvalent phenols It may contain a component such as a compound.

(Film, color filter, black matrix, liquid crystal display device and solid-state image sensor)
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.
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.
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 0.1 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.

（一般式（ＮＢｍ）中、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ およびＲ ^４ は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ _１ は０、１または２である。）
２． 前記モノマー組成物は、置換または無置換の、インデン、マレイミド、スチレン、およびノルボルナジエンから選択される少なくとも１種を含む、１．に記載のポリマー。
３． 当該ポリマーは、前記ポリマー前駆体をさらに塩基性触媒の存在下、水で処理し、前記ポリマー前駆体に含まれる無水マレイン酸から誘導される構造単位を開環して得られる、１．または２．に記載のポリマー。
４． ２官能以上の前記チオール基含有化合物は、下記化学式（ｓ－１）～（ｓ－２０）から選択される少なくとも１種の化合物を含む、１．～３．のいずれかに記載のポリマー。

５． 重量平均分子量が１０００以上１５０００以下である、１．～４．のいずれかに記載のポリマー。
６． １．～５．のいずれかに記載のポリマーを含む、樹脂組成物。
７． ２つ以上の（メタ）アクリロイル基を有する化合物をさらに含む、６．に記載の樹脂組成物。
８． １つの（メタ）アクリロイル基を有する化合物をさらに含む、６．または７．に記載の樹脂組成物。
９． チオール基を有する化合物をさらに含む、６．～８．のいずれに記載の樹脂組成物。
１０． 前記チオール基を有する化合物が、少なくとも２つのチオール基を有する化合物である、９．に記載の樹脂組成物。
１１． カラーフィルタまたはブラックマトリクスの形成に用いられる、６．～１０．のいずれかに記載の樹脂組成物。
１２． 式（Ｐ'）で表される構造を有する、ポリマー。

（一般式（Ｐ'）中、
ｍは、０～５の整数であり、
ｎは、１～６の整数であり、
ｎ＋ｍは、１～６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以上であるり、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１～６価の炭素数１以上３０以下の有機基であり、
Ａは、一般式（ＮＢ）で表される構造単位を含み、
Ｂは、一般式（１）で表される構造単位、および一般式（２）で表される構造単位から選択される少なくとも１つの構造単位を含み、
Ｃは、二重結合を有する共重合性化合物から誘導される２価の構造単位を含み、
複数存在するＡ同士、Ｂ同士またはＣ同士は同一でも異なっていてもよく、
Ｑは、Ａ、ＢおよびＣと同一または異なる有機基を含む。）

（一般式（ＮＢ）中、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ およびＲ ^４ は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ _１ は０、１または２である。）

（一般式（１）中、Ｒ ^ｐ は、２以上の（メタ）アクリロイル基を有する基である。）

（一般式（２）中、Ｒ ^ｓ は、１つの（メタ）アクリロイル基を有する基である。））
１３． 前記一般式（Ｐ'）で表される構造が、式（Ｐ）で表される構造である、１２．に記載のポリマー。

（一般式（Ｐ）中、
ｎ、ならびにｐ、ｑおよびｒは、一般式（Ｐ'）における定義と同じであり、
Ｘ、Ｙ、Ａ、ＢおよびＣは、一般式（Ｐ'）における定義と同じである。）
１４． ２官能以上の前記チオール基含有化合物は、下記化学式（ｓ－１）～（ｓ－２０）から選択される少なくとも１種の化合物を含む、１２．または１３．に記載のポリマー。

１５． 前記Ｂが、式（３）で表される構造単位をさらに含む、１２．～１４．のいずれかに記載のポリマー。

１６． 前記Ｂが、式（ＭＡ）で表される構造単位をさらに含む、１２．～１５．のいずれかに記載のポリマー。

１７． 前記Ｃは、置換または無置換の、インデン、マレイミド、スチレン、およびノルボルナジエンから選択される少なくとも１種の化合物から誘導される２価の構造単位を含む、１２．～１６．のいずれかに記載のポリマー。
１８． 重量平均分子量が１０００以上１５０００以下である、１２．～１７．のいずれかに記載のポリマー。
１９． １２．～１８．のいずれかに記載のポリマーを含む、樹脂組成物。
２０． ２つ以上の（メタ）アクリロイル基を有する化合物をさらに含む、１９．に記載の樹脂組成物。
２１． １つの（メタ）アクリロイル基を有する化合物をさらに含む、１９．または２０．に記載の樹脂組成物。
２２． チオール基を有する化合物をさらに含む、１９．～２１．のいずれに記載の樹脂組成物。
２３． 前記チオール基を有する化合物が、少なくとも２つのチオール基を有する化合物である、２２．に記載の樹脂組成物。
２４． カラーフィルタまたはブラックマトリクスの形成に用いられる、１９．～２３．のいずれかに記載の樹脂組成物。
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. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like to the extent that the object of the present invention can be achieved are included in the present invention.
Hereinafter, an example of the embodiment will be added.
1. 1. A polymer precursor obtained by polymerizing a monomer composition containing a monomer represented by the following general formula (NBm) and maleic anhydride in the presence of a bifunctional or higher thiol group-containing compound is used as a basic catalyst. A polymer obtained by reacting with a compound having a hydroxyl group and two or more (meth) acryloyl groups and / or a compound having a hydroxyl group and one (meth) acryloyl group in the presence of.

(In the general formula (NBm), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. .)
2. 2. 1. The monomer composition comprises at least one selected from indene, maleimide, styrene, and norbornadiene, substituted or unsubstituted. The polymer described in.
3. 3. The polymer is obtained by further treating the polymer precursor with water in the presence of a basic catalyst and opening a structural unit derived from maleic anhydride contained in the polymer precursor. Or 2. The polymer described in.
4. The bifunctional or higher functional thiol group-containing compound comprises at least one compound selected from the following chemical formulas (s-1) to (s-20). ~ 3. The polymer described in any of.

5. 1. The weight average molecular weight is 1000 or more and 15000 or less. ~ 4. The polymer described in any of.
6. 1. 1. ~ 5. A resin composition comprising the polymer according to any one of the above.
7. 6. Further comprising a compound having two or more (meth) acryloyl groups. The resin composition according to.
8. 6. Further comprising a compound having one (meth) acryloyl group. Or 7. The resin composition according to.
9. 6. Further comprising a compound having a thiol group. ~ 8. The resin composition according to any of the above.
10. 9. The compound having a thiol group is a compound having at least two thiol groups. The resin composition according to.
11. Used to form color filters or black matrices, 6. ~ 10. The resin composition according to any one of.
12. A polymer having a structure represented by the formula (P').

(In the general formula (P'),
m is an integer from 0 to 5 and
n is an integer of 1 to 6 and
n + m is 1 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 a 1- to hexavalent organic group having 1 to 6 carbon atoms and 30 or less carbon atoms derived from a bifunctional or higher functional thiol group-containing compound.
A includes a structural unit represented by the general formula (NB).
B comprises at least one structural unit selected from the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).
C comprises a divalent structural unit derived from a copolymer having a double bond.
A plurality of A's, B's, or C's may be the same or different.
Q contains the same or different organic groups as A, B and C. )

(In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. .)

(In the general formula (1), R ^p is a group having two or more (meth) acryloyl groups.)

(In the general formula (2), R ^s is a group having one (meth) acryloyl group.))
13. 12. The structure represented by the general formula (P') is a structure represented by the formula (P). The polymer described in.

(In general formula (P),
n, and p, q, and r are the same as the definitions in the general formula (P').
X, Y, A, B and C are the same as the definitions in the general formula (P'). )
14. The bifunctional or higher functional thiol group-containing compound comprises at least one compound selected from the following chemical formulas (s-1) to (s-20). Or 13. The polymer described in.

15. 12. The B further includes a structural unit represented by the formula (3). ~ 14. The polymer described in any of.

16. 12. The B further includes a structural unit represented by the formula (MA). ~ 15. The polymer described in any of.

17. 12. The C comprises a substituted or unsubstituted divalent structural unit derived from at least one compound selected from indene, maleimide, styrene, and norbornadiene. ~ 16. The polymer described in any of.
18. 12. The weight average molecular weight is 1000 or more and 15000 or less. ~ 17. The polymer described in any of.
19. 12. ~ 18. A resin composition comprising the polymer according to any one of the above.
20. 19. Further comprising a compound having two or more (meth) acryloyl groups. The resin composition according to.
21. 19. Further comprising a compound having one (meth) acryloyl group. Or 20. The resin composition according to.
22. 19. Further comprising a compound having a thiol group. ~ 21. The resin composition according to any of the above.
23. 22. The compound having a thiol group is a compound having at least two thiol groups. The resin composition according to.
24. Used to form color filters or black matrices, 19. ~ 23. The resin composition according to any one of.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. The present invention is not limited to the examples.

The compounds used in the examples may be indicated by the following abbreviations or trade names.
-MA: Maleic anhydride-NB: 2-Norbornene-MEK: Methyl ethyl ketone-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% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

TMMP: Trimethylolpropanetris (3-mercaptopropionate), a thiol group-containing compound of the above formula (s-1) (manufactured by SC Organic Chemistry Co., Ltd.)
-PEMP: Pentaerythritol tetrakis (3-mercaptopropionate), thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemistry Co., Ltd.)
DPMP: Dipentaerythritol hexakis (3-mercaptopropionate), thiol group-containing compound of the above formula (s-3) (manufactured by SC Organic Chemistry Co., Ltd.)
TEMPIC: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, a thiol group-containing compound of the above formula (s-5) (manufactured by SC Organic Chemistry Co., Ltd.)
-PEPT: Trimethylolpropanetris (3-mercaptopropionate), a thiol group-containing compound of the above formula (s-6) (manufactured by SC Organic Chemistry Co., Ltd.)
-Carens MT (registered trademark) PE1: Pentaerythritol tetrakis (3-mercaptobutyrate), thiol group-containing compound of the above formula (s-9) (manufactured by Showa Denko KK)
EGFP-4: Tetraethylene glycol bis (3-mercaptopropionate), thiol group-containing compound of the above formula (s-4) (manufactured by SC Organic Chemistry Co., Ltd.)

<Synthesis of raw material polymer>
(Synthesis of raw material polymer 1)
588.36 g (6.0 mol) of maleic anhydride, 564.90 g (6.0 mol) of 2-norbornene and dimethyl 2,2'-in an appropriately sized reaction vessel equipped with a stirrer and cooling tube. Azobis (2-methylpropionate) 55.26 g (0.24 mol) was weighed in. These were dissolved in a mixed solvent consisting of 1716.8 g of methyl ethyl ketone and 188.3 g of toluene to prepare a solution.
The solution is aerated with nitrogen for 30 minutes to remove oxygen, then heated at a temperature of 65 ° C. for 1.5 hours with stirring, and then heated at 80 ° C. for 6 hours to obtain maleic anhydride. And 2-norbornene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 14230.2 g of methanol to precipitate a white solid. The obtained white solid is further washed with 3557.5 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 1) 1027.2 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 7236, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.83. there were.

(Synthesis of raw material polymer 2)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 191.47 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and TMMP (6.38 g, 0.016 mol) in 16.23 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 2) 67.0 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3300, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.74. there were.

[Amount of sulfur in raw material polymer]
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 TMMP disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that TMMP was incorporated into the polymer.
The elemental analysis method is as follows.
-Test items 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 and used as a test solution.
(3) A test solution and a standard solution are introduced into an ion chromatograph analyzer, the concentration of sulfate ion is determined by a calibration curve method, and the amount of sulfur contained in the sample is calculated.
-Device used Dionex ICS-3000 type ion chromatograph

(Synthesis of raw material polymer 3)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 193.75 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and PEMP (3.91 g, 0.008 mol) in 16.42 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 3) 64.8 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3400, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.87. there were.

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.

(Synthesis of raw material polymer 4)
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 4]
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 1 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 4.

Further, in the ¹³ C-NMR measurement of the raw material polymer 1, 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 4 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 4 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) The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask combustion and ion chromatography, and it was confirmed that 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 4 was 2.4 wt%.

(Synthesis of raw material polymer 5)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 182.94 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and PEMP (15.64 g, 0.032 mol) in 15.51 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 5) 72.8 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 2000, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.58. there were.
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.

(Raw material polymer 6)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 185.80 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and DPMP (12.53 g, 0.016 mol) in 15.75 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 6) 77.3 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3100, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.71. there were.
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, the peak derived from DPMP disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and it was confirmed that DPMP was incorporated into the polymer.

(Raw material polymer 7)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 189.60 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and TEMPIC (8.41 g, 0.016 mol) in 15.75 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 7) 71.1 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3120, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.80. there were.
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 TEMPIC disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that TEMPIC was incorporated into the polymer.

(Raw material polymer 8)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 192.06 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and PEPT (5.74 g, 0.016 mol) in 15.75 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 8) 65.2 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3536, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.64. there were.
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. It was also confirmed that the peak derived from PEPT disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that PEPT was incorporated into the polymer.

(Raw material polymer 9)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 193.34 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and Karens MT® PE1 (4.36 g, 0.008 mol) in 15.75 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 9) 65.4 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 3120, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.76. there were.
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. It was also confirmed that the peak derived from Calends MT (registered trademark) PE1 disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that Calends MT (registered trademark) PE1 was incorporated into the polymer.

(Raw material polymer 10)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 189.32 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and Karens MT® PE1 (8.72 g, 0.016 mol) in 15.75 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 10) 64.5 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 2848, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.45. there were.
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. It was also confirmed that the peak derived from Calends MT (registered trademark) PE1 disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that Calends MT (registered trademark) PE1 was incorporated into the polymer.

(Raw material polymer 11)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 181.28 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and Karens MT® PE1 (17.43 g, 0.032 mol) in 15.75 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 11) 67.3 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 2005, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.45. there were.
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. It was also confirmed that the peak derived from Calends MT (registered trademark) PE1 disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and that Calends MT (registered trademark) PE1 was incorporated into the polymer.

(Raw material polymer 12)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 50.21 g (2-norbornene equivalent 37.66 g, 0.400 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MAN, 39.22 g). , 0.400 mol) and 202.18 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). A solution prepared by dissolving 3.68 g, 0.016 mol) and EGFP-4 (11.90 g, 0.032 mol) in 16.23 g of MEK was 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 1228.8 g of methanol to precipitate a white solid. The obtained white solid is further washed with 307.2 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 12) 64.5 g was obtained.
As a result of measuring the obtained polymer by gel permeation chromatography (GPC), the weight average molecular weight Mw was 2926, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.57. there were.
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, the peak derived from EGFP-4 disappeared in the GPC measurement of the reaction solution before the dropping of methanol, and it was confirmed that EGFP-4 was incorporated into the polymer.

<Preparation of resin composition>
(Formulation Example 1)
A resin mixture containing a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound and the polymer P1 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 (0.312 mol in terms of MA) 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 of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was 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 performed 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 were ring-opened polymer P1 with A-TMM-3LM-N, 4-HBA and water, and the residual (free) A-TMM-3LM-N and A resin mixture (resin composition) 1 containing residual (free) 4-HBA was obtained.
The obtained resin composition 1 was analyzed by a gel permeation chromatography method, and the amount of the polymer P1, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the polymer. The weight average molecular weight and polydispersity of P1 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 P 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 P: 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).

(Formulation Example 2)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 2 is used instead of the raw material polymer 1. A resin composition 2 containing the ringed polymer P2 was prepared.
GPC measurement was carried out on the obtained resin composition 2 to measure the weight average molecular weight and the degree of polydispersity of the polymer P2.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 2 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 3)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 3 is used instead of the raw material polymer 1. A resin composition 3 containing the ringed polymer P3 was prepared.
GPC measurement was carried out on the obtained resin composition 3 to measure the weight average molecular weight and the degree of polydispersity of the polymer P3.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 3 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 4)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 4 is used instead of the raw material polymer 1. A resin composition 4 containing the ringed polymer P4 was prepared.
GPC measurement was carried out on the obtained resin composition 4 to measure the weight average molecular weight and the degree of polydispersity of the polymer P4.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 4 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 5)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 5 is used instead of the raw material polymer 1. A resin composition 5 containing the ringed polymer P5 was prepared.
GPC measurement was carried out on the obtained resin composition 5 to measure the weight average molecular weight and the degree of polydispersity of the polymer P5.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 5 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 6)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 6 is used instead of the raw material polymer 1. A resin composition 6 containing the ringed polymer P6 was prepared.
GPC measurement was carried out on the obtained resin composition 6 to measure the weight average molecular weight and the degree of polydispersity of the polymer P6.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 6 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 7)
Polymer P7 was prepared by ring-opening the MA unit of the raw material polymer 1 with a monofunctional (meth) acrylic compound. The details will be described below.
First, 18.44 g of MEK was added to 10.00 g (MA equivalent of 0.052 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 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 12 hours.
From the above, 9.5 g of polymer P7 was obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with 4-HBA.
GPC measurement was carried out on the obtained polymer P7 to measure the weight average molecular weight and the degree of polydispersity of the polymer P7. 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 P7. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted monofunctional (meth) acrylic compound.

(Formulation Example 8)
Polymer P8 was prepared by ring-opening the MA unit of the raw material polymer 4 with a monofunctional (meth) acrylic compound. The details will be described below.
First, 18.44 g of MEK was added to 10.00 g (MA equivalent of 0.052 mol) of the raw material polymer 4 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 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 12 hours.
As described above, 8.7 g of polymer P8 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with 4-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.

(Formulation Example 9)
A resin mixture containing the polymer P9 in which the MA unit of the raw material polymer 4 was ring-opened with a monofunctional (meth) acrylic compound was prepared. The details will be described below.
First, 18.44 g of MEK was added to 10.00 g (MA equivalent of 0.052 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 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 in the same procedure as in Preparation Example 1 to obtain a resin composition 9.
For the obtained resin composition 9, GPC measurement was carried out to measure the amount of the polymer P9 and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and the degree of polydispersity of the polymer P9. .. The results are shown in Table 1.

(Formulation Example 10)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 7 is used instead of the raw material polymer 1. A resin composition 10 containing the ringed polymer P10 was prepared.
GPC measurement was carried out on the obtained resin composition 10 to measure the weight average molecular weight and the degree of polydispersity of the polymer P10.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 10 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 11)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 8 is used instead of the raw material polymer 1. A resin composition 11 containing the ringed polymer P11 was prepared.
GPC measurement was carried out on the obtained resin composition 11 to measure the weight average molecular weight and the degree of polydispersity of the polymer P11.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 11 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 12)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 9 is used instead of the raw material polymer 1. A resin composition 12 containing the ringed polymer P12 was prepared.
GPC measurement was carried out on the obtained resin composition 12 to measure the weight average molecular weight and the degree of polydispersity of the polymer P12.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 12 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 13)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 10 is used instead of the raw material polymer 1. A resin composition 13 containing the ringed polymer P13 was prepared.
GPC measurement was carried out on the obtained resin composition 13, and the weight average molecular weight and the polydispersity of the polymer P13 were measured.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 13 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 14)
The MA unit of the raw material polymer 2 is opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water in the same manner as in Formulation 1, except that the raw material polymer 11 is used instead of the raw material polymer 1. A resin composition 14 containing the ringed polymer P14 was prepared.
GPC measurement was carried out on the obtained resin composition 14, and the weight average molecular weight and the degree of polydispersity of the polymer P14 were measured.
Further, the amount of the free (meth) acrylic compound contained in the obtained resin composition 14 was measured by gel permeation chromatography. The results are shown in Table 1.

(Formulation Example 15)
A resin composition 15 containing a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and a polymer P16 ring-opened with water using the MA unit of the raw material polymer 4 was prepared. The details will be described below.
First, 100.30 g of MEK was added to 60.00 g (MA equivalent 0.312 mol) of the raw material polymer 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, 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 of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was 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 subsequently solvent substitution were carried out in the same procedure as in Formulation Example 1 to obtain a resin composition 15. The obtained resin composition 15 was subjected to GPC measurement, and the amount of the polymer P15, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight of the polymer P15. The average molecular weight and polydispersity were measured. The results are shown in Table 1.

(Formulation Examples 16 to 29)
The additives shown in Table 1 were mixed with the resin composition 15 in an amount shown in "Additive amount" in Table 1 to prepare resin compositions 16 to 29. Here, the amount of the additive was mixed by weight% with respect to the solid content (polymer P15, polyfunctional (meth) acrylic compound) in the resin composition 15.
The details of the "additives" shown in Table 1 are as follows.
-PEMP: Pentaerythritol tetrakis (3-mercaptopropionate), thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemistry Co., Ltd.)
-TMMP: Trimethylolpropanetris (3-mercaptopropionate), thiol group-containing compound of the above formula (s-1) (manufactured by SC Organic Chemistry Co., Ltd.)
-Calens MT (registered trademark) PE1: Pentaerythritol tetrakis (3-mercaptobutyrate), thiol group-containing compound of the above formula (s-9) (manufactured by Showa Denko KK)
-Carens MT (registered trademark) TPMB: Trimethylolpropane Tris (3-mercaptobutyrate), thiol group-containing compound of the above formula (s-8) (manufactured by Showa Denko KK)
-Light Ester P-1M: 2-Metachloroxyethyl Acid Phosphate, manufactured by Kyoeisha Chemical Co., Ltd.-KBM-3066: 1,6-bis (trimethoxysilyl) hexane, manufactured by Shin-Etsu Silicone Co., Ltd.-KBM-5103: 3-Acry Roxypropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.

(Formulation Example 30)
A resin composition 30 containing a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and a polymer P16 ring-opened with water using the MA unit of the raw material polymer 4 was prepared. The details will be described below.
First, 100.30 g of MEK was added to 60.00 g of the raw material polymer (0.312 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, 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 of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was 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 subsequently solvent substitution were carried out in the same procedure as in Formulation Example 1 to obtain a resin composition 30. The obtained resin composition 30 was subjected to GPC measurement, and the amount of the polymer P16, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight of the polymer P16. The average molecular weight and polydispersity were measured. The results are shown in Table 1.

(Formulation Example 31)
A resin composition 31 containing a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and a polymer P17 ring-opened with water using the MA unit of the raw material polymer 2 was prepared. The details will be described below.
First, 99.93 g of MEK was added to 60.00 g (MA equivalent 0.312 mol) of the raw material polymer to prepare a solution. Then, 77.49 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and 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 of the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was 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 in the same procedure as in Formulation Example 1. Then, it was further purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an 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 12 hours.
As described above, a polymer P17 in which the MA unit of the raw material polymer 2 was ring-opened with a trifunctional (meth) acrylic compound, a monofunctional (meth) acrylic compound and water was prepared.
GPC measurement was carried out on the obtained polymer P17 to measure the weight average molecular weight and the degree of polydispersity of the polymer P17. The results are shown in Table 1.
Moreover, the disappearance of the peaks of the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound used was confirmed by GPC measurement of the polymer P17. As a result, it was confirmed that the obtained polymer P17 did not contain the unreacted polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound.

Table 1 below also shows the components used in each synthesis example and the amount charged thereof (maleic anhydride (MA) conversion).

(Examples 1 to 13, 28 to 29, Comparative Examples 1 to 3)
In each Example and Comparative Example, a resin composition was prepared and evaluated for the following items.
<Evaluation>
[Alkaline dissolution rate of resin composition]
The polymers P7, P8 and P17 obtained in Formulation Examples 7, 8 and 31 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 resin compositions 1 to 6, 9 to 15, 30 obtained in Formulation Examples 1 to 6, 9 to 15, 30 are spin-coated on the wafer, PGMEA is dried, and the temperature is 100 ° C. By prebaking for 2 minutes, a resin film having a film thickness of about 2 μm was prepared.
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 140 nm / s or more, it can be used as a photosensitive material without any problem. In particular, if it is 350 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 90% 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 P7, P8, P17 (polymers P7, P8, P17 of Formulation Examples 7, 8, 31) or resin compositions 1 to 6, 9 to 15, 30: 100 parts by mass (here, resin compositions 1 to 6). , 9 to 15 and 30 were weighed so that the solid content (total amount of polymers P1 to P6, P9 to 15, P16) and polyfunctional (meth) acrylic compound was 100 parts by mass. )
-Polyfunctional acrylate (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass-Photopolymerization initiator (BASF, Ingacure OXE01): 5 parts by mass-Adhesion aid (Shin-Etsu Chemical Co., Ltd.) Industrial Co., Ltd., KBM-403): 1 part by mass ・ Surfactant (DIC Co., Ltd., F-556): 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 90% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 1. If the exposure amount at which the residual film ratio is 90% or more is 50 mJ / cm ² or less, it can be used as a photosensitive composition without any problem, and if it is 30 mJ / cm ² or less, it is considered to be particularly good. be able to.

[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-mentioned 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 (%) = (thin film thickness of thin film B / film thickness of thin film A at each exposure amount) × 100

(Remaining film ratio at an exposure of 10 mJ / cm ² )
The photosensitive resin composition prepared in the above-mentioned 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 of a light blocking 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 (%) = (thin film thickness of thin film B / film thickness of thin film A at each exposure amount) × 100

[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 250 nm / s or more, it can be used as a photosensitive material without any problem, and if it is 400 nm / s or more, it can be considered that the developability is 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. If the yellow index is 1.20 or less, the heat-resistant discoloration property can be considered to be good, if it is 1.10 or less, it can be considered to be better, and if it is 0.90 or less, it is particularly good. Can be regarded as.

(Examples 14 to 27)
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.
16 to 29: 100 parts by mass of the resin composition (weighed so that the total amount of the solid content (polymer P15, polyfunctional (meth) acrylic compound, additive shown in Table 1) was 100 parts by mass).
-Polyfunctional acrylate (Dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass-Photopolymerization initiator (BASF, Ingacure OXE01): 5 parts by mass-Adhesion aid (Shin-Etsu Chemical Co., Ltd.) Industrial Co., Ltd., KBM-403): 1 part by mass ・ Surfactant (DIC Co., Ltd., F-556): 0.5 part by mass

Regarding the obtained photosensitive resin composition, the above-mentioned "sensitivity evaluation 1 of the photosensitive resin composition (exposure amount at which the residual film ratio is 90% or more)" and "sensitivity evaluation 2 of the resin composition (at a low exposure amount)" "Remaining film ratio after exposure)", "Alkaline dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)", and "Yellow index" were measured and evaluated in the same manner.

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 90% or more is 50 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. Further, a photosensitive resin composition was compared with Examples 14 to 21 in which a thiol group-containing compound was blended as an additive and Examples 22 to 27 (reference) in which a compound other than the thiol group-containing compound was blended as an additive. It was found that by blending a thiol group-containing compound with the compound, yellowing is further suppressed, heat-resistant discoloration is further improved, the exposure amount at which the residual film ratio is 90% or more is smaller, and therefore the sensitivity is further improved. rice field.

<Making color filters>
A colored photosensitive resin composition was prepared by further adding an appropriate amount of the pigment dispersion liquid NX-061 (manufactured by Dainichiseika Kogyo Co., Ltd., green) to the photosensitive resin compositions prepared in Examples 1 to 21.
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 21.
A black matrix could be formed by forming a film on the substrate and performing exposure, alkaline development, and the like.

This application has priority based on Japanese application Japanese Patent Application No. 2019-189164 filed on October 16, 2019 and Japanese application Japanese Patent Application No. 2020-135597 filed on August 11, 2020. Claim and incorporate all of its disclosure here.

Claims (7)

A step of polymerizing a monomer composition containing a monomer represented by the following general formula (NBm) and maleic anhydride in the presence of a bifunctional or higher thiol group-containing compound to obtain a polymer precursor.
The polymer precursor is reacted with a compound having a hydroxyl group and two or more (meth) acryloyl groups and / or a compound having a hydroxyl group and one (meth) acryloyl group in the presence of a basic catalyst. A method for producing a polymer, which comprises a step of obtaining the polymer.

(In the general formula (NBm), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. .) The method for producing a polymer according to claim 1, wherein the monomer composition comprises at least one selected from indene, maleimide, styrene, and norbornadiene, which is substituted or unsubstituted. The polymer precursor was reacted with a compound having a hydroxyl group and two or more (meth) acryloyl groups and / or a compound having a hydroxyl group and one (meth) acryloyl group in the presence of a basic catalyst. The production of the polymer according to claim 1 or 2, further comprising a step of treating with water in the presence of a basic catalyst to open a ring of structural units derived from maleic anhydride contained in the polymer precursor. Method. The polymer according to any one of claims 1 to 3, wherein the bifunctional or higher functional thiol group-containing compound contains at least one compound selected from the following chemical formulas (s-1) to (s-20). Method.

The precursor polymer has a structural unit derived from a monomer represented by the general formula (NBm), a structural unit derived from maleic anhydride, and an organic group derived from the bifunctional or higher thiol group-containing compound. The method for producing a polymer according to any one of claims 1 to 4, which comprises. The polymer has a structural unit derived from a monomer represented by the general formula (NBm), an organic group derived from the bifunctional or higher thiol group-containing compound, a structural unit derived from maleic anhydride, a hydroxyl group, and the like. A structural unit obtained by reaction with the compound having two or more (meth) acryloyl groups and / or the compound having a hydroxyl group and one (meth) acryloyl group, and the bifunctional or higher thiol group-containing compound. The method for producing a polymer according to any one of claims 1 to 5, which comprises an organic group derived from. The method for producing a polymer according to any one of claims 1 to 6, wherein the polymer has a weight average molecular weight of 1000 or more and 15,000 or less.

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