JP2022082436A - Polymer solution, photosensitive resin composition and usage thereof - Google Patents

Abstract

To provide a photosensitive resin composition excellent in sensitivity while having high alkali solubility, thereby excellent in developability with reduced yellow hue and also to provide a polymer solution to be used for the same.SOLUTION: A polymer solution includes: a polymer including both of, a structural unit obtained by adding an epoxy group-containing unsaturated compound to a carboxyl group of a structural unit derived from an unsaturated carboxylic acid, and a structural unit obtained by binding, by an ester linkage, a hydroxyalkyl (meth)acrylate to a carboxyl group having a structure derived from an unsaturated carboxylic acid; and a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups. The amount of the polyfunctional (meth)acrylic compound is 1 to 40 mass%, inclusive, with regard to the polymer.SELECTED DRAWING: None

Description

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

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

International Publication No. 2012/147706

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

Further, when forming a color filter or a black matrix, especially when the content of the pigment in the photosensitive resin composition is high, the solubility of the pigment in the basic developer is low, so that the photosensitive resin composition is formed. It takes a long time to develop. Therefore, it is necessary to use a strong basic developer whose development speed is faster than that of the conventional basic developer. However, if the polymer has high alkali solubility, the alkali dissolution rate of the photosensitive resin composition containing the pigment or the photopolymerization initiator may be too fast, or the difference in dissolution rate between the pigment and the resin composition may become too large. Therefore, the pattern after exposure and development may not have the shape as designed.

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 addition, if the reproducibility of the photosensitive resin composition is too low, the fine line patterns such as the color filter and the black matrix do not have the shape as designed when patterning by exposure and development, and undissolved residue occurs in the vicinity of the pattern. As a result, the degree of opening is lowered and light does not pass through, so that dots with poor color reproducibility are generated, which may cause a problem that the yield of the panel is lowered. Such a problem is particularly remarkable when forming a black matrix that requires a finer fine line pattern or when patterning a thick film having a thickness of about 10 to 20 μm.

In the case of using a strongly basic developer, the present inventor adjusts the alkali solubility of the polymer contained in the photosensitive resin composition in order to make the pattern after exposure and development as designed. It has been found that it is necessary to maintain and improve the sensitivity, suppress the undissolved residue in the vicinity of the pattern after development, and have excellent adhesion to the substrate. Furthermore, the present inventors have found that the problem can be solved by improving the polymer structure, and have completed the present invention.

According to the present invention
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).
Containing a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups,
A polymer solution is provided in which the polyfunctional (meth) acrylic compound is in an amount of 1% by mass or more and 40% by mass or less with respect to the polymer.

（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り、
Ｑは、水素原子、または置換もしくは未置換の炭素数１～６のアルキル基であり、
Ｘは、酸素原子、または置換もしくは未置換の炭素数１～４のアルキレン基を表し、
Ｑが前記アルキル基であり、Ｘが前記アルキレン基である場合、ＱとＸが縮合して環式基を形成してもよい。）

(In 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 or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. )

（一般式（１－２）中、Ｒ^Ｄは、２つ以上の（メタ）アクリロイル基を含む基である。）

(In the general formula (1-2), ^RD is a group containing two or more (meth) acryloyl groups.)

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

Further, according to the present invention, there is provided a cured product formed from the above-mentioned photosensitive resin composition.

Further, according to the present invention, a film made of the above-mentioned cured product is provided.

According to the present invention, according to the present invention, a photosensitive resin composition having good sensitivity, high alkali solubility, and thus excellent developability and reduced yellowing, and used for the same. A polymer solution for this is provided.

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

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

In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The notation "(meth) acrylic" herein represents a concept that includes both acrylic and methacrylic. The same applies to similar notations such as "(meth) acrylate".
In particular, the "(meth) acryloyl group" in the present specification means an acryloyl group represented by -C (= O) -CH = CH ₂ and -C (= O) -C (CH ₃ ) = CH ₂ . Represents a concept including a methacryloyl group represented by.

[Polymer solution]
The polymer solution of this embodiment contains a polymer having a specific structure and a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups. In the polymer solution of the present embodiment, the polyfunctional (meth) acrylic compound is contained in an amount of 1% by mass or more and 40% by mass or less with respect to this polymer.

(Polymer P)
The polymer used in the polymer solution of the present embodiment (referred to as “polymer P” in the present specification) is a structural unit represented by the following general formula (1-1) and the following general formula (1-2). Includes the represented structural units.

The polymer P used in the polymer solution of the present embodiment has excellent sensitivity and is alkaline by containing the structural unit represented by the general formula (1-1) and the structural unit represented by the general formula (1-2). It has excellent solubility and can be suitably used as a color filter or a polymer for forming a black matrix. It is considered that this is because the curing reaction (polymerization reaction) is promoted by the (meth) acryloyl group contained in the structural unit represented by the formula (1-1) or the formula (1-2). In particular, the polymer P used in the polymer solution of the present embodiment has its alkali solubility adjusted and is excellent in sensitivity. Therefore, when a strong basic developer such as a tetramethylammonium hydroxide (TMAH) solution is used, it is exposed. The developed 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 polymer P has excellent sensitivity and alkali solubility (developability), in other words, an excellent balance between them.

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

In the formula (1-1), X is an alkylene having 1 to 4 carbon atoms and Z is a (meth) acryloyloxy group represented by the following general formula (1a), or X is an oxygen atom. The embodiment in which there is and Z is a (meth) acryloyl group is preferably used.

In the general formula (1a), R is a hydrogen atom or a methyl group.

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

^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 equation (1b),
k is 2 or 3
R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different.
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by —Z—X— (Z is —O— or —OCO—, and X is an alkylene group having 1 to 6 carbon atoms. ), And multiple ^X1s may be the same or different.
X ^1'is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'-(X'is an alkylene group having 1 to 6 carbon atoms, and Z'is -O- or -COO-),
X ² is a k + 1 valent organic group having 1 to 12 carbon atoms.
R is preferably a hydrogen atom because of further improvement in sensitivity (easiness of polymerization) and the like.
Although k may be 2 or 3, it is preferably 3 from the viewpoint of further improving the availability of raw materials and the sensitivity.

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

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

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

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

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

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

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

The proportion of the structural unit represented by the general formula (1-1) in the total structural unit of the polymer P is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%. The ratio of the structural unit represented by the general formula (1-2) is preferably 1 to 30 mol%, more preferably 2 to 20 mol%.

The polymer P can include a structural unit 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). ..

In the general formula (1), Q, X, and Z are synonymous with the general formula (1-1), and ^RD 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 P is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

The polymer P is a structural unit including a structural unit represented by the general formula (1-1), which is a structural unit represented by the general formula (3), a structural unit represented by the general formula (5), and a general formula (general formula (5), which will be described later. 6) It can also include the structural unit represented. These structural units will be described later.
Further, the polymer P may also include a structural unit represented by the general formula (8) described later as a structural unit including the structural unit represented by the general formula (1-2). This structural unit will be described later.

The polymer P can further contain a structural unit represented by the following general formula (2).

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

The structural unit represented by the general formula (2) is chemically robust. Therefore, the polymer P containing this as a structural unit has a small weight loss and is stable when subjected to heat treatment. Therefore, the photosensitive resin composition containing the polymer P can be suitably used for producing a film or a filter for use in a liquid crystal display device or a solid-state image sensor that requires heat resistance.

Examples of the organic group having 1 to 30 carbon atoms which can constitute R ¹ to R ⁴ in the general formula (2) include substituted or unsubstituted, linear or branched alkyl having 1 to 30 carbon atoms. More specifically, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, an alkoxy group, a heterocyclic group, a carboxyl group and the like can be mentioned.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group and a heptyl group. Examples thereof include an octyl group, a nonyl group and a decyl group.
Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group and the like.
Examples of the alkynyl group include an ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.

Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthrasenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaline group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group and a neopentyloxy group. , N-hexyloxy group and the like.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

In the structural unit represented by the general formula (2), 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 in the general formula (2) 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 (2), a ₁ is preferably 0 or 1, more preferably 0.

The proportion of the structural unit represented by the general formula (2) in the total structural units of the polymer P is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%. be.

The polymer P can further contain a structural unit represented by the following general formula (3-1).

In the general formula (3-1), ^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 P preferably further contains a structural unit represented by the general formula (3-1), whereby both sensitivity and developability are well balanced. It can be compatible.

^RS is, for example, a group represented by the following general formula (3a).

In the general formula (3a), 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 (3-1) 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 (3-1) in the total structural unit of the polymer P is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

The polymer P can include a structural unit represented by the following general formula (3) consisting of a structural unit represented by the general formula (1-1) and a structural unit represented by the general formula (3-1). ..

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 (3-1).

When the polymer P contains the structural unit represented by the general formula (3), the ratio of the structural unit represented by the general formula (3) to the total structural unit of the polymer P is preferably 3 to 35 mol%. More preferably, it is 7 to 25 mol%.

The polymer P may also contain a structural unit represented by the general formula (8) described later as a structural unit including the structural unit represented by the general formula (3-1). This structural unit will be described later.

The polymer P 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 P is alkaline-dissolved. The sex can be adjusted. As a result, the photosensitive resin composition containing the polymer P has an excellent balance between sensitivity and developability even when subjected to a photolithography process using a strong basic developer.

When the polymer P contains the structural units represented by the general formula (4), the ratio of the structural units represented by the general formula (4) to the total structural units of the polymer P is preferably 1 to 15 mol%. More preferably, it is 2 to 10 mol%.

The polymer P can further contain a structural unit represented by the following general formula (5) including 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 P contains the structural units represented by the general formula (5), the ratio of the structural units represented by the general formula (5) to the total structural units of the polymer P is preferably 1 to 12 mol%. More preferably, it is 1 to 9 mol%.

From the viewpoint of the effect of the present invention, the polymer P can further include a structural unit represented by the following general formula (6) consisting of two structural units represented by the general formula (1-1). 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 P contains the structural unit represented by the general formula (6), the ratio of the structural unit represented by the general formula (6) to the total structural unit of the polymer P is preferably 1 to 10 mol%. More preferably, it is 1 to 8 mol%.

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

In the general formula (7), ^RD is synonymous with the general formula (1-2).
When the polymer P contains the structural unit represented by the general formula (7), the ratio of the structural unit represented by the general formula (7) to the total structural unit of the polymer P is preferably 0.5 to 25 mol. %, More preferably 1-18 mol%.

In the general formula (8), Q, X and Z are synonymous with the general formula (3-1).
When the polymer P contains the structural unit represented by the general formula (8), the ratio of the structural unit represented by the general formula (8) to the total structural unit of the polymer P is preferably 0.5 to 35 mol. %, More preferably 2 to 25 mol%.

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

The polymer P may contain an organic group having a thioether group (—S—). Since the polymer P has a thioether group, it has excellent sensitivity in the photolithography method, has higher alkali solubility, and thus has better developability, and resin curing with reduced yellowing and excellent transparency. Can provide things.

When the polymer P contains an organic group having a thioether group, the organic group having a thioether group is a thioether-containing organic having 1 to 6 valences having 1 to 6 carbon atoms derived from a bifunctional or higher thiol group-containing compound and having 1 to 30 carbon atoms. The group (referred to as "thioether group-containing organic group (i)" in the present specification "is preferable. Here, the number of functional groups in the" bifunctional or higher thiol group-containing compound "refers to the number of thiol groups. That is, the thiol group-containing compound means a compound containing two or more thiol groups. When the polymer P contains a thioether group-containing organic group (i), the polymer P is a thiol group contained in the thiol group-containing compound. It has a structure in which the above structural units are bonded via 1 to 6 thioether groups derived from the above. The thioether group-containing organic group (i) derived from the thiol group-containing compound is the same as the above-mentioned structural units. The polymer P may have a thiol group that does not participate in the bond, and the polymer P has a different number of 1 to 6-valent thioether-containing organic groups having 1 to 6 carbon atoms derived from a bifunctional or higher thiol group-containing compound. It can be a mixture of polymers to which the structural units described above are attached.

The thioether group-containing organic group (i) is bifunctional or higher, preferably trifunctional or higher. The upper limit is not particularly limited, but is 6 functional or less.
The valence of the thioether group-containing organic group (i) is 1 to 6 valences, preferably 2 to 6 valences, and more preferably 3 to 6 valences from the viewpoint of the effect of the present invention.

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

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

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

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

Specific examples of the bifunctional or higher functional thiol group-containing compound capable of inducing the thioether group-containing organic group (i) include, but are not limited to, the following formulas (s-1) to (s-21).

In the present embodiment, the bifunctional or higher functional thiol group-containing compound preferably contains a trifunctional or higher functional thiol group-containing compound from the viewpoint of the effect of the present invention. Further, it is more preferable that the thiol group-containing compound contains an ester structure.
In the present embodiment, the bifunctional or higher functional thiol group-containing compound has the chemical formulas (s-1) to (s-3), among the compounds represented by the chemical formulas (s-1) to (s-21). It is more preferable to contain the compounds represented by (s-5) and (s-8) to (s-10), and the chemical formulas (s-1) to (s-3), (s-5) and (s) are more preferable. It is particularly preferable to include the compound represented by -9).

As the bifunctional or higher functional thiol group-containing compound, one kind may be used alone, or two or more kinds may be used in combination.
The 1- to 6-valent thioether group-containing organic group (i) has a thioether group (-S- * (* is a bond)) derived from the thiol group of these thiol group-containing compounds at the end, and this thioether. It binds to the structural units described above via a group. The thioether group-containing organic group (i) may have a thiol group that does not participate in the bond with the above-mentioned structural unit.

The polymer P may contain additional structural units derived from the norbornene monomer and the monomer polymerizable with maleic anhydride. Such structural units include substituted or unsubstituted inden, maleimide, styrene, acenaphtylene, norbornadien, dihydrofuran, terpene compounds (eg, pinen, limonene, etc.), linear alkenes (eg, penten, etc.), cyclic alkenes. (Eg, cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth) acrylic acid compounds (eg, methyl methacrylate). , Methyl acrylate), vinyl acetate, structural units derived from vinyl ethers (eg, 2-hydroxyethylvinyl ether, etc.). Examples of the substituent that these monomers can have include an alkyl group and an aryl group. More specifically, examples of the substituted indene include methyl indene and the like. Examples of the substituted maleimide include cyclohexylmaleimide and phenylmaleimide. Examples of the substituted styrene include methylstyrene and vinyltoluene.

Of these, the structural unit is preferably a structural unit represented by the general formula (IN) (a divalent structural unit derived from a substituted or unsubstituted inden) or a structural unit represented by the general formula (MI) (MI). A divalent structural unit derived from substituted or unsubstituted maleimide), a structural unit represented by the general formula (ST) (a divalent structural unit derived from substituted or unsubstituted styrene), or a general formula ( Includes structural units represented by NBD) (divalent structural units derived from substituted or unsubstituted norbornadien).

In the general formula (IN), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (MI), R ³ represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (ST), R ⁴ to R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (NBD), R ⁷ to R ¹⁰ independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

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

The weight average molecular weight Mw of the polymer P 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 to 80. It is 000. By appropriately adjusting the weight average molecular weight, the sensitivity and the solubility in an alkaline developer can be adjusted.

The dispersity of the polymer P (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 8.0, more preferably 1.5 to 7.0, and even more preferably 2.0 to 6. It is 0. By appropriately adjusting the dispersity, the physical properties of the polymer P can be made uniform, which is preferable. These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

(Manufacturing method of polymer P)
The polymer P of the present embodiment can be produced (synthesized) by any method. The method for producing the polymer P will be described with reference to the first embodiment, the second embodiment, and the third 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 P of the above may contain a structural unit represented by the general formula (8) and a structural unit represented by the general formula (3).

(First Embodiment)
The method for producing the polymer P of the present embodiment is as follows.
(I) The structural unit represented by the following general formula (2), 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). A first step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing a structural unit represented; 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 (2), 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). , A second step of preparing the polymer P, optionally comprising a structural unit represented by the following general formula (MA).

Hereinafter, a method for producing (synthesizing) the polymer P 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 (2) 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 the structural unit represented by the following general formula (2), the structural unit represented by the following general formula (7), and the following general formula (MA). The step of preparing a first polymer precursor containing structural units; and

(I-iii) A compound having a first polymer precursor obtained in the step (I-iii), 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 structural unit represented by the following general formula (2), the structural unit represented by 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-iii) 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 (2) 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) the monomer to be produced and maleic anhydride. The definitions of R ¹ , R ² , R ³ and R ⁴ and a ₁ of the general formula (NBm) are the same as those of the general formula (2). The same applies to the preferred embodiment.

Examples of the monomer represented by the general formula (NBm) include bicyclo [2.2.1] -hept-2-ene (conventional name: 2-norbornene), 5-methyl-2-norbornene, and 5-ethyl-. 2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-Methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene- Examples thereof include methyl 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 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.

(Step (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 (2) 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).

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 (2), 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 the 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 (2) is formed by the general formula (2). 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-iii). 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-iii) and the step of reacting the monofunctional (meth) acrylic compound (I-iii) are not performed at the same time, but are sequentially performed 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 (Ii) can be used as it is. Therefore, in the step (I-iii), the first polymer precursor is isolated and purified from the reaction mixture containing the first polymer precursor obtained in the step (I-iii), or is contained in the mixture. By adding a monofunctional (meth) acrylic compound to the reaction mixture containing the first polymer precursor obtained in step (I-ii) in situ without neutralizing the basic catalyst. It is preferable to carry out.

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. A structural unit represented by the general formula (1) and a structural unit represented by the general formula (3) are formed by the reaction of the (meth) acrylic compound with the epoxy group, and the structure represented by the general formula (1) is formed. The unit, the structural unit represented by the above-mentioned general formula (2), the structural unit represented by the above-mentioned general formula (3), the structural unit represented by the above-mentioned general formula (7), and the above-mentioned general formula (8). ), And optionally the polymer P containing the structural unit represented by the above general formula (MA).

The 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 the 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 can be 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. preferable.

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 polymer P 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 P.

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

An excess amount of toluene is added to the obtained organic solution of the polymer P to reprecipitate the polymer P. In addition, the polymer powder obtained by reprecipitation is washed with toluene several times (for example, twice).
Further, in order to remove the acid and the basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (for example, three times).
High-purity polymer P 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 P of the present embodiment is as follows.
(A) The structural unit represented by the following general formula (2), 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). First step of preparing a polymer precursor (hereinafter referred to as "polymer precursor P'") containing the structural unit to be used;

(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 (2) 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 containing (hereinafter referred to as "polymer precursor P"); 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 (2), 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). Includes a third step of preparing a polymer containing the structural units to be made.

Hereinafter, a method for producing (synthesizing) the polymer P 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 is represented by the structural unit represented by the general formula (2), the structural unit represented by the general formula (4), and the general formula (7). 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 the structures of general formula (2), 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 a catalyst similar to the basic catalyst used in the above step (I-iii) 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-mentioned step (I-iii), and the obtained reaction solution is preferably 0 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 prepare the polymer P. Since the reaction conditions of the third step (c) are the same as those of the second step (ii) of the first embodiment, 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 P.

(Third embodiment)
The method for producing the polymer P of the present embodiment is as follows.
(A) Structural unit represented by the following general formula (2), structural unit represented by the following general formula (7), structural unit represented by the following general formula (8), bifunctional or higher thiol group-containing compound. A polymer precursor containing a thioether-containing organic group (i) (thioether-containing organic group (i)) having 1 to 6 valent carbon atoms of 1 to 30 carbon atoms derived from the above, and a structural unit represented by the following general formula (MA). First step of preparing a compound (hereinafter referred to as "polymer precursor P'"); and

(B) 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 (2), 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). , A second step of preparing the polymer P, which comprises the thioether-containing organic group (i) and optionally the structural unit represented by the following general formula (MA).

Hereinafter, a method for producing (synthesizing) the polymer P of the present embodiment by these steps will be described. In the third embodiment, only the first step (A) for preparing the polymer precursor is different from the first step (I) for preparing the polymer precursor of the first embodiment. Therefore, the description of the step (B) will be omitted.

The first step (A) for preparing the polymer precursor P'is
(A-i) A step of preparing a raw material polymer containing a structural unit represented by the following general formula (2), a structural unit represented by the following general formula (MA), and a thioether-containing organic group (i);

(A-ii) The raw material polymer obtained in step (A-i) and a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as "polyfunctional (meth) acrylic compound"). In the presence of a basic catalyst, the structural unit represented by the following general formula (2), the structural unit represented by the following general formula (7), the thioether-containing organic group (i), and the following general The step of preparing the first polymer precursor containing the structural unit represented by the formula (MA); and

(A-iii) A compound having a first polymer precursor obtained in the step (A-iii), 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 structural unit represented by the following general formula (2), the structural unit represented by 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, the thioether-containing organic group (i), and the structural unit represented by the following general formula (MA).

(Step (A))
In the step (A-i), the step of preparing the raw material polymer containing the structural unit represented by the general formula (2), the structural unit represented by the general formula (MA), and the thioether-containing organic group (i) is , The monomer represented by the general formula (NBm) and maleic anhydride can be carried out by polymerization (addition polymerization) in the presence of the bifunctional or higher functional thiol group-containing compound. The definitions of R ¹ , R ² , R ³ and R ⁴ and a ₁ of the general formula (NBm) are the same as those of the general formula (2). The same applies to the preferred embodiment. Further, the polymerization conditions are the same as those in the step (Ii) of the first embodiment.

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

The steps (A-iii) and (A-iii) of the present embodiment use the same conditions as in the steps (I-ii) and (I-iii) of the first embodiment, respectively. Can be carried out.

Also in this embodiment, after the step (B), 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 P.

(Polyfunctional (meth) acrylic compound)
The polymer solution of this embodiment contains a polyfunctional (meth) acrylic compound. By containing the polyfunctional (meth) acrylic compound, the alkali solubility of the photosensitive resin composition is improved, the yellowing of the photosensitive resin composition is reduced, and a cured product having excellent transparency can be obtained. It will be possible. Furthermore, by containing the polyfunctional (meth) acrylic compound, when the polymer solution is used for manufacturing a color filter, a black matrix, etc., the generation of undissolved residue near the pattern of the fine line pattern is further suppressed, and the desired shape is obtained. Therefore, the yield is further improved, the yellowing of the fine line pattern is further reduced, and the transparency is improved.

Examples of the polyfunctional (meth) acrylic compound to be blended in the polymer solution of the present embodiment include a compound represented by the following formula (1bp), a compound represented by the formula (1cp), and a compound represented by the following formula (1cp). Examples thereof include compounds represented by the formula (1d-p), but the present invention is not limited thereto. The definitions and specific embodiments of k, R, X ¹ , X ^1'and X ² in the formula (1bp) are the same as those in the above formula (1b). Further, the definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in the formula (1c-p) are the same as those in the above formula (1c). N and R in the formula (1d-p) are the same as those in the above formula (1d). Y in formula (1bp), formula (1c-p) and formula (1d-p) is a hydrogen atom or (meth) acryloyl group, or a combination thereof.

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 is blended in an amount of 1% by mass or more and 40% by mass or less with respect to the polymer P, and in an amount of 4% by mass or more and 30% by mass or less. It is more preferably blended, more preferably 5% by mass or more and 25% by mass or less, and even more preferably 5.5% by mass or more and 20% by mass or less. As a result, when the polymer solution is used in the production of color filters, black matrices, etc., the generation of undissolved residue in the vicinity of the fine line pattern is further suppressed, and the desired shape is obtained, so that the yield is further improved and the yield is further improved. The yellowing of the fine line pattern is further reduced and the transparency is improved.

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

Examples of the monofunctional (meth) acrylic compound that may be used in the photosensitive resin composition of the present embodiment include compounds represented by the following formula (3am). The definitions of ^X10 and R in the formula (3am) are as described above.

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.

When the polymer solution of the present embodiment contains a monofunctional (meth) acrylic compound, the amount thereof is, for example, in the range of 1% by mass to 5% by mass with respect to the polymer P.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The film thickness of the photosensitive resin film is not particularly limited and may be appropriately adjusted according to the pattern to be finally obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by adjusting the content of the solvent in the photosensitive resin composition, the coating method, and the like.

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

Examples of the active ray include X-rays, electron beams, ultraviolet rays, visible rays and the like. In terms of wavelength, light having a wavelength of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp, and i-line is particularly preferable. Further, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is preferable.
The amount of light for exposure may be appropriately adjusted depending on the amount of the photosensitive agent in the photosensitive resin film and the like, and is, for example, about 100 to 500 mJ / cm ² .

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

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

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

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

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

In the present embodiment, it is preferable to use an alkaline aqueous solution as a developer, and it is more preferable to use a tetramethylammonium hydroxide, a sodium carbonate aqueous solution, or a potassium hydroxide aqueous solution.
The concentration of the alkaline aqueous solution is preferably 0.1 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.

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

・ＴＭＭＰ：トリメチロールプロパントリス（３－メルカプトプロピオネート）、下記式（ｓ－１）で表される化合物 （ＳＣ有機化学株式会社製）

・ＤＰＭＰ：ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、下記式（ｓ－３）で表される化合物（ＳＣ有機化学株式会社製）

・４－ＨＢＡ：４－ヒドロキシブチルアクリレート
・ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
・ＧＭＡ：メタクリル酸グリシジル
・Ａ－ＴＭＭ－３ＬＭ－Ｎ：以下２種の化合物の混合物、ガスクロマトグラフ測定に基づく混合物中の左の化合物の量は約５７％（新中村化学工業株式会社製）

The compounds used in the examples may be indicated by the following abbreviations or trade names.
-MA: maleic anhydride-NB: 2-norbornene-MEK: methyl ethyl ketone-PEMP: pentaerythritol tetrakis (3-mercaptopropionate), a compound represented by the following formula (s-2) (manufactured by SC Organic Chemistry Co., Ltd.) )

-TMMP: Trimethylolpropanetris (3-mercaptopropionate), a compound represented by the following formula (s-1) (manufactured by SC Organic Chemistry Co., Ltd.)

-DPMP: Dipentaerythritol hexakis (3-mercaptopropionate), a compound represented by the following formula (s-3) (manufactured by SC Organic Chemistry Co., Ltd.)

4-HBA: 4-hydroxybutyl acrylate-HEMA: 2-hydroxyethyl methacrylate-GMA: glycidyl methacrylate-A-TMM-3LM-N: A mixture of the following two compounds, left in the mixture based on gas chromatograph measurement The amount of compound in 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.).

<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.

(Synthesis of raw material polymer 2)
In a reaction vessel equipped with a stirrer, a condenser and a dropping funnel, 602.56 g (NB equivalent 451.92 g, 4.8 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MA, 470.69 g, 4). 8.8 mol) and 2238.50 g of methyl ethyl ketone (MEK) were added, and the mixture was stirred and dissolved. Next, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 80 ° C., dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601). , 44.21 g, 0.19 mol) and PEMP (pentaerythritol tetrakis (3-mercaptopropionate)) (140.73 g, 0.29 mol) dissolved in MEK189.74 g were added over 1 hour. Then, the reaction was further carried out at 80 ° C. for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid is further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120 ° C. to provide a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (a polymer having a structural unit derived from maleic anhydride. Raw material polymer 2) 908.1 g was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2700, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.57. there were.

[Structural analysis of raw material polymer 2]
At the start of the reaction, the synthesis of the raw material polymer 2 is started with the monomer and PEMP dissolved in the solvent, and then the reaction proceeds to form the polymer. Analysis of each of the reaction solution and the obtained polymer gave the following results.

(A) Analysis of reaction solution No peak of PEMP alone was observed in the GPC measurement of the reaction solution before reprecipitation purification. That is, it was confirmed that no PEMP remained in the reaction solution. In addition, in the GC (gas chromatography) measurement of the reaction solution before reprecipitation and purification, the peaks of 2-norbornen alone and maleic anhydride alone in the reaction solution after the reaction were reduced compared to before the reaction, and 2-. It was confirmed that norbornene and maleic anhydride reacted to form a polymer.
The measurement conditions for gas chromatography measurement were as follows.
-GC equipment: GC-2030 (Shimadzu Corporation)
・ Carrier gas: N ₂
-Detector: Hydrogen flame ionization (FID) detector, FID temperature: 300 ° C
-Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Co., Ltd.)
・ Vaporization chamber temperature: 210 ℃
-Column flow rate: 0.64 mL / min
-Column temperature rise conditions: 50 ° C 5 min hold, 20 ° C / min temperature rise to 300 ° C, 300 ° C 10 min hold

(B) Polymer analysis In the GPC measurement of the polymer after reprecipitation and purification, no peaks of PEMP alone, 2-norbornene alone, and maleic anhydride alone were observed. That is, it was confirmed that PEMP, 2-norbornene alone and maleic anhydride did not remain in the polymer.

The amount of sulfur in the obtained raw material polymer 2 was confirmed by elemental analysis by flask combustion and ion chromatography, and it was confirmed that the sulfur element was present in the raw material polymer 2. Further, in the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained. Therefore, it was confirmed that PEMP was incorporated into the raw material polymer 2.

The elemental analysis method is as follows.
-Test item Flask combustion-Quantification of total sulfur by ion chromatography-Test method Flask combustion-Ion chromatography (1) Completely burn about 50 mg of a sample in a sealed flask replaced with oxygen.
(2) The generated gas is collected in a hydrogen peroxide-absorbing 57-collecting liquid in a flask to which a pre-added gas has been added, and a constant volume of 50 ml is used as a test solution.
(3) A test solution and a standard solution are introduced into an ion chromatographic analyzer, the concentration of sulfate ion is determined by the calibration curve method, and the amount of sulfur contained in the sample is calculated.
-Device used Dionex ICS-3000 type ion chromatograph

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

ＰＥＭＰを使用して合成した原料ポリマー１の^１３Ｃ－ＮＭＲ測定において、６２．０ｐｐｍ付近に、炭素ｂ由来のピークｂの出現を確認した。反応溶液のＧＰＣ測定で、ＰＥＭＰ単体のピークが認められず、未反応のＰＥＭＰが残っていないことから、ＰＥＭＰが原料ポリマー１中に取り込まれたことを確認した。
また、原料ポリマー１の^１３Ｃ－ＮＭＲ測定では、炭素ａ由来のピークａが確認されず、代わりに２８ｐｐｍ付近に６２．０ｐｐｍチオエーテル（Ｒ－Ｓ－Ｒ'）に対応するピークｃが出現した。このピークｃの積分値はピークｂの積分値のおよそ２倍になっていることから、原料ポリマー２は下記のようなチオエーテル基を有する骨格を備えており、チオール基は消失していた。原料ポリマー２を用いて合成した実施例のポリマーも同様の骨格を備えると考えられる。

In the ¹³ C-NMR measurement of the raw material polymer 1 synthesized using PEMP, the appearance of the peak b derived from carbon b was confirmed at around 62.0 ppm. In the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained. Therefore, it was confirmed that PEMP was incorporated into the raw material polymer 1.
Further, in the ¹³ C-NMR measurement of the raw material polymer 1, the peak a derived from carbon a was not confirmed, and instead, the peak c corresponding to 62.0 ppm thioether (RSR') appeared in the vicinity of 28 ppm. Since the integrated value of the peak c is about twice the integrated value of the peak b, the raw material polymer 2 has a skeleton having a thioether group as described below, and the thiol group has disappeared. It is considered that the polymer of the example synthesized by using the raw material polymer 2 also has a similar skeleton.

^１３Ｃ－ＮＭＲ測定の条件は以下の通りである。
（試験条件）測定サンプルは、秤量した試料に測定溶媒を加えて濃度調製した後、ＮＭＲ測定用試料管に規定分量注いで作製した。
・測定装置：日本電子ＪＮＭ－ＥＣＡ４００超伝導ＦＴ－ＮＭＲ装置
・共鳴周波数：１００．５３ＭＨｚ
・測定核：^１３Ｃ
・測定法：ＮＮＥ測定（インバースゲートデカップリング法）
・パルス幅：３．８３μｓｅｃ
・パルス繰り返し待ち時間：３０ｓ
・積算回数：４０９６回
・測定温度：室温
・測定溶媒：ＤＭＳＯ－ｄ６（重水素化ジメチルスルホキシド）
・試料濃度：２０％（ｗ／ｖ）

¹³ The conditions for C-NMR measurement are as follows.
(Test conditions) The measurement sample was prepared by adding a measurement solvent to the weighed sample to adjust the concentration, and then pouring a specified amount into a sample tube for NMR measurement.
・ Measuring device: JEOL JNM-ECA400 superconducting FT-NMR device ・ Resonance frequency: 100.53MHz
・ Measurement nucleus: ¹³ C
-Measurement method: NNE measurement (inverse gate decoupling method)
-Pulse width: 3.83 μsec
・ Pulse repetition waiting time: 30s
・ Number of integrations: 4096 times ・ Measurement temperature: Room temperature ・ Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide)
-Sample concentration: 20% (w / v)

(Synthesis of raw material polymer 3)
Similar to the raw material polymer 2, it has a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride, except that TMMP (101.99 g, 0.25 mol) is used instead of PEMP. 900.1 g of a polymer (raw material polymer 3) was obtained.
As a result of measuring the obtained raw material polymer 3 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,100, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was. It was 1.74.
In the GPC measurement of the reaction solution, no peak of TMMP alone was observed, and no unreacted TMMP remained. Therefore, it was confirmed that TMMP was incorporated into the raw material polymer 3.
Further, it was confirmed by ¹³ C-NMR measurement of the raw material polymer 3 that TMMP was incorporated into the raw material polymer 3.
The amount of sulfur in the obtained raw material polymer 3 was confirmed by elemental analysis by flask combustion and ion chromatography, and it was confirmed that the sulfur element was present in the raw material polymer 3.

(Synthesis of raw material polymer 4)
Similar to the raw material polymer 2, it has a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride, except that DPMP (100.23 g, 0.13 mol) is used instead of PEMP. 890.2 g of a polymer (raw material polymer 4) was obtained.
As a result of measuring the obtained raw material polymer 4 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,600, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was. It was 2.02.
In the GPC measurement of the reaction solution, no peak of DPMP alone was observed, and no unreacted DPMP remained. Therefore, it was confirmed that DPMP was incorporated into the raw material polymer 4.
Further, it was confirmed by ¹³ C-NMR measurement of the raw material polymer 4 that DPMP was incorporated into the raw material polymer 4.
The amount of sulfur in the obtained raw material polymer 4 was confirmed by elemental analysis by flask combustion and ion chromatography, and it was confirmed that the sulfur element was present in the raw material polymer 4.

<Synthesis of polymer P>
(Preparation Example 1: Preparation of polymer P1)
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 (HEMA), and then an epoxy group-containing (meth) acrylic compound (meth). The polymer P1 obtained by reacting with GMA) was prepared. The details will be described below.
First, 102.26 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, 50.78 g (0.390 mol) of HEMA 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 1 was ring-opened with A-TMM-3LM-N and HEMA to obtain a polymer P1 reacted with GMA.
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 by the polymer P1 GPC measurement. 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. ..

(Preparation Example 2: Preparation of polymer P2)
The MA unit of the raw material polymer 1 is ring-opened with a trifunctional (meth) acrylic compound (A-TMM-3LM-N), water is further added to open the ring, and then an epoxy group-containing (meth) acrylic compound (GMA) is opened. ) To prepare the obtained polymer P2. The details will be described below.
First, 103.92 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, 1.50 g (0.083 mol) of water was added, and the mixture was reacted at a temperature of 70 ° C. for 2 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 1 was ring-opened with A-TMM-3LM-N and water to obtain a polymer P2 reacted with GMA.
By GPC measurement of the polymer P2, the disappearance of the peaks of the polyfunctional (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, and an unreacted epoxy group-containing (meth) acrylic compound. ..

(Preparation Example 3: Preparation of Polymer P3)
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 P3 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 1 was ring-opened with A-9550 and 4-HBA to obtain a polymer P3 reacted with GMA.
By GPC measurement of the polymer P3, 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 P3 does not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, and an unreacted epoxy group-containing (meth) acrylic compound. ..

(Preparation Example 4: Preparation of Polymer P4)
The MA unit of the raw material polymer 2 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 (GMA) was prepared. The details will be described below.
First, 100.54 g of MEK was added to 260 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, 40.51 g (0.281 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-TMM-3LM-N and 4-HBA to obtain a polymer P4 reacted with GMA.
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, and an unreacted epoxy group-containing (meth) acrylic compound. ..

(Preparation Example 5: Preparation of Polymer P5)
Polymer P5 was prepared in the same manner as in Preparation Example 4 except that the amount of 4-HBA added was 54.02 g, GMA was 33.28 g, and MEK was replaced with 100.91 g.

(Preparation Example 6: Preparation of Polymer P6)
Polymer P13 obtained by opening the MA unit of the raw material polymer 2 with a trifunctional (meth) acrylic compound (A-TMM-3LM-N) and then reacting with an epoxy group-containing (meth) acrylic compound (GMA). Was produced. The details will be described below.
First, 100.57 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, 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 to obtain a polymer P6 reacted with GMA.
By GPC measurement of the polymer P6, the disappearance of the peaks of the polyfunctional (meth) acrylic compound, the monofunctional (meth) acrylic compound, and the epoxy group-containing (meth) acrylic compound used was confirmed. As a result, it was confirmed that the obtained polymer P6 does not contain an unreacted (meth) acrylic compound, a (meth) acrylic compound having no hydroxyl group, and an unreacted epoxy group-containing (meth) acrylic compound. ..

(Preparation Example 7: Preparation of Polymer P7)
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 P7 obtained by reacting with compound (GMA) was prepared. The details will be described below.
First, 100.14 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, 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 MA unit of the raw material polymer 3 is ring-opened with a trifunctional (meth) acrylic compound (A-TMM-3LM-N) and a monofunctional (meth) acrylic compound (4-HBA), and then contains an epoxy group ( A polymer P7 obtained by reacting with a meta) acrylic compound (GMA) was prepared.

(Preparation Example 8: Preparation of Polymer P8)
The MA unit of the raw material polymer 4 is the trifunctional (meth) acrylic compound (A-TMM-3LM-N) and the monofunctional (meth) in the same manner as in Preparation Example 7 except that the raw material polymer 3 is replaced with the raw material polymer 4. A polymer P8 obtained by opening the ring with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth) acrylic compound (GMA) was prepared.

Table 1 shows the components used in each preparation 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 integral value. And shown in terms of maleic anhydride (MA).

(Physical characteristics of polymer P)
The following physical characteristics of the polymer P obtained in each preparation example were measured. The results are shown in Table 1.

(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

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

(Double bond equivalent)
The double bond equivalent of the polymer was measured by the following method.
¹ H-NMR was measured in the same manner as in the above acid value measuring method. From the integral ratio of the signal derived from the acryloyl group (5.6-5.8 ppm, 3H) of the obtained spectrum chart and the signal of the phenyl group of the internal standard substance (8.1 ppm, 4H), the amount of acryloyl group in the polymer (Mol / g) is calculated, and from the integral ratio of the signal derived from the methacryloyl group (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard substance (8.1 ppm, 4H), in the polymer. The amount of methacryloyl group (mol / g) was calculated. Here, since the signal derived from the methacryloyl group of 6.0-6.1 ppm is minute and overlaps with the signal of the acryloyl group, it was calculated as the signal of the acryloyl group. The double bond amount (mol / g) is calculated from the total of the acryloyl group amount (mol / g) and the methacryloyl group (mol / g) in the calculated polymer, and the double bond equivalent (g / g) is calculated from the double bond amount. mol) was calculated.
The results are shown in Table 1. The smaller the value of the double bond equivalent, the larger the amount of C = C double bonds per unit mass of polymer. Since the double bond equivalent is 450 g / mol or less, it can be regarded as (the double bond having the density required for high sensitivity is present in the polymer).

(Examples 1 to 8, comparative examples 1 to 9)
(Preparation of polymer solution)
The obtained polymers P1 to P8 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution having a solid content concentration of 30% by mass. In Examples 1 to 8 and Comparative Example 1, the polyfunctional (meth) acrylic compound (A-TMM-3LM-N) shown in Table 2 was added.

(Alkaline dissolution rate of polymer solution)
The alkali dissolution rates of the polymer solutions of each example and comparative example were measured using the following methods.
The above polymer solution was spin-coated on the wafer, PGMEA was dried, and prebaked at a temperature of 100 ° C. for 2 minutes to prepare a resin film having a film thickness of about 2 μm.
This resin film was immersed in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution at a temperature of 23 ° C. for each wafer, and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern disappearing, and dividing the film thickness by that time. The results are shown in Table 2. When the alkali dissolution rate is 200 nm / s or more and 2200 nm / s or less, it can be considered that the developability is good.

(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 the polymer solution (total amount of polymer P and polyfunctional (meth) acrylic compound when polyfunctional (meth) acrylic compound is contained): 100 parts by mass-Polyfunctional acrylate (dipentaerythritol hexaacrylate) ( Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass ・ Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass ・ Adhesion aid (Shinetsu Chemical Industry Co., Ltd., KBM-403): 1 part by mass ・ Surface active agent (manufactured by DIC Co., Ltd., F-556): 0.5 parts by mass The obtained photosensitive resin composition is filtered with a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) as necessary. And the insoluble matter was removed.

The obtained photosensitive resin composition was evaluated for the following items.

[Developability evaluation (dissolution rate of photosensitive resin composition in alkaline developer)]
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a wafer, PGMEA was dried, and prebaked at a temperature of 100 ° C. for 2 minutes to form a resin film having a film thickness of 2 μm ± 0.2. Made.
This resin film was immersed in a 0.5% 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 2. When the alkali dissolution rate is 200 nm / s or more and 3000 nm / s or less, it can be considered that the developability is good.

[Sensitivity evaluation of photosensitive resin composition (0.5% 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 with a shading rate of 1 to 100%.
After the exposure, the thin film is developed (immersed together with the wafer) at 23 ° C. in a 0.5 mass% TMAH (tetramethylammonium hydroxide) aqueous solution for the development time shown in Table 2, and each exposure is 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 (%) = (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 50 mJ / cm ² or less, it can be used as a photosensitive composition without any problem, and if it is 20 mJ / cm ² or less, the sensitivity is considered to be good. be able to.

(Exposure amount with residual film ratio of 95% or more)
The exposure amount having a residual film ratio of 95% or more was measured by the same method as described above (exposure amount having a residual film ratio of 90% or more). The results are shown in Table 2. If the exposure amount at which the residual film ratio is 95% or more is 50 mJ / cm ² or less, it can be used as a photosensitive composition without any problem, and if it is 20 mJ / cm ² or less, the sensitivity is considered to be good. be able to.

[Adhesion during development]
(Adhesion to line pattern)
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 a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. at an exposure amount of 18 mJ / cm ² . 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 10 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)
Adhesion: The line pattern after development was in close contact with the substrate, and no peeling was observed.
Peeling: In the line pattern after development, a part peeling from the substrate was observed.

(Adhesion to dot pattern)
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.
Canon's g + h + i line via a photomask that owns a total of 3 patterns of this thin film with a glass part (exposed part) with a width of 50 μm and a length of 50 μm and a chrome part (light-shielding part) around the glass part. The g + h + i line was exposed with a mask aligner (PLA-501F) at an exposure amount of 18 mJ / cm ² . 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 an unexposed part because it does not transmit light, and a dot pattern having an exposure amount of 50 μm in width and 50 μm in height. was gotten. After the exposure, the thin film was developed with a 0.5 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 18 mJ / cm ² . Obtained. The presence or absence of pattern peeling was observed with a microscope for a total of three dot patterns having a width of 50 μm and a height of 50 μm after exposure and development.
Further, in the same procedure as above, the presence or absence of pattern peeling was observed with a microscope for dot patterns having a width and a height of 40 μm, 30 μm, 20 μm, 10 μm, 8 μm, 6 μm, 4 μm, 2 μm, and 1 μm, respectively.
Regarding the dot pattern after development, the minimum dot pattern width in which no peeling was observed was used as the close contact dot pattern. Here, in the dot pattern after development with a width of 50 μm and a height of 50 μm, a portion where peeling from the substrate was observed was referred to as “peeling”.

(Confirmation of undissolved residue near the pattern)
A fine line pattern of the photosensitive resin composition was created by the following procedure, and the occurrence of undissolved residue near the pattern of the fine line pattern was confirmed. The results are shown in Table 3.
In each Example and Comparative Example, the photosensitive resin composition was prepared so that the total solid content concentration was 30% by mass.
The obtained photosensitive resin composition was rotationally coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100 ° C. for 120 seconds to a thickness of 3.0 μm (± 0.3 μm). A thin film A was obtained.
2 mJ / cm with a Canon g + h + i-line mask aligner (PLA-501F) via a photomask having 20 μm wide glass parts (exposed parts) and 20 μm wide chrome parts (light-shielding parts) alternately in this thin film A. G + h + i lines were exposed at each exposure amount of ^{2 to 24 mJ / cm 2 at} intervals of 2, and a total of 12 patterns exposed at each exposure amount of 2 to 24 mJ / cm ² were obtained. By this exposure, the glass part of the photo mask is exposed with a specified exposure amount because it transmits light, and the chrome part becomes an unexposed part because it does not transmit light, and it is exposed for each exposure amount of 2 to 24 mJ / cm ² . A pattern having alternating portions and unexposed portions was obtained. After the exposure, the thin film was developed with a 0.5% TMAH (tetramethylammonium hydroxide) aqueous solution at 23 ° C. for 10 seconds (immersion together with the wafer) to expose and then develop at each exposure amount of 2 to 24 mJ / cm ² . A thin film B containing a total of 12 patterns was obtained. Of the 12 patterns exposed with an exposure amount of 2 to 24 mJ / cm ² of the thin film B, the pattern exposed with an exposure amount having a width of 20.0 ± 1.0 μm is left undissolved in the vicinity of the pattern. The presence or absence of the occurrence of was observed with a microscope.
(criterion)
Yes: Undissolved residue was found near the pattern.
None: No undissolved residue was observed near the pattern.

The photosensitive resin composition of the example had a good alkali dissolution rate, and was therefore excellent in developability. In the photosensitive resin composition of the example, the exposure amount at which the residual film ratio is 90% or 95% or more is 20 mJ / cm ² or less, in other words, it is cured at a low exposure amount, and it can be said that the sensitivity is high. Therefore, the photosensitive resin composition of the example has a good balance of high developability, high sensitivity, and low yellow index. Further, the photosensitive resin composition of the example suppresses the generation of undissolved residue in the vicinity of the pattern, can be formed into a desired shape, adheres to a finer dot pattern, suppresses peeling of the pattern, and also has adhesiveness. It was excellent.

<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 6.
A green color filter could be formed by forming a film on the substrate and performing exposure, alkaline development, and the like.
Further, as the pigment dispersion liquid, NX-053 (blue), NX-032 (red) and the like manufactured by the same company could be used instead of NX-061 to form a blue or red color filter.

<Making a black matrix>
A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Kogyo Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 6.
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 (17)

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).
Containing a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups,
The polyfunctional (meth) acrylic compound is in an amount of 1% by mass or more and 40% by mass or less with respect to the polymer.
Polymer solution.

(In 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 or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
When Q is the alkyl group and X is the alkylene group, Q and X may be condensed to form a cyclic group. )

(In the general formula (1-2), ^RD is a group containing two or more (meth) acryloyl groups.) The polyfunctional (meth) acrylic compound is composed of a compound represented by the general formula (1bp), a compound represented by the general formula (1cp), and a compound represented by the general formula (1d-p). The polymer solution of claim 1, comprising at least one selected.

(In the general formula (1bp),
k is 2 or 3 and
R is a hydrogen atom or a methyl group, and a plurality of 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— (where Z is —O— or —OCO—, and X is carbon number 1). It is an alkylene group of up to 6), and a plurality of X ^1s existing 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'-(where 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.
Y is a hydrogen atom, or a (meth) acryloyl group, or a combination thereof. )

(In the general formula (1c-p),
k is 2 or 3 and
R is a hydrogen atom or a methyl group, and a plurality of 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— (where Z is —O— or —OCO—, and X is carbon number 1). It is an alkylene group of up to 6), and a plurality of X ^1s existing may be the same or different.
X ² is a k + 1 valent organic group having 1 to 12 carbon atoms.
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.
Y is a hydrogen atom, or a (meth) acryloyl group, or a combination thereof. )

(In the general formula (1d-p),
n is an integer of 2 to 5,
R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different.
Y is a hydrogen atom, or a (meth) acryloyl group, or a combination thereof. ) The polymer solution according to claim 1 or 2, wherein in the structural unit represented by the general formula (1-1), Z contains a (meth) acryloyloxy group represented by the general formula (1a).

(In the general formula (1a), R is a hydrogen atom or a methyl group.) The polymer solution according to any one of claims 1 to 3, wherein the polymer further contains a structural unit represented by the general formula (2).

(In the general formula (2), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms, and a ₁ is 0, 1 or 2. be.) In the structural unit represented by the general formula (1-2), ^RD comprises at least one of the groups represented by the following general formulas (1b), (1c) and (1d). 4. The polymer solution according to any one of 4.

(In the general formula (1b),
k is 2 or 3 and
R is a hydrogen atom or a methyl group, and a plurality of 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— (where Z is —O— or —OCO—, and X is carbon number 1). It is an alkylene group of up to 6), and a plurality of X ^1s existing 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'-(where 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 is 2 or 3 and
R is a hydrogen atom or a methyl group, and a plurality of 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— (where Z is —O— or —OCO—, and X is carbon number 1). It is an alkylene group of up to 6), and a plurality of X ^1s existing may be the same or different.
X ² is a k + 1 valent organic group having 1 to 12 carbon atoms.
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, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different.) The polymer solution according to any one of claims 1 to 5, wherein the polymer further contains a structural unit represented by the general formula (3-1).

(In the general formula (3-1), ^RS is a group containing a single (meth) acryloyl group.) The polymer solution according to any one of claims 1 to 6, wherein the polymer further contains a structural unit represented by the general formula (4).

The polymer solution according to any one of claims 1 to 7, wherein the polymer contains a structural unit represented by the general formula (5).

(In the general formula (5), Q, X and Z are synonymous with those in the general formula (1-1).) The polymer solution according to any one of claims 1 to 8, wherein the polymer further contains a structural unit represented by the general formula (6).

(In the general formula (6), Q, X and Z are synonymous with those in the general formula (1-1).) The polymer solution according to any one of claims 1 to 9, wherein the polymer further contains a structural unit represented by the general formula (MA).

The polymer solution according to any one of claims 1 to 10, wherein the polymer further contains an organic group having a thioether group. The organic group having a thioether group has 1 to 6 valent carbon atoms of 1 to 30 or less derived from a bifunctional or higher functional thiol group-containing compound represented by the following chemical formulas (s-1) to (s-21). The polymer solution according to claim 11, which comprises an organic group.

The bifunctional or higher functional thiol group-containing compound is selected from the compounds represented by the following chemical formulas (s-1) to (s-3), (s-5) and (s-8) to (s-10). 12. The polymer solution of claim 12, comprising at least one of the above.

The polymer solution according to any one of claims 1 to 13, which is used for forming a color filter or a black matrix. The polymer solution according to any one of claims 1 to 13, and the polymer solution.
Including a photopolymerization initiator,
Photosensitive resin composition. A cured product formed from the photosensitive resin composition according to claim 15. A film comprising the cured product according to claim 16.

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