JP2022114042A - Polymer, polymer solution, photosensitive resin composition, and cured product - Google Patents

Abstract

To provide a polymer having excellent sensitivity and also having excellent alkali solubility.SOLUTION: A polymer contains a constitutional unit represented by formula (IN) and a specific constitutional unit containing a (meth)acryloyl group. (In the formula (IN), R1-R8 independently represent a hydrogen atom or a C1-30 organic group).SELECTED DRAWING: None

Description

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

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

WO2012/147706

A photosensitive resin composition for forming a color filter or a black matrix uses a resin having a property of being cured by a polymerization reaction caused by light. Color filters and black matrices are produced by patterning a photosensitive resin composition by exposure and development, followed by curing. In photosensitive resin compositions, "increase in sensitivity" seems to be a general issue, but with the increasing complexity and spread of display devices and imaging devices, there is a demand for a higher level of sensitivity. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the productivity can be improved. Moreover, the photosensitive resin composition is required to have excellent processability in photolithography using an alkaline developer.

The present inventors have found that by improving the polymer used in the photosensitive resin composition, it is possible to obtain a photosensitive resin composition that has good sensitivity, high alkali solubility, and thus excellent developability. This discovery led to the present invention.

（式（ＩＮ）において、Ｒ^１～Ｒ^８は、それぞれ独立して、水素原子または炭素数１～３０の有機基である。）

（式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基である。） The present invention provides a polymer comprising a structural unit represented by formula (IN) and a structural unit represented by formula (1).

(In Formula (IN), R ¹ to R ⁸ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.)

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

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

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

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

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a resin composition as a resin material for use in a photosensitive resin composition that has good sensitivity, high alkali solubility, and excellent developability.

1 is a diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging device; FIG.

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

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

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

[Polymer P]
The polymer of this embodiment (herein referred to as "polymer P") includes a structural unit represented by formula (IN) and a structural unit represented by formula (1).

In formula (IN), R ¹ to R ⁸ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

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

The polymer P of the present embodiment contains an indene-derived structural unit represented by the general formula (IN). This structural unit (IN) is chemically robust. Therefore, the polymer P containing this as a structural unit undergoes little 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 films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

In the structural unit represented by the general formula (IN) constituting the polymer P, the organic group having 1 to 30 carbon atoms that can constitute R ¹ to R ⁸ includes a substituted or unsubstituted linear or branched C1-C30 alkyl, more specifically alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, alkoxy group, heterocyclic group, carboxyl and the like.

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

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

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

In the structural unit represented by the general formula (IN), R ¹ to R ⁸ are preferably hydrogen or alkyl groups, more preferably hydrogen.
The hydrogen atoms in the organic groups having 1 to 30 carbon atoms of R ¹ to R ⁸ may be substituted with any atomic group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, a fluorinated alkyl group or the like may be selected as the organic group having 1 to 30 carbon atoms for R ¹ to R ⁸ .

The ratio of the structural unit represented by the general formula (IN) 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 of this embodiment contains a structural unit represented by general formula (1). In the structural unit represented by the general formula (1) that can constitute the polymer P, R ^p is a group containing two or more (meth)acryloyl groups, preferably two to six (meth)acryloyl groups. more preferably a group containing 3 to 5 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups contained in R ^p , the sensitivity of the polymer P containing this in exposure processing can be further enhanced. Moreover, it becomes easy to make the sensitivity and alkali solubility of the polymer P compatible more highly. Furthermore, the heat resistance of the polymer P can be improved.

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

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

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

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

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

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

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

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

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

The proportion of the structural unit represented by general formula (1) in the total structural units of polymer P is preferably 3 to 40 mol %, more preferably 3 to 30 mol %.

In one embodiment, the polymer P may contain a structural unit represented by general formula (2) in addition to the structural units described above. By including the structural unit represented by the general formula (2), the polymer P can have high sensitivity and high alkali solubility. As a result, the photosensitive resin composition containing the polymer P can have excellent developability when subjected to photolithography processing using an alkaline aqueous solution as a developer.

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

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

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

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

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

When the polymer P contains the structural unit represented by the general formula (2), the ratio of the structural unit represented by the general formula (2) in the total structural units of the polymer P is preferably 5 to 40 mol%, More preferably 10 to 30 mol %.

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

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

When the polymer P contains the structural unit represented by the general formula (3), the proportion of the structural unit represented by the general formula (3) in the total structural units of the polymer P is preferably 1 to 15 mol%, It is more preferably 2 to 10 mol %.

In one embodiment, the polymer P may contain a structural unit represented by formula (MA) in addition to the structural units described above. The structural unit represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P containing the structural unit has excellent developability. When the polymer P contains structural units represented by the formula (MA), the proportion of the structural units represented by the formula (MA) in the total structural units of the polymer P is preferably 1 to 10 mol%, More preferably, it is 2 to 7 mol %.

In addition, the content (ratio) of each structural unit contained in the polymer P is determined by the amount (molar amount) of the raw material charged when synthesizing the polymer, the amount of the raw material remaining after synthesis, various spectra (e.g., IR spectrum , ¹ H-NMR spectrum, ¹³ C-NMR spectrum) and peak areas.

The weight average molecular weight Mw of the polymer P is, for example, 1,000 to 80,000, preferably 2,000 to 70,000, more preferably 3,000 to 60,000, still more preferably 3,000 to 55,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust sensitivity and solubility in an alkaline developer.

Further, the degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P is preferably 1.0 to 10.0, more preferably 1.0 to 8.0, still more preferably 1.0 to 7.0. 0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer P can be made uniform, which is preferable. These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer P is preferably 150-250°C, more preferably 170-230°C. The polymer P has a relatively high glass transition temperature mainly due to including the structural unit represented by the formula (IN). This is preferable in that the pattern formed on the substrate can exist stably in manufacturing liquid crystal display devices and solid-state imaging devices. The glass transition temperature can be determined by, for example, differential thermal analysis (DTA).

The acid value of the polymer P is, for example, 105 mgKOH/g or more and 150 mgKOH/g or less, preferably 110 mgKOH/g or more and 150 mgKOH/g or less, more preferably 120 mgKOH/g or more and 150 mgKOH/g or less. . Further, the double bond equivalent of the polymer P is, for example, 300 g/mol or more and 500 g/mol or less, preferably 320 g/mol or more and 500 g/mol or less, more preferably 350 g/mol or more and 500 g/mol or more. mol or less.
Favorable developability can be obtained because the acid value of the polymer P is 100 mgKOH/g or more. Further, when the double bond equivalent is 500 g/mol or less, the sensitivity of the photosensitive resin composition containing the polymer P can be increased.

If the acid value of the polymer P is higher than the above upper limit, the exposed portion is likely to dissolve during development with an alkaline developer, resulting in an increase in the amount of exposure required for photocuring, or an undesirable pattern shape. There is concern that it will be enough. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH/g.
In addition, when the double bond equivalent of the polymer P is lower than the above lower limit (that is, when the double bond density in the polymer is too high), the unexposed areas and underexposed areas dissolve during development with an alkaline developer. It tends to become difficult, and a residual film tends to occur at the time of development. On the other hand, if the double bond equivalent is too small, the molecular weight will excessively increase due to cross-linking, and there is a concern that the solubility will be excessively lowered. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 300 g/mol.

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

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

The acid value and double bond equivalent of the polymer P are determined by the ratio of the structural units introduced into the polymer P, particularly the (meth)acryloyl groups contained in the structural units represented by the formulas (1) and (2). By appropriately designing the number of carbon-carbon double bonds, it can be adjusted to a desired value.

[Method for producing polymer P]
Here, a method for producing the polymer P described above will be described.
The polymer P can be produced (synthesized) by any method. Polymer P is, for example,
Step (I): A step of preparing a raw material polymer containing a structural unit represented by formula (IN) and a structural unit represented by formula (MA), and Step (II): A raw material polymer, a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylic monomer"), and / or a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic monomer") is reacted in the presence of a basic catalyst to obtain a structural unit represented by the formula (IN) and a structural unit represented by the formula (1) and/or a structural unit represented by formula (2), and optionally further comprising a structural unit represented by formula (MA).

In step (II), when both a polyfunctional (meth)acrylic monomer and a monofunctional (meth)acrylic monomer are used, the polyfunctional (meth)acrylic monomer is first reacted with the starting polymer, and the resulting reaction mixture is added with It is preferable to react a monofunctional (meth)acrylic monomer.

When the polymer P further contains a structural unit represented by formula (3), in step (II), the structural unit represented by formula (IN), the structural unit represented by formula (1) and/or the formula A step of preparing a polymer comprising a structural unit represented by (2) and a structural unit represented by formula (MA), and then treating the polymer with water in the presence of a base catalyst ( Step (III)).

(Step (I))
The step of preparing a raw material polymer containing a structural unit represented by formula (IN) and a structural unit represented by formula (MA) in step (I) includes a monomer represented by formula (INm), A step of polymerizing (addition polymerization) with maleic anhydride is included. The definitions of R ¹ to R ⁸ in formula (INm) are the same as those in formula (IN). The same applies to preferred embodiments.

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

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

The raw material polymer is synthesized by dissolving the monomer represented by the formula (INm), maleic anhydride and a polymerization initiator in a solvent and charging it into a reaction vessel, followed by heating to produce the above bifunctional or higher thiol group-containing compound. It is carried out by allowing addition polymerization to proceed while dropping. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the formula (INm) to maleic anhydride when charged into the reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1. A "raw material polymer" can be obtained by such a process.
The raw material polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. Typically they are random or alternating copolymers. Maleic anhydride is generally known as a monomer having strong alternating copolymerizability.

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

(Step (II))
By reacting the raw material polymer obtained in step (I) with a polyfunctional (meth)acrylic monomer and/or a monofunctional (meth)acrylic monomer in the presence of a basic catalyst, the formula contained in the raw material polymer Part of the structural unit represented by (MA) is ring-opened to form the structural unit represented by formula (1) and/or the structural unit represented by formula (2), and the formula (IN) and a structural unit represented by formula (1) and/or a structural unit represented by formula (2), and optionally a structural unit represented by formula (MA). can get.

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

Next, a polyfunctional (meth)acrylic monomer is added to the above solution. Additionally, a basic catalyst is added. Then, the solutions are mixed appropriately to form a uniform solution to obtain a polymer containing at least the structural unit of formula (IN) and the structural unit of formula (1) (step (II-i)).

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

Then, the polymer obtained in step (II-i) is reacted with a monofunctional (meth)acrylic monomer in the presence of a basic catalyst to obtain at least the structural unit of formula (IN), the Structural units and polymers containing structural units of formula (2) can be obtained (step (II-ii).

Monofunctional (meth)acrylic compounds that can be used include, for example, compounds represented by the following general formulas (2a-m). In general formula (2a-m), the definitions of X ¹⁰ and R are the same as in general formula (2a).

Specific examples of the compound represented by the general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 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.

Only step (II-i) may be performed, but it is preferable to perform both step (ii-i) and step (II-i). When performing both step (II-i) and step (II-ii), it is preferable to perform step (II-i) followed by step (II-ii).

(Step (III))
When performing step (III), a step of treating the polymer obtained in step (II) with water in the presence of a basic catalyst is used. Through the step (III), the structural unit represented by the formula (MA) contained in the polymer obtained in the step (II) is ring-opened to form the structural unit represented by the formula (3) to form the formula ( IN), a structural unit represented by formula (1) and/or a structural unit represented by formula (2), and a structural unit represented by formula (3). can do. When part of the structural units represented by the formula (MA) are ring-opened and part of the structural units of the formula (MA) remain unopened, the polymer P has the formula (IN), the formula ( In addition to structural units of 1) and/or formula (2) and formula (3), structural units represented by formula (MA) are included.

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

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

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

First, the reaction product containing the polymer P obtained above is diluted with an organic solvent, and an acid (for example, formic acid, etc.) is added to the reaction solution. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. An organic solution of the polymer P is thus obtained. The obtained organic solution containing the polymer P is purified using a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the resulting organic solution of polymer P is added to an excess amount of toluene or water to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is further washed several times with toluene or water. Furthermore, in order to remove formic acid and a basic catalyst, an operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (about 1 to 3 times). A high-purity polymer can be obtained by drying the polymer powder washed with ion-exchanged water, for example, at 30 to 60° C. for 16 hours or longer.

In the liquid-liquid extraction method, water is added to the resulting organic solution of polymer P and vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. Further, water is added to the organic solution of the polymer after removal of the aqueous phase and stirred vigorously with a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. An organic solution of the polymer is thus obtained. If necessary, the steps of adding water and removing the aqueous phase may be further performed.
The resulting organic solution of polymer P is heated under reduced pressure with a rotary evaporator to concentrate it, and then the final solvent (PGMEA, etc.) is added to repeat the dilution operation to obtain a polymer P solution dissolved in the final solvent. be able to.

Moreover, the polymer solution may contain the polyfunctional (meth)acrylic compound and/or the monofunctional (meth)acrylic compound used in synthesizing the polymer P. When the polymer solution contains these (meth) acrylic compounds, the peak area derived from the polyfunctional (meth) acrylic compound in the gel permeation chromatography (GPC) chart is 5 to 50% with respect to the peak area of the polymer P. It is preferable that the amount is 10 to 35%, and the peak area derived from the monofunctional (meth) acrylic compound is 5 to 50% with respect to the peak area of the polymer P, particularly 10 An amount of ~35% is preferred. As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[Polymer solution]
The polymer solution of this embodiment contains the polymer P described above.
In the polymer solution of the present embodiment, together with the polymer (A), at least one selected from polyfunctional (meth)acrylic compounds, monofunctional (meth)acrylic compounds, compounds having a thiol group and an alkoxy group, or oligomers thereof may include

(Polyfunctional (meth)acrylic compound)
The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of the present embodiment may be an unreacted product of the (meth)acrylic compound used in the production of the polymer P. However, it may be added separately.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the above general formula, a:b (molar ratio) is from 2:1 to 4:1. The weight average molecular weight is 1000-1500. * is a bond. Examples of the compound include X-12-1154 (manufactured by Shin-Etsu Silicone Co., Ltd.).
Moreover, compound (B) or its oligomer may be used individually by 1 type, and may be used in mixture of 2 or more types.

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

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

Specific examples of organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyllactone, N-methylpyrrolidone and cyclohexanone. These may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the organic solvent used is not particularly limited, but it 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.

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

[Photosensitive resin composition]
The photosensitive resin composition of this embodiment contains the polymer P described above and a radical photopolymerization initiator. That is, the photosensitive resin composition of this embodiment contains the polymer solution described above and a radical photopolymerization initiator. Each component is explained below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The compounds used in Examples may be indicated by the following abbreviations or trade names.
・MA: maleic anhydride ・IN: indene ・NB: 2-norbornene ・ST: styrene ・MEK: methyl ethyl ketone ・PGMEA: propylene glycol monomethyl ether acetate ・KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
・4-HBA: 4-hydroxybutyl acrylate ・A-TMM-3LM-N: A mixture of the following two compounds, the amount of the left compound in the mixture based on gas chromatograph measurement is about 57% (Shin-Nakamura Chemical Co., Ltd. manufactured by the company)

・ A-TMM-3L: A mixture of the following two compounds, the amount of the left compound in the mixture based on gas chromatograph measurement is about 55% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Synthesis of raw polymer>
(Synthesis of Raw Polymer 1)
122.4 g (1.05 mol) of indene, 1376.7 g of methyl ethyl ketone, and dimethyl 2,2′-azobis(2-methylpropionate) 9 were placed in an appropriately sized reaction vessel equipped with a stirrer and condenser. .70 g (0.042 mol) was weighed in and stirred to dissolve. Next, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., 103.2 g (1.05 mol) of maleic anhydride is dissolved in 741.30 g of MEK, nitrogen A solution from which dissolved oxygen in the system was removed by bubbling was added over 3 hours. After that, the mixture was further heated at 80° C. for 4 hours to polymerize maleic anhydride and indene to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 2047.94 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2047.94 g of methanol and then vacuum-dried at a temperature of 120° C. to obtain a polymer having structural units derived from indene and structural units derived from maleic anhydride (raw material polymer 1) 320.1 g was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 9248, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.31. there were.

(Synthesis of Raw Polymer 2)
In an appropriately sized reaction vessel equipped with a stirrer and condenser, 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene and dimethyl 2,2'- 33.16 g (0.144 mol) of azobis(2-methylpropionate) were weighed in. These were dissolved in a mixed solvent consisting of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.
The solution was purged with nitrogen for 30 minutes to remove oxygen, then heated with stirring at a temperature of 65° C. for 1.5 hours, followed by heating at 80° C. for 6 hours to give maleic anhydride. and 2-norbornene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was 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 607.5 g of a polymer (raw material polymer 2) having structural units derived from 2-norbornene and structural units derived from maleic anhydride. .
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 7000, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.82. there were.

(Synthesis of Raw Polymer 3)
XIRAN (registered trademark) 1000 (manufactured by Tomoe Kogyo Co., Ltd., styrene maleic anhydride copolymer, (styrene: maleic acid ratio = 1:1)) was prepared and used as the starting polymer 3.
The weight average molecular weight Mw of the raw material polymer 3 was 6478, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.51.

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

(Preparation Example 1)
A polymer P1 was prepared by ring-opening the MA unit of the raw material polymer 1 with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound. Details will be described below.
First, 99.71 g of MEK was added to 60 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. After that, 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 excessive amount of toluene was repeated twice.
- The operation of washing the polymer powder after washing twice with an excessive amount of water was repeated three times.
• The resulting reaction product was dried at 40°C for 16 hours.
As a result, 48.12 g of polymer P1 was obtained in which the maleic anhydride-derived structural unit in raw material polymer 1 was ring-opened with A-TMM-3LM-N and 4-HBA.
GPC measurement of polymer P1 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. As a result, it was confirmed that the obtained polymer P1 contained neither an unreacted (meth)acrylic compound nor a (meth)acrylic compound having no hydroxyl group. Table 1 shows the weight average molecular weight (Mw) and polydispersity (Mw/Mn) of polymer P1, determined by GPC measurement.
It was confirmed by ¹ H-NMR that polymer P1 has a ring-opened structure with A-TMM-3LM-N and 4-HBA.

(Preparation Example 2)
The MA unit of the starting polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a polymer P2. Details will be described below.
99.71 g of MEK was added to 60 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Then, 3.00 g (0.167 mol) of water was added to the reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours.
The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. After that, 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 excessive amount of toluene was repeated twice.
- The operation of washing the polymer powder after washing twice with an excessive amount of water was repeated three times.
• The resulting reaction product was dried at 40°C for 12 hours.
As a result, 45.12 g of polymer P2 was obtained in which the maleic anhydride-derived structural unit in raw material polymer 1 was ring-opened with A-TMM-3LM-N, 4-HBA and water.
GPC measurement of polymer P2 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. As a result, it was confirmed that the obtained polymer P7 contained neither an unreacted (meth)acrylic compound nor a (meth)acrylic compound having no hydroxyl group. Table 1 shows the weight average molecular weight (Mw) and polydispersity (Mw/Mn) of polymer P2, determined by GPC measurement.
It was confirmed by ¹³ C-NMR that polymer P2 has a ring-opened structure with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 3)
The MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a resin mixture containing the polymer P3. Details will be described below.
First, 99.71 g of MEK was added to 60.00 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Then, 3.00 g (0.167 mol) of water was added to the reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Furthermore, liquid-liquid extraction and then solvent replacement were performed in the following procedure.
Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and then the same operation was performed once.
- Solvent replacement: The solvent was removed from the resulting reaction mixture at 50°C under reduced pressure using a rotary evaporator. After confirming that the solid content concentration of the polymer solution reached 27±2% by mass as measured by a heat drying moisture meter, the solvent removal operation was discontinued. After that, PGMEA was added so that the solid content concentration was 18% by mass, and mixed until uniform. The solvent is removed at 50° C. under reduced pressure in the same manner, and after adjusting the solid content concentration to 27±2% by mass as measured by a heat drying moisture meter, PGMEA is added so that the solid content concentration becomes 18% by mass. and mixing until uniform was repeated two more times. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the mixture was stirred until uniform. The above operation removes the solvent used for the reaction and replaces the solvent with PGMEA.
Subsequently, 5% by mass of KBM-803 was added to the solid content in the resulting polymer solution.
As described above, the structural units derived from maleic anhydride in the starting polymer 1 are A-TMM-3LM-N, polymer P3 ring-opened with 4-HBA and water, and residual (free) A-TMM-3LM-N. and residual (free) 4-HBA, and polymer solution 3 containing KBM-803.
The resulting polymer solution 3 was analyzed by gel permeation chromatography to determine the amount of polymer P3, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and polymer P3. were measured for weight average molecular weight and polydispersity. Table 1 shows the results. The amount of the free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the polymer P3 in the gel permeation chromatography (GPC) chart of the resin mixture.
The measurement conditions for the gel permeation chromatography method are as follows.
・As a GPC measurement device, HLC-8320GPC EcoSEC manufactured by Tosoh Corporation was used. The column temperature was set to 40.0° C. and the pump flow rate to 0.350 mL/min.
・Peak position (retention time)
- Polymer P3: peak detected before 20 minutes (peak with shorter retention time and higher molecular weight than A-TMM-3LM-N and 4-HBA)
-A-TMM-3LM-N: sum of two peaks from 20.0 to 20.6 minutes and 20.6 to 21.5 minutes -4-HBA: 21.7 to 22.4 minutes Measurement conditions: differential refraction Analyzed with a rate detector (RI detector).

(Preparation Example 4)
A polymer P4 was prepared by ring-opening the MA unit of the raw material polymer 2 with a trifunctional (meth)acrylic compound containing a hydroxyl group and a monofunctional (meth)acrylic compound. Details will be described below.
First, 49.86 g of MEK was added to 30 g of raw polymer 2 (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, and then 9.00 g (0.089 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 28.13 g (0.195 mol) of 4-HBA was added and reacted at 70° C. for 4 hours to prepare a reaction solution.
The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. After that, the polymer was purified by the following reprecipitation method.
- Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The resulting reaction product was dried at 40° C. for 12 hours.
As a result, 24.64 g of polymer P4 was obtained in which the maleic anhydride-derived structural unit in raw material polymer 2 was ring-opened with A-TMM-3L and 4-HBA. Table 1 shows the weight average molecular weight (Mw) and polydispersity (Mw/Mn) of polymer P4, determined by GPC measurement.
GPC measurement of polymer P4 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. As a result, it was confirmed that the obtained polymer P4 contained neither an unreacted (meth)acrylic compound nor a (meth)acrylic compound having no hydroxyl group.
¹ H-NMR measurement confirmed that the polymer P4 had a ring-opened structure with A-TMM-3L and 4-HBA.

(Preparation Example 5)
A-TMM-3LM-N and 4- 23.41 g of polymer P5, ring-opened with HBA, were obtained. Table 1 shows the weight average molecular weight (Mw) and polydispersity (Mw/Mn) of polymer P5, determined by GPC measurement.
GPC measurement of polymer P5 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. As a result, it was confirmed that the obtained polymer P4 contained neither an unreacted (meth)acrylic compound nor a (meth)acrylic compound having no hydroxyl group.
¹ H-NMR measurement confirmed that polymer P5 has a ring-opened structure with A-TMM-3LM-N and 4-HBA.

(Preparation Example 6)
The MA unit of the starting polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a polymer P6. Details will be described below.
99.71 g of MEK was added to 60 g of raw polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. Then, 3.00 g (0.167 mol) of water was added to the reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours.
The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. After that, the polymer was purified by the following reprecipitation method.
- Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The resulting reaction product was dried at 40° C. for 12 hours.
As a result, 25.77 g of polymer P6 was obtained by ring-opening the maleic anhydride-derived structural unit in raw material polymer 2 with A-TMM-3LM-N, 4-HBA, and water. Table 1 shows the weight average molecular weight (Mw) and polydispersity (Mw/Mn) of polymer P6, determined by GPC measurement.
GPC measurement of polymer P6 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used. As a result, it was confirmed that the obtained polymer P6 contained neither an unreacted (meth)acrylic compound nor a (meth)acrylic compound having no hydroxyl group.
It was confirmed by ¹³ C-NMR that the polymer P6 has a ring-opened structure with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 7)
Polymer P7 was prepared by ring-opening the MA unit of starting polymer 3 with a monofunctional (meth)acrylic compound. Details will be described below.
First, 18.44 g of MEK was added to 10.00 g of raw polymer 3 (0.052 mol in terms of MA) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added and reacted at a temperature of 70° C. for 6 hours to obtain a reaction solution. was made.
The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. After that, the polymer was purified by the following reprecipitation method.
- Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The resulting reaction product was dried at 40° C. for 12 hours.
As a result, 8.0 g of polymer P7 was obtained in which the maleic anhydride-derived structural unit in raw material polymer 3 was ring-opened with 4-HBA.
GPC measurements were performed on the resulting polymer P7 to determine the weight average molecular weight and polydispersity of polymer P7. Table 1 shows the results.
Also, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P7. As a result, it was confirmed that the obtained polymer P7 contained no unreacted monofunctional (meth)acrylic compound.
¹ H-NMR measurement confirmed that the polymer P7 had a structure opened with 4-HBA.

(Preparation Example 8)
The MA unit of the raw material polymer 3 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water to prepare a resin mixture containing the polymer P8. Details will be described below.
First, 99.71 g of MEK was added to 60.00 g of raw polymer 3 (0.312 mol in terms of MA) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Then, 3.00 g (0.167 mol) of water was added to the reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. After that, the polymer was purified by the following reprecipitation method.
- Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The resulting reaction product was dried at 40° C. for 12 hours.
As a result, 45.20 g of polymer P8 was obtained by ring-opening the maleic anhydride-derived structural unit in raw material polymer 3 with A-TMM-3LM-N, 4-HBA and water.
GPC measurements were performed on the resulting polymer P8 to determine the weight average molecular weight and polydispersity of polymer P8. Table 1 shows the results.
GPC measurement of polymer P8 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used. As a result, it was confirmed that the obtained polymer P8 contained neither an unreacted (meth)acrylic compound nor a (meth)acrylic compound having no hydroxyl group.
It was confirmed by ¹³ C-NMR that polymer P8 has a ring-opened structure with A-TMM-3LM-N, 4-HBA and water.

(Preparation Example 9)
Polymer P9 was prepared by ring-opening the MA unit of starting polymer 1 with a monofunctional (meth)acrylic compound. Details will be described below.
First, 18.44 g of MEK was added to 10.00 g of raw polymer 1 (0.052 mol in terms of MA) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added and reacted at a temperature of 70° C. for 6 hours to obtain a reaction solution. was made.
The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. After that, the polymer was purified by the following reprecipitation method.
- Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The resulting reaction product was dried at 40° C. for 12 hours.
As a result, 9.1 g of polymer P9 was obtained in which the maleic anhydride-derived structural unit in raw material polymer 1 was ring-opened with 4-HBA.
GPC measurements were performed on the resulting polymer P9 to determine the weight average molecular weight and polydispersity of polymer P9. Table 1 shows the results.
Also, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P9. Thereby, it was confirmed that the obtained polymer P9 contained no unreacted monofunctional (meth)acrylic compound.
¹ H-NMR measurement confirmed that the polymer P9 had a structure opened with 4-HBA.

(Evaluation of the physical properties)
The acid value and double bond equivalent of each polymer P produced in the above preparation examples were measured by the methods described below.

(acid value)
The acid value of the polymer was measured by the following method.
About 50 mg of polymer and about 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was subjected to ¹ H-NMR measurement using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). Based on the integrated value of the 4H peak (around 8.1 ppm) of the phenyl group of the dimethyl terephthalate internal standard measured by ¹ H-NMR, the H peak (around 12.4 ppm) of the carboxyl group (—COOH) of the polymer Calculate the amount of carboxyl groups from the integrated value of . Then, the acid value (mgKOH/g) can be calculated from the amount. A larger acid value indicates a larger amount of carboxyl groups per unit mass of the polymer.
Table 1 shows the results. When the acid value is 105 gKOH/g or more, it can be considered that the carboxy groups necessary for the polymer to have sufficient developability are present in the polymer.

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

(Examples 1-3, Comparative Examples 1-6)
In each example and comparative example, the following items were evaluated.

<Evaluation>
[Alkaline dissolution rate of polymer P (dissolution rate of polymer P in alkaline developer)]
The polymers P1, P2, P4 to P9 obtained in Preparation Examples 1, 2, 4 to 9 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare solutions having a solid concentration of 30% by mass.
Then, the above solution and polymer solution 3 were spin-coated on the wafer, the PGMEA was dried, and prebaked at a temperature of 100° C. for 2 minutes to form a resin film with a film thickness of 2 μm±0.2.
This resin film was immersed together with the wafer in a 2.0 mass % sodium carbonate aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film dissolved and the interference pattern disappeared, and dividing the film thickness by that time. Table 2 shows the results. If the alkali dissolution rate is 300 nm/s or more, it can be considered that the developability is good, and if it is 400 nm/s or more, it can be considered that the developability is better.

[Sensitivity evaluation of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)]
First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid concentration was 30% by mass.
Polymer P (Polymers P1, P2, P4 to P9 obtained in Preparation Examples 1, 2, 4 to 9): 100 parts by mass (For polymer solution 3, solid content (polymer P3 and polyfunctional (meth) acrylic compound Polymer solution 3 was weighed so that the total amount of KBM-803) was 100 parts by mass.)
· Polyfunctional acrylate (dipentaerythritol hexaacrylate, A-DPH): 50 parts by mass · Photopolymerization initiator (manufactured by BASF, Irgacure OXE01): 5 parts by mass · Adhesion aid (manufactured by Shin-Etsu Chemical Co., Ltd., KBM- 403): 1 part by mass ・Surfactant (F-556, manufactured by DIC Corporation): 0.5 parts by mass ) to remove insoluble matter.

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

[Alkaline dissolution rate of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)]
The photosensitive resin composition prepared in the sensitivity evaluation described above was spin-coated on a wafer, the PGMEA was dried, and prebaked at a temperature of 100° C. for 2 minutes to prepare a resin film having a thickness of about 2 μm.
This resin film was immersed together with the wafer in a 2% sodium carbonate aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film dissolved and the interference pattern disappeared, and dividing the film thickness by that time. Table 1 shows the results. If the alkali dissolution rate is 350 nm/s or more, it can be used as a photosensitive material without any problem. can be considered particularly good.

Table 2 shows the results of alkali dissolution rate and sensitivity evaluation.

The photosensitive resin compositions of Examples had a good alkali dissolution rate and, therefore, excellent developability. The photosensitive resin compositions of Examples have an exposure amount of 20 mJ/cm ² or less for a residual film rate of 95% or more. Therefore, the photosensitive resin compositions of Examples had a good balance between high developability and high sensitivity.

<Production of color filter>
Colored photosensitive resin compositions were prepared by adding an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichiseika Kogyo Co., Ltd., green) to the photosensitive resin compositions prepared in Examples 1 to 3.
A green color filter could be formed by forming a film of this on a substrate, and performing exposure, alkali development, and the like.
Further, by using NX-053 (blue), NX-032 (red), etc. manufactured by the same company as the pigment dispersion instead of NX-061, a blue or red color filter could be formed.

<Preparation of black matrix>
A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Kogyo Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 3.
A black matrix was formed by forming a film of this on a substrate, and subjecting it to exposure, alkali development, and the like.

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

Claims (12)

A polymer comprising a structural unit represented by formula (IN) and a structural unit represented by formula (1).

(In Formula (IN), R ¹ to R ⁸ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.)

(In formula (1), R ^p is a group having two or more (meth)acryloyl groups.) 2. The polymer of claim 1, further comprising a structural unit represented by formula (2).

(In formula (2), R ^s is a group having one (meth)acryloyl group.) 3. The polymer according to claim 1, further comprising a structural unit represented by formula (3).

4. The polymer according to any one of claims 1 to 3, further comprising a structural unit represented by formula (MA).

R ^p in the structural unit represented by formula (1) is selected from a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d) 5. The polymer of any one of claims 1-4, which is at least one.

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

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

(In formula (1d),
n is an integer from 2 to 5,
R is a hydrogen atom or a methyl group, and multiple R's may be the same or different. ) 3. The polymer according to claim 2, wherein R ^s in the structural unit represented by formula (2) is a group represented by formula (2a).

(In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.) 7. The polymer according to any one of claims 1 to 6, which has an acid value of 105 mg OKH/g or more and 150 mg OKH/g or less and a double bond equivalent of 300 g/mol or more and 500 g/mol or less. A polymer solution comprising a polymer according to any one of claims 1-7. The polymer solution according to claim 8, further comprising at least one selected from a polyfunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and a compound having a thiol group and an alkoxy group or an oligomer thereof. 10. The polymer solution according to claim 8 or 9, used for forming color filters or black matrices. a polymer according to any one of claims 1 to 7;
and a photoradical polymerization initiator,
A photosensitive resin composition. A cured product formed from the photosensitive resin composition according to claim 11 .

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