JP2022046309A - Polymer solution, photosensitive resin composition, and use thereof - Google Patents

Abstract

To provide a polymer solution giving a hardened resin excellent in sensibility, excellent in transparency with reduced yellowing, and excellent in adhesion to a substrate or the like.SOLUTION: A polymer solution contains (A) a polymer containing two kinds of structural units, namely, a structural unit of acrylic ester having a hydroxy group and a (meth) acryloyl group bonded through an alkylene group, on an ester residue, and a structural unit of acrylic ester having a (meth) acryloyl group on an ester residue, and (B) a compound or the like having a thiol group and an alkoxy group.SELECTED DRAWING: None

Description

The present invention relates to polymer solutions, photosensitive resin compositions and their uses.

A liquid crystal display device or a solid-state image sensor usually includes a color filter or a black matrix. A photosensitive resin composition is often used for forming a color filter or a black matrix.

For example, claim 1 of Patent Document 1 states that an alkali-soluble resin having an acidic group and two or more different polymerizable unsaturated groups in at least a side chain, a polymerizable compound, and a photopolymerization initiator. A photosensitive resin composition containing the above 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.

Patent Document 2 describes a resin composition containing a resin containing an epoxy group and an acid group, a polybasic acid monoester of a hydroxyl group-containing polyfunctional (meth) acrylate, and a solvent, wherein the epoxy group and the acid group are contained. Described is a resin composition characterized in that the epoxy group is 0.5 to 3.0 mol with respect to 1 mol of the acid group in the resin containing the above.

Patent Document 3 discloses a method for producing a polymer, which comprises a step of reacting a precursor polymer having a maleic anhydride moiety ringed with a compound having an epoxy group. As a compound having an epoxy group, glycidyl methacrylate has been described.

International Publication No. 2012/147706 International Publication No. 2016/103844 International Publication No. 2017/154439

As a photosensitive resin composition for forming a color filter or a black matrix, a polymer 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 (the better the sensitivity) of the photosensitive resin composition, the shorter the time required for exposure, and the higher the productivity can be improved.

Further, the cured product of the photosensitive resin composition needs to be excellent in transparency and heat-resistant discoloration by suppressing yellowing. Further, when a photosensitive resin composition is applied to a substrate or the like, the obtained coating film is exposed and developed to form a pattern, adhesion to the substrate or the like is obtained from the viewpoint of product yield and product reliability. Is required to be excellent.
In Patent Documents 1 to 3, there is room for improvement in these characteristics.

By improving the polymer and formulation used in the photosensitive resin composition, the present inventors have good sensitivity, high heat-resistant discoloration with suppressed yellowing, and excellent adhesion to the substrate. We have found that a cured resin product can be obtained, and have reached the present invention.
That is, the present invention can be shown below.

（一般式（１－１）中、Ｚは１以上の（メタ）アクリロイル基を含む基である。Ｑは水素原子または置換または未置換の炭素数１～６のアルキル基である。Ｘは酸素原子、置換または未置換の炭素数１～４のアルキレン基を表し、Ｑの前記アルキル基とＸの前記アルキレン基の何れかの炭素原子とが結合して環を形成してもよい。一般式（１－２）中、Ｒ^Ａは、１以上の（メタ）アクリロイル基を含む基である。） According to the present invention
(A) A polymer containing a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-2).
(B) A compound having a thiol group and an alkoxy group, or an oligomer thereof,
A polymer solution containing the above can be provided.

(In the general formula (1-1), Z is a group containing one or more (meth) acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X is oxygen. It represents an atomic, substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. In (1-2), ^RA is a group containing one or more (meth) acryloyl groups.)

According to the present invention
With the polymer solution
With polyfunctional (meth) acrylate monomer,
With a photopolymerizable initiator,
A photosensitive resin composition comprising the above can be provided.

According to the present invention
A cured product of the photosensitive resin composition can be provided.

According to the polymer solution of the present invention, it is possible to provide a cured resin product having good sensitivity, reduced yellowing, excellent transparency, and excellent adhesion to a substrate or the like. In other words, the polymer solution of the present invention can provide a cured resin product having an excellent balance of these properties.

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. 6 is a ¹ H-NMR chart of the polymer P1 obtained in Example 1. This is an enlargement of the peak near 6.0 ppm in the ¹ H-NMR chart in Fig. 2.

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) acrylic group" in the present specification refers to 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.

The polymer solution of this embodiment is
(A) Polymer and
(B) A compound having a thiol group and an alkoxy group, or an oligomer thereof,
including.

[Polymer (A)]
The polymer (A) of the present embodiment includes a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-2).

In the general formula (1-1), Z is a group containing one or more (meth) acryloyl groups. Q is a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X represents an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. ..
In the general formula (1-2), ^RA is a group containing one or more (meth) acryloyl groups.

The polymer (A) of the present embodiment has excellent sensitivity and alkali solubility by containing the structural unit represented by the general formula (1-1) and the structural unit represented by the general formula (1-2). It is excellent and can be suitably used as a color filter or a polymer for forming a black matrix. In particular, the polymer (A) of the present embodiment has its alkali solubility adjusted and is excellent in sensitivity. Therefore, when a strongly basic developer such as a tetramethylammonium hydroxide (TMAH) solution is used, after exposure and development. The pattern can be shaped as designed.

In the general formula (1-1), Z is not particularly limited as long as it is a group containing one or more (meth) acryloyl groups, but is more preferably a group containing 1 to 4 (meth) acryloyl groups. It is more preferable that the group contains 1 to 3 (meth) acryloyl groups. By optimizing the number of (meth) acryloyl groups contained in Z, the sensitivity is excellent and the alkali solubility (developability) is excellent, in other words, the balance between them is excellent.
From the viewpoint of these characteristics, Z is preferably a group containing one (meth) acryloyl group, and more preferably a group represented by the following general formula (1a).

In the general formula (1a), R is a hydrogen atom, a methyl group or an ethyl group.
In the general formula (1-1), Q is a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Examples of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group and the like.

In the general formula (1-1), X is an oxygen atom, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group. Examples of the substituted allene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group and the like.

In the general formula (1-1), the carbon atom of any of the alkyl group of Q and the alkylene group of X may be bonded to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, a naphthalene ring and the like.

In the general formula (1-2), ^RA is not particularly limited as long as it is a group containing one or more (meth) acryloyl groups, but is more preferably a group containing 1 to 6 (meth) acryloyl groups. , A group containing 1 to 5 (meth) acryloyl groups is more preferable, and a group containing 2 to 5 (meth) acryloyl groups is particularly preferable. Sensitivity can be further increased by optimizing the number of (meth) acryloyl groups contained in ^RA . In addition, it becomes easier to achieve both sensitivity and developability at a higher level. Furthermore, it becomes easier to increase the heat resistance.

The ratio of the structural unit represented by the general formula (1-1) to all the structural units contained in the chain of the polymer (A) of the present embodiment is preferably 0.5 to 20 mol%, more preferably 1. ~ 15 mol%. The ratio of the structural unit represented by the general formula (1-2) is preferably 6 to 40 mol%, more preferably 12 to 30 mol%.

Examples of the structural unit represented by the general formula (1-2) include the structural unit represented by the following general formula (1-2a) and the structural unit represented by the following general formula (1-2b). can.

In the general formula ( ^1-2a ), RS is a group containing only one (meth) acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while an attempt is made to improve the developability. In some cases, curing tends to be insufficient, so the polymer (A) preferably contains a structural unit represented by the general formula (1-2a), whereby both sensitivity and developability are well balanced. Can be compatible with.

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

In the general formula (a), 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 the general formula (a), 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 general formula (1-2a) 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.

The proportion of the structural unit represented by the general formula (1-2a) in the total structural units of the polymer (A) of the present embodiment is preferably 5 to 40 mol%, more preferably 10 to 30 mol%. ..

In the general formula (1-2b), ^RD is not particularly limited as long as it is a group containing two or more (meth) acryloyl groups, but is more preferably a group containing 2 to 6 (meth) acryloyl groups. , A group containing 3 to 5 (meth) acryloyl groups is more preferable. Sensitivity can be further increased by optimizing the number of (meth) acryloyl groups contained in ^RD . In addition, it becomes easier to achieve both sensitivity and developability at a higher level. Furthermore, it becomes easier to increase the heat resistance.

From the viewpoint of further improving the sensitivity, it is preferable that the ^RD contains two or more acryloyl groups (group represented by −C (= O) −CH = _CH2 ) in terms of steric hindrance and the like. ..

^RD is preferably a group represented by the following general formula (1b), (1c) or (1d). With such a group, it tends to be easy to obtain the above-mentioned various effects.

In the general formula (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 even more 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 the general formula (1c),
k, R, X ¹ and X ² are synonymous with R, k, X ¹ and X ² in the above general formula (1b), respectively, and a plurality of R may be the same as or different from each other. , Multiple 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 the general formula (1d), n is an integer of 2 to 5, preferably 2 or 3.

The polymer (A) of the present embodiment has a structure represented by the following general formula (1) consisting of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (1-2). Can include units.

In the general formula (1), Q, X, and Z are synonymous with the general formula (1-1), and ^RA is synonymous with the general formula (1-2).

The proportion of the structural unit represented by the general formula (1) in the total structural units of the polymer (A) of the present embodiment is preferably 0.25 to 35 mol%, more preferably 0.5 to 25 mol%. Is.

The polymer (A) of the present embodiment has a structure represented by the following general formula (2) consisting of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (1-2b). Can include units.

In the general formula (2), Q, X, and Z are synonymous with the general formula (1-1), and ^RD is synonymous with the general formula (1-2b).
The proportion of the structural unit represented by the general formula (2) in the total structural units of the polymer (A) of the present embodiment is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. Is.

The polymer (A) of the present embodiment has the following general formula (3) as a structural unit composed of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (1-2a). It can include the structural unit represented.

In the general formula (3), Z, Q, and X are synonymous with the general formula (1-1), and RS is synonymous with the general formula ( ^1-2a ).

When the polymer (A) contains the structural units represented by the general formula (3), the ratio of the structural units represented by the general formula (3) to the total structural units of the polymer (A) is preferably 3 to 3. It is 35 mol%, more preferably 7 to 25 mol%.

The polymer (A) of the present embodiment is represented by a structural unit represented by the general formula (5) and a general formula (6) described later as structural units including the structural unit represented by the general formula (1-1). It can also include structural units. These structural units will be described later.

Further, the polymer (A) of the present embodiment has a structural unit represented by the general formula (7) and a general formula (8), which will be described later, as a structural unit including the structural unit represented by the general formula (1-2). It can also include structural units to be made. This structural unit will be described later.

The polymer (A) of the present embodiment can further contain a structural unit represented by the following general formula (NB).

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 a1 is 0, 1 or 2.

The structural unit represented by the general formula (NB) is chemically robust. Therefore, the polymer (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 polymer (A) can be suitably used for producing a film or a filter for use in a liquid crystal display device or a solid-state image sensor that requires heat resistance.

Examples of the organic group having 1 to 30 carbon atoms which can constitute R ¹ to R ⁴ include substituted or unsubstituted, linear or branched alkyl having 1 to 30 carbon atoms, and more specifically, an alkyl. Examples thereof include a group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group, a heterocyclic group and a carboxyl group.

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), a1 is preferably 0 or 1, more preferably 0.

The proportion of the structural unit represented by the general formula (NB) in the total structural unit of the polymer (A) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%. %.
The polymer (A) of the present embodiment can further contain a structural unit represented by the following general formula (4).

By including the structural unit represented by the general formula (1-1) and the structural unit represented by the general formula (1-2) as well as the structural unit represented by the general formula (4), the polymer (A) can be made. Alkaline solubility can be adjusted. As a result, the photosensitive resin composition containing the polymer (A) is excellent in balance between sensitivity and developability even when it is subjected to a photolithography process using a strong basic developer.

When the polymer (A) contains the structural units represented by the general formula (4), the ratio of the structural units represented by the general formula (4) to the total structural units of the polymer (A) is preferably 1 to 1. It is 15 mol%, more preferably 2-10 mol%.

The polymer (A) of the present embodiment can further include a structural unit represented by the following general formula (5), which comprises a structural unit represented by the general formula (1-1). By including the structural unit, both sensitivity and developability can be achieved in a better balance.

In the general formula (5), Z, X, and Q are synonymous with the general formula (1-1).

When the polymer (A) contains the structural units represented by the general formula (5), the ratio of the structural units represented by the general formula (5) to the total structural units of the polymer (A) is preferably 1 to 1. It is 12 mol%, more preferably 1-9 mol%.

From the viewpoint of the effect of the present invention, the polymer (A) of the present embodiment further comprises a structural unit represented by the following general formula (6) consisting of two structural units represented by the general formula (1-1). Can include. By including the structural unit, the sensitivity can be further improved.

In the general formula (6), Z, X, and Q are synonymous with the general formula (1-1). A plurality of Zs, a plurality of Qs, and a plurality of Xs may be the same or different.

When the polymer (A) contains the structural units represented by the general formula (6), the ratio of the structural units represented by the general formula (6) to the total structural units of the polymer (A) is preferably 1 to 1. It is 10 mol%, more preferably 1-8 mol%.

From the viewpoint of the effect of the present invention, the polymer (A) of the present embodiment may further contain a structural unit represented by the following general formula (7) and / or a structural unit represented by the following general formula (8). can.

In the general formula (7), ^RD is synonymous with the general formula (1-2b).

When the polymer (A) contains the structural units represented by the general formula (7), the ratio of the structural units represented by the general formula (7) to the total structural units of the polymer (A) is preferably 0. It is 5 to 25 mol%, more preferably 1 to 18 mol%.
From the viewpoint of the effect of the present invention, the polymer (A) of the present embodiment can further contain a structural unit represented by the following general formula (8).

In the general formula (8), RS is synonymous with the general formula ( ^1-2a ).

When the polymer (A) contains the structural units represented by the general formula (8), the ratio of the structural units represented by the general formula (8) to the total structural units of the polymer (A) is preferably 3 to 3. It is 35 mol%, more preferably 5 to 25 mol%.

In the present embodiment, the polymer (A) may contain a structural unit represented by the general formula (MA) in addition to the above structural unit. The structural unit represented by the general formula (MA) is ring-opened with an alkaline developer to generate two carboxyl groups. Therefore, the polymer (A) containing the structural unit has excellent developability. When the polymer (A) contains a structural unit represented by the general formula (MA), the structural unit represented by the general formula (MA) among all the structural units of the polymer (A) is preferably 1 to 1. It is 30 mol%, more preferably 2 to 25 mol%.

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

In the present embodiment, the polymer (A) may contain a divalent structural unit derived from a copolymerizable compound having a double bond as "other structural units" other than the above-mentioned structural units.
Other structural units include, for example, substituted or unsubstituted, inden, maleimide, styrene, acenaphtylene, norbornadiene, dihydrofuran, terpene compounds (eg, pinen, limonene, etc.), linear alkenes (eg, penten, etc.), cyclic alkenes. (Cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth) acrylic acid compounds (eg, methyl methacrylate, acrylic). It contains at least one structural unit derived from methyl acid), vinyl acetate, vinyl ether (eg, 2-hydroxyethyl vinyl ether, etc.) and the like.

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 other structural units are preferably structural units represented by the general formula (10) (divalent structural units derived from substituted or unsubstituted inden) and structural units represented by the general formula (11). (Divalent structural unit derived from substituted or unsubstituted maleimide), structural unit represented by the general formula (12) (divalent structural unit derived from substituted or unsubstituted styrene), or general formula. The structural unit represented by (13) (divalent structural unit derived from substituted or unsubstituted norbornadiene) is included.

In the general formula (10), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (11), R ³ represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (12), R ⁴ to R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (13), R ⁷ to R ¹⁰ independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.
The proportion of "other structural units" in the total structural units of the polymer (A) of the present embodiment is preferably 0 to 50 mol%, more preferably 0 to 25 mol%, and particularly preferably 0 to 10 mol%. Is.

The weight average molecular weight Mw of the polymer (A) is, for example, 2,000 to 200,000, preferably 3,000 to 150,000, more preferably 5,000 to 100,000, still more preferably 8,000. It is ~ 80,000. 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 polymer (A) is preferably 1.0 to 8.0, more preferably 1.5 to 7.0, and even more preferably 2.0 to 2.0. It is 6.0. By appropriately adjusting the dispersity, the physical properties of the polymer (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 polymer (A) is preferably 150 to 250 ° C, more preferably 170 to 230 ° C. The polymer (A) has a relatively high glass transition temperature by containing a structural unit mainly 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 acid value of the polymer (A) is 70 mgKOH / g or more and 150 mgKOH / g or less, preferably 80 mgKOH / g or more and 140 mgKOH / g or less.
When the acid value is in the above range, the sensitivity is excellent and the alkali solubility is excellent, in other words, the balance of these characteristics is excellent.
The acid value can be measured by the following method.

Specifically, the H of the carboxyl group (-COOH) of the polymer (A) is based on the integrated value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, which is the standard in ¹ H-NMR measurement. The amount of carboxyl group is obtained from the integrated value of the peak (around 12.4 ppm). Then, the acid value (mgKOH / g) can be calculated from the amount.

(Manufacturing of polymer (A))
The polymer (A) of the present embodiment can be produced (synthesized) by any method. The method for producing the polymer (A) will be described with reference to the first embodiment and the second embodiment.

In the first embodiment and the second embodiment, the polymer precursor P'is shown by an example including a structural unit represented by the general formula (8), but the structural unit is arbitrary and is the present embodiment. The polymer (A) of the above may contain a structural unit represented by the general formula (8).

(First Embodiment)
The method for producing the polymer (A) of the present embodiment is as follows.
(I) The structural unit represented by the following general formula (NB), the structural unit represented by the following general formula (7), the structural unit represented by the following general formula (8), and the following general formula (MA). The first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing the represented structural unit, and

(II) The polymer precursor P'obtained in the first step is reacted with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst, and the structural unit represented by the following general formula (1) is described below. The structural unit represented by the general formula (NB), the structural unit represented by the following general formula (3), the structural unit represented by the following general formula (7), and the structural unit represented by the following general formula (8). In the second step of preparing the polymer (A) containing the structural unit represented by the following general formula (MA), in some cases,
including.

Hereinafter, a method for producing (synthesizing) the polymer (A) of the present embodiment by these steps will be described.
The first step (I) for preparing the polymer precursor P'is
(Ii) A step of preparing a raw material polymer containing a structural unit represented by the following general formula (NB) and a structural unit represented by the following general formula (MA).

(I-ii) The raw material polymer obtained in step (I-i) and a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as “polyfunctional (meth) acrylic compound”). Is reacted in the presence of a basic catalyst, and is represented by a structural unit represented by the following general formula (NB), a structural unit represented by the following general formula (7), and a following general formula (MA). The step of preparing the first polymer precursor containing the structural unit, and

(I-iii) A compound having a first polymer precursor obtained in step (I-ii), a hydroxyl group and one (meth) acryloyl group (hereinafter referred to as "monofunctional (meth) acrylic compound"). ) Is reacted in the presence of a basic catalyst, and is represented by the following general formula (NB), the following structural unit, the following general formula (7), and the following general formula (8). It is preferable to include a step of preparing a second polymer precursor containing the structural unit and the structural unit represented by the following general formula (MA). Here, the second polymer precursor obtained in the step (I-iiii) corresponds to the polymer precursor P'described in the above step (I).

(Step (I-i))
In the step (Ii), the step of preparing the raw material polymer containing the structural unit represented by the general formula (NB) and the structural unit represented by the general formula (MA) is represented by the general formula (NBm). It can be produced by polymerizing (addition polymerization) a monomer composition containing the above-mentioned monomer and maleic anhydride. The definitions of R ¹ , R ² , R ³ and R ⁴ and a1 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 general formula (NBm) include norbornene, bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-. Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-Methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5- Examples thereof include methyl norbornene-2-carboxylate and 5-norbornene-2,3-dicarboxylic acid anhydride. At the time of polymerization, only one type of monomer represented by the general formula (NBm) may be used, or two or more types may be used in combination.

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, for example, substituted or unsubstituted, inden, maleimide, styrene, acenaphtylene, norbornadiene, dihydrofuran, terpene compounds (eg, pinen, limonene, etc.), linear alkenes (eg, penten, etc.), cyclic alkenes. (Cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth) acrylic acid compounds (eg, methyl methacrylate, acrylic). Methyl acid acid), vinyl acetate, vinyl ether (for example, 2-hydroxyethyl vinyl ether, etc.) and the like. In this step, the monomer represented by the general formula (2 m), maleic anhydride, and if necessary, other monomers are polymerized (added) in the presence of the monofunctional or higher thiol group-containing compound. Can be polymerized).

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 polymerization solvent, 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.

The synthesis of the raw material polymer is carried out by dissolving the monomer represented by the general formula (NBm), maleic anhydride and the polymerization initiator in a solvent, charging the reaction vessel, and then heating to proceed the addition polymerization. To. 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 general 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.
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.

(Process (I-ii))
By reacting the raw material polymer obtained in the step (Ii) with the polyfunctional (meth) acrylic compound in the presence of a basic catalyst, it is represented by the general formula (MA) contained in the raw material polymer. A part of the structural unit is opened to form the structural unit represented by the general formula (7), and the structural unit represented by the general formula (NB) and the structural unit represented by the general formula (MA) are formed. And the first polymer precursor containing the structural unit represented by the general formula (7) is obtained.

More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF) can be used. However, various organic solvents used in the synthesis of organic compounds and polymers can be used.

Next, a polyfunctional (meth) acrylic compound is added to the above solution. In addition, a basic catalyst is added. Then, the solutions are appropriately mixed to obtain a uniform solution.

Examples of the polyfunctional (meth) acrylic compound include a compound represented by the general formula (1 bm), a compound represented by the general formula (1 cm), or a compound represented by the general formula (1 dm). Compounds can be mentioned. The definitions and specific embodiments of k, R, X ¹ , X ^1'and X ² in the general formula (1b-m) are the same as those in the general formula (1b) described above. The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in the general formula (1c-m) are the same as those in the general formula (1c) described above. be. Further, the definition of n in the general formula (1 dm) is the same as that in the above general formula (1d).

Specific examples of the polyfunctional (meth) acrylic compound represented by the general formula (1bm) include, but are not limited to, the following compounds.

Specific examples of the polyfunctional (meth) acrylic compound represented by the general formula (1 cm) include, but are not limited to, the following compounds.

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.

By heating the above solution at preferably 60 to 80 ° C. for about 3 to 9 hours, a part of the structural unit of the general formula (MA) contained in the raw material polymer is opened and the general formula (7) is used. A first polymer precursor in which a structural unit is formed and comprises a structural unit represented by the general formula (NB), a structural unit represented by the general formula (MA), and a structural unit represented by the general formula (7). The body produces.

(Step (I-iii))
Then, the first polymer precursor obtained in step (I-ii) and the monofunctional (meth) acrylic compound are reacted in the presence of a basic catalyst to be contained in the first polymer precursor. A part of the structural unit represented by the general formula (MA) is opened, the structural unit represented by the general formula (8) is formed, and the structural unit represented by the general formula (NB) is formed by the general formula (NB). The second polymer precursor containing the structural unit represented by MA), the structural unit represented by the general formula (7), and the structural unit represented by the general formula (8), that is, the polymer precursor P'. can get.

The step (I-iii) is preferably carried out by adding a monofunctional (meth) acrylic compound to the reaction system containing the first polymer precursor obtained in the step (I-ii). From the viewpoint of steric hindrance of the reaction, the monofunctional (meth) acrylic compound tends to react more easily with the raw material polymer than the polyfunctional (meth) acrylic compound. Therefore, the step of reacting the monofunctional (meth) acrylic compound (I-ii) and the step of reacting the monofunctional (meth) acrylic compound (I-iii) are not carried out at the same time, but are carried out in this order. Is preferable.

Further, the reaction between the monofunctional (meth) acrylic compound and the first polymer precursor proceeds in the presence of a basic catalyst. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (I-ii) can be used as it is. Therefore, in step (I-iii), the first polymer precursor is isolated and purified from the reaction mixture containing the first polymer precursor obtained in step (I-ii), or is contained in the mixture. Performed in situ by adding a monofunctional (meth) acrylic compound to the reaction mixture containing the first polymer precursor obtained in step (I-ii) without neutralizing the basic catalyst. It is preferable to do so.

Specifically, the reaction solution obtained by adding a monofunctional (meth) acrylic compound to the reaction mixture containing the first polymer precursor is heated at preferably 60 to 80 ° C. for about 1 to 9 hours. Then, a part of the structural unit represented by the general formula (MA) contained in the first polymer precursor is opened to form the structural unit represented by the general formula (8), and the polymer precursor P' Is generated.

Examples of the monofunctional (meth) acrylic compound used in the step (I-iii) include compounds represented by the following general formula (3am). In the general formula (3a-m), the definitions of ^X10 and R are the same as those in the general formula (3a).

Specific examples of the compound represented by the general formula (3am) 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.

(Step II))
The polymer precursor P'obtained in the first step (I) is reacted with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst to contain the carboxyl group of the polymer precursor P'and the epoxy group. By the reaction of the meta) acrylic compound with the epoxy group, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) are formed, and the structure represented by the general formula (1) is formed. A unit, a structural unit represented by the above-mentioned general formula (NB), a structural unit represented by the above-mentioned general formula (3), a structural unit represented by the above-mentioned general formula (7), and the above-mentioned general formula (8). ), And in some cases, the polymer (A) containing the structural unit represented by the above-mentioned general formula (MA) is prepared.

Step (II) is preferably carried out by adding an epoxy group-containing (meth) acrylic compound to the reaction system containing the polymer precursor P'obtained in step (I-iii).

The reaction between the polymer precursor P'and the epoxy group-containing (meth) acrylic compound proceeds in the presence of a basic catalyst. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (I-iii) can be used as it is. Therefore, in step (II), the polymer precursor P'is isolated and purified from the reaction mixture containing the polymer precursor P'obtained in step (I-iii), or the basic catalyst contained in the mixture is used. It is preferably carried out in situ by adding an epoxy group-containing (meth) acrylic compound to the reaction mixture containing the polymer precursor P'obtained in step (I-iii) without neutralization. ..

Specifically, the reaction solution obtained by adding an epoxy group-containing (meth) acrylic compound to the reaction mixture containing the polymer precursor P'is heated at preferably 60 to 80 ° C. for about 1 to 9 hours. The structural unit represented by the general formula (1) and the structure represented by the general formula (3) are formed by the reaction between the carboxyl group of the polymer precursor P'and the epoxy group of the epoxy group-containing (meth) acrylic compound. Units are formed and the polymer (A) is produced.

Examples of the epoxy group-containing (meth) acrylic compound include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethylacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and acrylic acid. Examples include glycidyl and the like, and one or more selected from these can be used.
The amount of the epoxy group-containing (meth) acrylic compound added is preferably 0.1 to 3.0 mol with respect to 1 mol of the carboxyl group of the polymer precursor P'.
After the step (II), it is preferable to appropriately perform the following steps in order to remove unnecessary components other than the desired polymer (A).

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

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

(Second embodiment)
The method for producing the polymer (A) of the present embodiment is as follows.
(A) The structural unit represented by the following general formula (NB), the structural unit represented by the following general formula (7), the structural unit represented by the following general formula (8), and the following general formula (MA). The first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing the structural unit to be used, and

(B) By treating the polymer precursor P'obtained in the first step with water in the presence of a catalyst, the structural unit represented by the following general formula (NB) can be expressed by the following general formula (4). A structural unit represented by the following general formula (7), a structural unit represented by the following general formula (8), and in some cases a structural unit represented by the following general formula (MA). A second step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P") containing the polymer precursor, and

(C) The polymer precursor P "obtained in the second step is reacted with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst, and the structural unit represented by the following general formula (1) is described below. The structural unit represented by the general formula (NB), the structural unit represented by the following general formula (3), the structural unit represented by the following general formula (4), and the structural unit represented by the following general formula (5). , The structural unit represented by the following general formula (6), the structural unit represented by the following general formula (7), the structural unit represented by the following general formula (8), and in some cases, the following general formula (MA). A third step of preparing a polymer containing the structural units to be
including.

Hereinafter, a method for producing (synthesizing) the polymer of the present embodiment by these steps will be described. Since the first step (a) for preparing the polymer precursor is the same as the first step (I) of the present embodiment, the description thereof will be omitted.

(Step (b))
By treating the polymer precursor P'obtained in the step (a) with water in the presence of a catalyst, the structural unit represented by the general formula (MA) contained in the polymer precursor P'is ring-opened. Then, the structural unit represented by the general formula (4) is formed, and the structural unit represented by the general formula (NB), the structural unit represented by the general formula (4), and the structural unit represented by the general formula (7) are represented. The polymer precursor P "containing the structural unit represented by the general formula (8) and the structural unit represented by the general formula (8) can be produced. If some of the structural units of formula (MA) remain unopened, the polymer will have structures of general formula (NB), general formula (4), general formula (7), and general formula (8). In addition to the unit, the structural unit represented by the general formula (MA) is included.

The step (b) is preferably carried out by adding water to the reaction system containing the polymer precursor P'obtained in the above-mentioned step (I-iii). As the catalyst used in the step (b), a basic catalyst can be used, and the same catalyst as the basic catalyst used in the above step (I-ii) or the step (I-iii) can be used. .. Specific examples of the basic catalyst include amine compounds such as triethylamine, pyridine and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

In step (b), water is added to the reaction system containing the polymer precursor P'obtained in the above step (I-iii), and the obtained reaction solution is prepared at 0, preferably at 60 to 80 ° C. . By heating for about 25 to 6 hours, the structural unit of the general formula (MA) contained in the polymer precursor P'is ring-opened, and the structural unit represented by the general formula (4) is generated. This reaction proceeds in the presence of a basic catalyst. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (I-iii) can be used as it is. Therefore, in step (b), the polymer precursor P'is isolated and purified from the reaction mixture containing the polymer precursor P'obtained in step (I-iii), or the basic catalyst contained in the mixture is used. It is preferably carried out in situ by adding water to the reaction mixture containing the polymer precursor P'obtained in step (I-iii) without neutralization.

In the third step (c), the polymer precursor P "obtained in the second step (b) is reacted with an epoxy group-containing (meth) acrylic compound in the presence of a catalyst to obtain the polymer (A). The reaction conditions of the third step (c) are the same as those of the second step (ii) of the first embodiment, and thus the description thereof will be omitted.
After the third step (c), it is preferable to appropriately perform a cleaning step or the like as in the first embodiment in order to remove unnecessary components other than the desired polymer (A).

Compound (B) having a thiol group and an alkoxy group or an oligomer thereof The polymer solution of the present embodiment contains a compound (B) having a thiol group and an alkoxy group or an oligomer thereof together with the polymer (A).
As the compound (B), as long as it has a thiol group and an alkoxy group, known compounds can be used as long as the effects of the present invention are exhibited.

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

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

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

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

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

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

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

In the polymer solution of the present embodiment, the compound (B) or an oligomer thereof is 0.25 to 20% by mass, preferably 1.0 to 15% by mass, based on the polymer (A) from the viewpoint of the effect of the present invention. It is% by mass, more preferably 2.0 to 12% by mass.

[Polymer solution]
The polymer solution of the present embodiment contains the above-mentioned polymer (A) and a compound (B) having a thiol group and an alkoxy group or an oligomer thereof.
Further, the polymer solution may contain at least one selected from a polyfunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound as long as it does not affect the effect of the present invention.

[Polyfunctional (meth) acrylic compound]
As the polyfunctional (meth) acrylate compound, which is a compound having two or more (meth) acryloyl groups, conventionally known compounds can be used as long as the effects of the present invention can be exhibited.

Examples of the polyfunctional (meth) acrylic compound include a compound represented by the following general formula (1bp), a compound represented by the general formula (1cp), and a compound represented by the general formula (1dp). Examples include, but are not limited to, the following compounds.

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

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

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

Specific examples of the polyfunctional (meth) acrylic compound represented by the general formula (1bp) include, but are not limited to, compounds having the following structures. In the following compounds, Y represents a hydrogen atom, a (meth) acryloyl group, or a combination thereof.

Specific examples of the polyfunctional (meth) acrylic compound represented by the general formula (1c-p) include, but are not limited to, the following compounds.

In the polymer solution of the present embodiment, the polyfunctional (meth) acrylic compound can be blended within a range that does not affect the effect of the present invention, and is used in the gel permeation chromatography (GPC) chart of the resin composition. The peak area derived from the polyfunctional (meth) acrylic compound can be blended in an amount preferably 10% or less, more preferably 5% or less, still more preferably 2% or less with respect to the peak area of the resin.

[Monofunctional (meth) acrylic compound]
The polymer solution of the present embodiment may contain a monofunctional (meth) acrylic compound which is a compound having one (meth) acryloyl group.

Examples of the monofunctional (meth) acrylic compound include compounds represented by the following general formula (2am). The monofunctional (meth) acrylic compound may be an unreacted monomer or may be added separately.
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.

In the polymer solution of the present embodiment, the monofunctional (meth) acrylic compound can be blended within a range that does not affect the effect of the present invention, and is simply used in the gel permeation chromatography (GPC) chart of the resin composition. The peak area derived from the functional (meth) acrylic compound can be blended in an amount preferably 10% or less, more preferably 5% or less, still more preferably 2% or less with respect to the peak area of the resin.

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

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

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

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution and a photosensitive agent. That is, the photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution (varnish, resin composition) of the present embodiment and a photosensitive agent. Each component will be described below.

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

By containing the above components, the photosensitive resin composition of the present embodiment has high sensitivity in photolithography processing and has excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method. Further, since the yellowing of the photosensitive resin composition is suppressed, the article obtained by curing the photosensitive resin composition has transparency.

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

The photosensitive resin composition of the present embodiment may contain a compound having one (meth) acryloyl group (monofunctional (meth) acrylic compound) in addition to the above-mentioned polymer, polyfunctional (meth) acrylic compound and photosensitive agent. good. The monofunctional (meth) acrylic compound is similar to that described above. By including the monofunctional (meth) acrylic compound, the alkali solubility of the obtained photosensitive resin composition is further improved, and yellowing is reduced.

When the photosensitive resin composition of the present embodiment contains a monofunctional (meth) acrylic compound, the amount thereof is the monofunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart of the photosensitive resin composition. The peak area derived from the above is preferably blended in an amount of 5 to 50% with respect to the peak area of the polymer, 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.

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

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

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

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

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

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

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

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

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

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

(solvent)
The photosensitive resin composition can typically contain a solvent. 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), methyl-. Examples thereof include n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof.
The amount of the solvent used is not particularly limited, but is used in such an amount that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

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

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

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

The cross-linking agent is, for example, a polyfunctional compound having two or more polymerizable double bonds in one molecule, and a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups in one molecule. (However, the cross-linking agent does not correspond to the above-mentioned polymer). It is preferable to use a cross-linking agent having the same kind of cross-linking group as the cross-linking group (polymerizable double bond) of the polymer in terms of uniform curability and further improvement of sensitivity.
The upper limit of the functional number (the number of polymerizable double bonds) per molecule of the cross-linking agent is not particularly limited, but is, for example, 8 or less, preferably 6 or less.

Specific examples of the cross-linking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and hexanediol di. (Meta) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol Falkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) Acrylate, glycerintri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropanetri (meth) acrylate, ethylene oxide-added ditrimethylol Propanetetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropanetri (meth) acrylate, propylene oxide-added dimethylolpropanetetra (meth) Acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added trimethylolpropane tetra (meth) acrylate , Ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, and other polyfunctional (meth) acrylates;
Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimetylol propanetrivinyl ether, ditri Methylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylol propanetrivinyl ether, ethylene oxide-added ditrimethylol propanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide. Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether;
2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylic acid, 1-methyl-2-vinyloxyethyl (meth) acrylic acid, 2-vinyloxypropyl (meth) acrylic acid, 4 (meth) acrylic acid -Vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyloxyhexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, ( Contains vinyl ether groups (meth) such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate. Acrylic acid esters;
Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol Falkylene oxide diallyl ether, trimethyl propanetriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;
Allyl group-containing (meth) acrylic acid esters such as allyl (meth) acrylic acid;
Polyfunctional (meth) acryloyl such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, and alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate. Group-containing isocyanates;
Polyfunctional allyl group-containing isocyanates such as triallyl isocyanurate;
Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Polyfunctional urethane (meth) acrylates obtained in
Polyfunctional aromatic vinyls such as divinylbenzene;
And so on.

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

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

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

[Film, color filter, black matrix, liquid crystal display 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.
Since the photosensitive resin film made of the photosensitive resin composition containing the polymer solution of the present embodiment has excellent adhesion to the substrate, peeling of the pattern is suppressed in the developing process.

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

Specific examples of the alkaline aqueous solution include (i) an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine and triethanolamine, and (iii). Examples thereof include an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

Since the polymer of the present embodiment has excellent adhesion to the substrate, it is possible to suppress pattern peeling during development even when a strong basic developer such as TMAH (tetramethylammonium hydroxide) solution is used. , Product yield and product reliability are improved.

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.

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, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The compounds used in the examples may be indicated by the following abbreviations or trade names.
-MA: maleic anhydride-NB: 2-norbornen-MEK: methyl ethyl ketone-4-HBA: 4-hydroxybutyl acrylate-HEMA: 2-hydroxyethyl methacrylate-GMA: glycidyl methacrylate-4HBAGE: 4-hydroxybutyl acrylate glycidyl ether 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.)

A-9550: The amount of the compound on the left in the mixture of the following two compounds and the mixture estimated from the hydroxyl value is about 50% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd.)
KBM-802: 3-mercaptopropylmethyldimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd.)

<Synthesis of raw material polymer>
(Synthesis of raw material polymer 1)
Maleic anhydride 353.02 g (3.6 mol), 2-norbornene 338.94 g (3.6 mol) and dimethyl 2,2'-azobis (3.6 mol) in an appropriately sized reaction vessel equipped with a stirrer and a condenser. 2-Methylpropionate) 41.45 g (0.180 mol) was weighed and added. These were dissolved in a mixed solvent consisting of 578.98 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.
The solution was aerated with nitrogen for 30 minutes to remove oxygen, and then heated at a temperature of 63 ° C. for 9.5 hours with stirring to polymerize maleic anhydride and 2-norbornene. A polymerization solution was prepared.
The polymerization solution obtained above was diluted with 712.92 g of methyl ethyl ketone and then added dropwise to 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum dried at a temperature of 120 ° C. to obtain 550.4 g of a polymer (raw material polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. ..
As a result of GPC measurement of the obtained polymer, the weight average molecular weight Mw was 11,600, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.79.

[Example 1]
(Polymer synthesis)
The MA unit of the raw material polymer 1 is ring-opened with a trifunctional (meth) acrylic compound (A-TMM-3LM-N) and a monofunctional (meth) acrylic compound (4-HBA), and then an epoxy group-containing (meth) acrylic. The polymer P1 obtained by reacting with the compound (GMA) was prepared. The details will be described below.
First, 102.63 g of MEK was added to 160 g of the raw material polymer (0.312 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, 27.12 g (0.187 mol) of 4-HBA was added, and the mixture was reacted at a temperature of 70 ° C. for 4 hours. After that, 13.31 g (0.094 mol) of GMA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.

As described above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3LM-N and 4-HBA to obtain a polymer P1 reacted with GMA.

By GPC measurement of the polymer P1, the disappearance of the peaks of the polyfunctional (meth) acrylic compound, the monofunctional (meth) acrylic compound, and the epoxy group-containing (meth) acrylic compound used was confirmed. As a result, it was confirmed that the obtained polymer P1 did not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, and an unreacted epoxy group-containing (meth) acrylic compound. ..
Table 1 shows the components used in the synthesis example and the amount of each component charged in terms of maleic anhydride (MA), and the amount of each structural unit (molar fraction, mol%) is analyzed by ¹ H-NMR integrated value. It was calculated and shown in terms of maleic anhydride (MA).
FIG. 2 shows a ¹ H-NMR chart of polymer P1, and FIG. 3 shows a partially enlarged peak near 6.0 ppm.

In addition to the peak corresponding to 3H of the 5.8-6.7 ppm acryloyl group (-CH = CH ₂ ) shown in the ¹ H-NMR chart of the polymer P1 in FIG. 3, it is indicated by ×. Peaks corresponding to 2H of the methacryloyl group (-C (CH ₃ ) = CH ₂ ) (-C (CH ₃ ) = CH ₂ of CH ₂ ) appeared at 6-5.8 ppm and 6.0-6.1 ppm. In GPC measurement of polymer P1, unreacted trifunctional (meth) acrylic compound (A-TMM-3LM-N) and monofunctional (meth) acrylic compound (4-HBA), epoxy group-containing (meth) acrylic compound (meth) Since no peak of GMA) is observed, it can be seen that an acryloyl group and a methacryloyl group derived from GMA are introduced into the polymer.

In addition, in the GPC measurement of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction, the peak derived from the trifunctional (meth) acrylic compound (A-TMM-3LM-N) decreased before and after the ring-opening reaction, and GMA addition occurred. From the fact that the peak derived from GMA decreased before and after the reaction, it can be seen that A-TMM-3LM-N and GMA were introduced into the polymer.

(Preparation of polymer solution)
100 parts by mass of the obtained polymer P1 and 5 parts by mass of KBM-803 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 1 having a solid content concentration of 30% by mass.

(Preparation of photosensitive resin composition)
The following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a photosensitive resin composition so that the total solid content concentration was 30% by mass.
-Solid content in polymer solution 1 (total of polymer P1 and KBM-803): 100 parts by mass-Polyfunctional acrylate (dipentaerythritol hexaacrylate) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 mass Part ・ Photopolymerization initiator (BASF, Ingacure OXE01): 5 parts by mass ・ Adhesion aid (Shinetsu Chemical Industry Co., Ltd., KBM-403): 1 part by mass ・ Surface active agent (DIC Corporation, F- 556): 0.5 parts by mass The obtained photosensitive resin composition was filtered with a PTFE membrane filter Millex-LS (manufactured by Merck Millipore), if necessary, to remove insoluble matter.

[Example 2]
Polymer P2 was prepared in the same manner as in Example 1 except that the amount of 4-HBA added was changed to 13.50 g and MEK was changed to 100.80 g. Using the polymer P2, the amount of KBM-803 added was as shown in Table 1. The polymer solution 2 was prepared in the same manner as in Example 1 except that the polymer solution 2 was changed to. The photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 3]
Using the polymer P2, the polymer solution 3 was prepared in the same manner as in Example 2 except that the amount of KBM-803 added was changed as shown in Table 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 4]
The polymer solution 4 was prepared in the same manner as in Example 3 except that the polymer P2 was used and KBM-802 was used. The photosensitive resin composition was prepared in the same manner as in Example 1.

[Example 5]
(Polymer synthesis)
The MA unit of the raw material polymer 1 was ring-opened with a monofunctional (meth) acrylic compound (HEMA) and then reacted with an epoxy group-containing (meth) acrylic compound (GMA) to prepare a polymer P3. The details will be described below.
First, 111.43 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Then, 25.38 g (0.195 mol) of HEMA was added to this lysate, then 6.00 g (0.059 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 6 hours. After that, 13.31 g (0.094 mol) of GMA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess of water.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of water was repeated twice.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with HEMA to obtain a polymer P3 which was reacted with GMA.
By GPC measurement of the polymer P3, the disappearance of the peak of the monofunctional (meth) acrylic compound used and the peak of the epoxy group-containing (meth) acrylic compound was confirmed. As a result, it was confirmed that the obtained polymer P3 contained neither an unreacted (meth) acrylic compound nor an epoxy group-containing (meth) acrylic compound.
Table 1 shows the components used in the synthesis example and the amount of each component charged in terms of maleic anhydride (MA), and the amount of each structural unit (molar fraction, mol%) is analyzed by ¹ H-NMR integrated value. It was calculated and shown in terms of maleic anhydride (MA).
¹ It was confirmed by 1 H-NMR measurement that the polymer P3 had a structure opened by HEMA and a structure reacted by GMA.
Using the polymer P3, the polymer solution 5 and the photosensitive resin composition were prepared in the same manner as in Example 1.

[Example 6]
(Polymer synthesis)
The MA unit of the raw material polymer 1 is ring-opened with a trifunctional (meth) acrylic compound (A-TMM-3LM-N) and a monofunctional (meth) acrylic compound (4-HBA), and then an epoxy group-containing (meth) acrylic. The polymer P4 obtained by reacting with the compound (4HBAGE) was prepared. The details will be described below.
First, 99.49 g of MEK was added to 160 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 the mixture was reacted at a temperature of 70 ° C. for 4 hours. After that, 28.13 g (0.140 mol) of 4HBAGE was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3LM-N and 4-HBA to obtain a polymer P4 which was reacted with 4HBAGE.
By GPC measurement of the polymer P4, the disappearance of the peaks of the polyfunctional (meth) acrylic compound, the monofunctional (meth) acrylic compound, and the epoxy group-containing (meth) acrylic compound used was confirmed. As a result, it was confirmed that the obtained polymer P4 does not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, or an unreacted epoxy group-containing (meth) acrylic compound. ..
Using the polymer P4, the polymer solution 6 and the photosensitive resin composition were prepared in the same manner as in Example 1.

[Example 7]
(Polymer synthesis)
The MA unit of the raw material polymer 1 is ring-opened with a pentafunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth) acrylic compound (GMA). The resulting polymer P5 was prepared. The details will be described below.
First, 102.36 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Then, 52.54 g of A-9550 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 the mixture was reacted at a temperature of 70 ° C. for 4 hours. After that, 26.62 g (0.187 mol) of GMA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-9550 and 4-HBA to obtain a polymer P5 reacted with GMA.
By GPC measurement of the polymer P5, the disappearance of the peaks of the polyfunctional (meth) acrylic compound, the monofunctional (meth) acrylic compound, and the epoxy group-containing (meth) acrylic compound used was confirmed. As a result, it was confirmed that the obtained polymer P5 does not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, and an unreacted epoxy group-containing (meth) acrylic compound. ..
Using the polymer P5, the polymer solution 7 and the photosensitive resin composition were prepared in the same manner as in Example 1.

[Comparative Example 1]
(Preparation of polymer solution)
Polymer P1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 8 having a solid content concentration of 30% by mass.
(Preparation of photosensitive resin composition)
The following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a photosensitive resin composition so that the total solid content concentration was 30% by mass.
-Polymer P1: 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 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-403): 1 part by mass ・ Initiator (manufactured by DIC Corporation, F-556): 0.5 parts by mass Obtained photosensitive resin composition If necessary, the material was filtered through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble matter.

[Comparative Example 2]
A polymer solution 9 was prepared in the same manner as in Comparative Example 1 except that the polymer P2 was used. The photosensitive resin composition was prepared in the same manner as in Comparative Example 1.

[Comparative Example 3]
The polymer solution 10 was prepared in the same manner as in Comparative Example 1 except that the polymer P3 was used. The photosensitive resin composition was prepared in the same manner as in Comparative Example 1.

[Comparative Example 4]
The polymer solution 11 was prepared in the same manner as in Comparative Example 1 except that the polymer P4 was used. The photosensitive resin composition was prepared in the same manner as in Comparative Example 1.

[Comparative Example 5]
The polymer solution 12 was prepared in the same manner as in Comparative Example 1 except that the polymer P5 was used. The photosensitive resin composition was prepared in the same manner as in Comparative Example 1.

<Evaluation method>
The polymers, polymer solutions, and photosensitive resin compositions synthesized in Examples and Comparative Examples were evaluated according to the following. The results are shown in Tables 1 and 2.

(Weight average molecular weight (Mw) / molecular weight distribution (PDI))
For the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (PDI: Mw / Mn), polystyrene-equivalent values obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement are used. The measurement conditions are as follows. The results are shown in Table 1.
Tosoh gel permeation chromatography device HLC-8320GPC
Column: Tosoh TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / ml

(Developability evaluation (dissolution rate of polymer (or photosensitive resin composition) in alkaline developer))
The polymer solution (or photosensitive resin composition) obtained in Examples and Comparative Examples was spin-coated on a wafer, PGMEA was dried, and prebaked at a temperature of 100 ° C. for 2 minutes to obtain a film thickness of 2 μm ± 0. The resin film of 2 was prepared.
This resin film was immersed in a 2.38 mass% TMAH 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. When the alkali dissolution rate is 200 nm / s or more and 2000 nm / s or less, it can be considered that the developability is good.

[Sensitivity evaluation of photosensitive resin composition (2.38% by mass TMAH aqueous solution)]
(Exposure amount at which the residual film ratio is 90% or more)
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), baked at 100 ° C. for 120 seconds on a hot plate, and about 3.0 μm thick. A thin film A (± 0.3 μm) 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 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. in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution for the development time shown in Table 2, and each exposure was 1 to 100 mJ / cm ² . A thin film B exposed and developed by quantity was obtained.
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
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 2. If the exposure amount at which the residual film ratio is 90% or more is 20 mJ / cm ² or less, it can be used as a photosensitive composition without any problem, and if it is 15 mJ / cm ² or less, the sensitivity is considered to be particularly good. be able to.

(Exposure amount with residual film ratio of 95% or more)
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), baked at 100 ° C. for 120 seconds on a hot plate, and about 3.0 μm thick. A thin film A (± 0.3 μm) 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 immersed in a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23 ° C. for the development time shown in Table 2 (immersion together with the wafer), so that each exposure amount was 1 to 100 mJ / cm ² . The thin film B exposed and developed in 1 was obtained.
From the film thicknesses of the thin films A and B obtained by the above method, the residual film ratio was calculated from the following formula.
Remaining film ratio (%) = (film thickness of thin film B / film thickness of thin film A at each exposure amount) × 100
The exposure amount at which the residual film ratio was 95% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. If the exposure amount at which the residual film ratio is 95% or more is 20 mJ / cm ² or less, it can be used as a photosensitive composition without any problem, and if it is 15 mJ / cm ² or less, the sensitivity is considered to be particularly good. be able to.

[Yellow index]
The photosensitive resin composition was spin-coated on Eagle XG glass (Corning Inc., thickness 0.5 mm) and baked on a hot plate at 100 ° C. for 120 seconds to a thickness of about 3.0 μm (± 0.1 μm). A thin film 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 with a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23 ° C. for 10 seconds (immersed together with the wafer) to expose and develop the thin film at an exposure amount of 100 mJ / cm ² . Obtained.
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 2. If the yellow index is 1.10 or less, it can be considered that the heat-resistant discoloration property is good.

[Adhesion during development]
The photosensitive resin composition was spin-coated on Eagle XG glass (Corning Inc., thickness 0.5 mm) and baked on a hot plate at 100 ° C. for 120 seconds to a thickness of about 3.0 μm (± 0.1 μm). A thin film was obtained.
A photomask having a total of five glass parts (exposed parts), alternately having a glass part (exposed part) having a width of 40 μm and a vertical width of 400 μm and a chrome part (light-shielding part) having a width of 40 μm and a vertical width of 400 μm, is passed through this thin film. Then, the g + h + i line was exposed with an exposure amount of 18 mJ / cm ² with a g + h + i line mask aligner (PLA-501F) manufactured by Canon. By this exposure, the glass part of the photomask is exposed with a specified exposure amount because it transmits light, and the chrome part is unexposed because it does not transmit light, and a line pattern having exposed parts and unexposed parts alternately is formed. Obtained. After the exposure, the thin film was developed with a 0.5 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23 ° C. for 15 seconds (immersed together with the wafer) to expose and develop the thin film at an exposure amount of 18 mJ / cm ² . Obtained. The presence or absence of peeling of the line pattern was observed with a microscope at a total of 5 line patterns having a width of 40 μm and a height of 400 μm after exposure and development.
(criterion)
◯: The line pattern after development was in close contact with the substrate, and no peeled part was observed.
X: In the line pattern after development, a portion peeled from the substrate was observed.

Each of the polymers synthesized in Examples 1 to 7 has a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (1-2) in the polymer structure. Therefore, the alkali dissolution rate was good, and therefore the developability was excellent. Further, since the polymer solutions of Examples 1 to 7 contained a predetermined coupling agent (compound (B)), they were excellent in sensitivity, reduced yellowing, and were excellent in adhesion to a substrate.

<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 7.
A green color filter could be formed by forming a film on a 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 7.
A black matrix could be formed by forming a film on a substrate and performing exposure, alkaline development, and the like.

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

Claims (18)

(A) A polymer containing a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (1-2).
(B) A compound having a thiol group and an alkoxy group, or an oligomer thereof,
Polymer solution containing.

(In the general formula (1-1), Z is a group containing one or more (meth) acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X is oxygen. It represents an atomic, substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and any carbon atom of the alkylene group of X may be bonded to form a ring. In (1-2), ^RA is a group containing one or more (meth) acryloyl groups.) The polymer solution according to claim 1, wherein the polymer (A) further contains a structural unit represented by the following general formula (NB).

(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 a1 is 0, 1 or 2. ) The polymer solution according to claim 1 or 2, wherein the Z of the polymer (A) contains a group represented by the following general formula (1a).

(In the general formula (1a), R is a hydrogen atom, a methyl group or an ethyl group.) The polymer solution according to any one of claims 1 to 3, wherein the RA of the polymer ( ^A ) contains at least one group containing 2 to 5 (meth) acryloyl groups. The polymer solution according to any one of claims 1 to 4, wherein the RA of the polymer ( ^A ) contains at least one group represented by the following general formula (1b), (1c) or (1d).

(In the general formula (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. )

(In the general formula (1c),
k, R, X ¹ and X ² are synonymous with R, k, X ¹ and X ² in the general formula (1b), respectively, and a plurality of R may be the same as or different from each other. Multiple X1s may be the same or different from ^each other
X3 is a divalent organic group having 1 to ⁶ carbon atoms.
X ⁴ and X ⁵ are independently single-bonded or divalent organic groups having 1 to 6 carbon atoms, respectively.
X ⁶ is a divalent organic group having 1 to 6 carbon atoms. )

(In the general formula (1d), n is an integer of 2 to 5.) The polymer solution according to any one of claims 1 to 5, wherein the alkoxy group contained in the compound (B) is an alkoxy group having 1 to 3 carbon atoms. The compound (B) has a structure in which a thiol group and an alkoxy group are bonded to an organic chain which may contain one or more atoms selected from O, N, S, P and Si, according to claims 1 to 6. The polymer solution according to any one of. The polymer solution according to any one of claims 1 to 7, wherein the compound (B) contains a compound represented by the following general formula (i).

(In the general formula (i), R independently represent an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two Rs are alkoxy groups having 1 to 3 carbon atoms. ..
L represents an m + n valent organic chain which may contain one or more atoms selected from O, N, S, P and Si.
X represents a single bond or a divalent organic group which may contain a carbonyl group, a (thio) ester group or a (thio) amide group.
Q represents a single bond or a divalent organic group which may contain a carbonyl group or a (thio) ester group or a (thio) amide group.
The m: n (molar ratio) is 1: 1 to 1: 8, and the weight average molecular weight of the compound is 100 to 2000. ) The polymer solution according to any one of claims 1 to 8, wherein the compound (B) or an oligomer thereof is contained in an amount of 0.25% by mass or more and 20% by mass or less with respect to the polymer (A). The polymer solution according to any one of claims 1 to 9, wherein the polymer (A) contains a structural unit represented by the following general formula (1).

(In the general formula (1), Q, X, and Z are synonymous with the general formula (1-1), and ^RA is synonymous with the general formula (1-2).) The polymer solution according to any one of claims 1 to 10, further comprising a structural unit represented by the following general formula (4).

The polymer solution according to any one of claims 1 to 11, further comprising a structural unit represented by the following general formula (5).

(In the general formula (5), Q, X and Z are synonymous with the general formula (1-1).) The polymer solution according to any one of claims 1 to 12, further comprising a structural unit represented by the following general formula (6).

(In the general formula (6), Q, X and Z are synonymous with the general formula (1-1). A plurality of Zs exist, a plurality of Qs exist, and a plurality of Xs exist even if they are the same. May be good.) The polymer solution according to any one of claims 1 to 13, further comprising a structural unit represented by the following general formula (MA).

The polymer solution according to any one of claims 1 to 14, wherein the acid value of the polymer (A) is 70 mgKOH / g or more and 150 mgKOH / g or less. The polymer solution according to any one of claims 1 to 15, which is used for forming a color filter or a black matrix. The polymer solution according to any one of claims 1 to 16 and
With polyfunctional (meth) acrylate monomer,
With a photopolymerizable initiator,
A photosensitive resin composition comprising. The cured product of the photosensitive resin composition according to claim 17.

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