CN114556214A

CN114556214A - Resin composition, photosensitive resin composition, and cured product thereof

Info

Publication number: CN114556214A
Application number: CN202080072259.0A
Authority: CN
Inventors: 田边润壹
Original assignee: Sumitomo Bakelite Co Ltd
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2019-10-16
Filing date: 2020-10-14
Publication date: 2022-05-27
Also published as: KR20220084087A; JP6930679B1; WO2021075448A1; TW202124486A; JPWO2021075448A1

Abstract

A resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); and a compound having 2 or more (meth) acryloyl groups. In the formula (NB), R¹、R²、R³And R⁴Each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a₁Is 0, 1 or 2. In the formula (1), R^pA group having 2 or more (meth) acryloyl groups.

Description

Resin composition, photosensitive resin composition, and cured product thereof

Technical Field

The present invention relates to a resin composition, a photosensitive resin composition and a cured product thereof. More specifically, the present invention relates to a resin composition, a photosensitive resin composition containing the resin composition, and a cured product of the photosensitive resin composition.

Background

A liquid crystal display device or a solid-state imaging device generally includes a color filter or a black matrix. The color filter or the black matrix is formed by forming a structure such as a colored pattern or a protective film on a substrate. As a method for forming a colored pattern or a protective film in these structures, a method of forming a colored pattern or a protective film by photolithography using a photosensitive resin composition has been mainstream. For example, patent document 1 describes a photosensitive resin composition containing an alkali-soluble resin containing a group having an acid group and at least 2 or more polymerizable unsaturated groups different from each other in a side chain, a polymerizable compound, and a photopolymerization initiator. In the examples of patent document 1, the following are described: a methacrylic acid/allyl methacrylate/glycidyl adduct was synthesized as an alkali-soluble resin, and used to prepare a photosensitive resin composition.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/147706.

Disclosure of Invention

Technical problem to be solved by the invention

A resin having a property of being cured by a polymerization reaction of light is used for a photosensitive resin composition for forming a color filter or a black matrix. The color filter or the black matrix is produced by patterning a photosensitive resin composition by exposure and development, and then curing the patterned composition. In the photosensitive resin composition, "high sensitivity" is also considered to be a general problem, but higher levels of high sensitivity are required with the complexity and spread of display devices and imaging devices. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the higher the productivity. Further, the photosensitive resin composition is required to have excellent processability in a developing treatment using an alkaline developer.

The present inventors have found that a photosensitive resin composition having good sensitivity and high alkali solubility and excellent developability can be obtained by improving the polymer used in the photosensitive resin composition or the blending of the composition, and have reached the present invention.

Means for solving the technical problem

According to the present invention, there is provided a resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); and a compound having 2 or more (meth) acryloyl groups.

(in the formula (NB), R¹、R²、R³And R⁴Each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a₁Is 0, 1 or 2. )

(in the formula (1), R^pA group having 2 or more (meth) acryloyl groups. )

Further, according to the present invention, there is provided a photosensitive resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); a compound having 2 or more (meth) acryloyl groups; and a photosensitizer.

(in the formula (1), R^pA group having 2 or more (meth) acryloyl groups. )

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

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there is provided a resin composition as a resin material for a photosensitive resin composition excellent in developability due to good sensitivity and having high alkali solubility.

Drawings

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

Detailed Description

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

In the expression of a group (group, atomic group) in the present specification, an expression not labeled with substituted or unsubstituted includes both of no substituent and having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The expression "(meth) acrylic acid" in the present specification means a concept including both acrylic acid and methacrylic acid. The same applies to "(meth) acrylate" and the like.

In particular, "(meth) acryloyl" in the present specification means a compound containing-C (═ O) -CH ═ CH₂Acryloyl and-C (═ O) -C (CH) as shown₃)＝CH₂The concept of methacryloyl groups is shown.

(resin composition)

The resin composition of the present embodiment is used as a resin material for producing a photosensitive resin composition. The resin composition of the present embodiment contains: a polymer P containing a structural unit described in detail below; and a compound having 2 or more (meth) acryloyl groups.

(Polymer P)

The polymer P used in the resin composition of the present embodiment contains a structural unit represented by formula (NB) and a structural unit represented by formula (1). In addition, these structural units typically constitute the main chain of the polymer P.

In the formula (NB), R¹、R²、R³And R⁴Each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a₁Is 0, 1 or 2.

In the formula (1), R^pA group having 2 or more (meth) acryloyl groups.

The polymer P used in the resin composition of the present embodiment contains a structural unit represented by formula (1). Thus, the photosensitive resin composition containing the polymer P has excellent sensitivity when subjected to a photolithography method. This is considered to be because the curing reaction (polymerization reaction) is accelerated by 2 or more (meth) acryloyl groups contained in the structural unit represented by formula (1). The polymer P contains a structural unit represented by formula (NB). The building block (NB) is chemically strong. Therefore, the polymer P containing the same as a structural unit is less lost in weight and is stable when subjected to heat treatment. Therefore, a photosensitive resin composition containing the polymer P can be suitably used for producing a film or a filter used for a liquid crystal display device or a solid-state imaging device which requires heat resistance.

In one embodiment, the polymer P contains a structural unit represented by formula (2) in addition to the above structural unit.

In the formula (2), R^sIs a group having 1 (meth) acryloyl group.

By containing the structural unit represented by the formula (2) in addition to the structural unit represented by the formula (1), the polymer P has higher sensitivity and high alkali solubility, and thus can be suitably used for processing by photolithography.

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

In one embodiment, the polymer P may contain a structural unit represented by the formula (MA) in addition to the structural unit described above. The structural unit represented by formula (MA) is opened by an alkali developing solution to generate 2 carboxyl groups. Therefore, the polymer P containing the structural unit has excellent developability. When the polymer P contains a structural unit represented by the formula (MA), the structural unit represented by the formula (MA) in all the structural units of the polymer P is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

In one embodiment, the polymer P may contain a thioether group (-S-) in addition to the above structure. The thioether group is a group derived from a thiol group-containing compound used as a chain transfer agent in synthesizing the polymer P.

In the structural unit represented by the formula (NB) constituting the polymer P, R is defined as a structural unit capable of constituting R¹～R⁴Examples of the organic group having 1 to 30 carbon atoms include a substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms, and more specifically, an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, a carboxyl group and the like.

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

Examples of the alkenyl group include allyl, pentenyl, and vinyl.

Examples of the alkynyl group include an ethynyl group and the like.

Examples of the alkylene group include a methylene group and an ethylene group.

Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl.

Examples of the aralkyl group include a benzyl group and a phenethyl group.

Examples of the alkylaryl group include tolyl group and xylyl group.

Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

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

Examples of the heterocyclic group include an epoxy group and an oxetane group.

R in the structural unit represented by the formula (NB)¹、R²、R³And R⁴Preferably hydrogen or alkyl, more preferably hydrogen.

In addition, R¹、R²、R³And R⁴The hydrogen atom in the organic group having 1 to 30 carbon atoms may be substituted with an arbitrary atomic group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group or the like. More specifically, as R¹、R²、R³And R⁴The organic group having 1 to 30 carbon atoms may be a fluorinated alkyl group or the like.

In the structural unit represented by the formula (NB), a₁Preferably 0 or 1, more preferably 0.

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

In the present embodiment, the polymer P has a structural unit represented by formula (1), that is, a polymer having a structure containing 2 or more (meth) acryloyl groups (— C (═ O) -CH ═ CH)₂) The structural unit of (1). This can improve the sensitivity of the polymer P in the exposure treatment.

In the structural unit represented by the formula (1) constituting the polymer P, R^pThe group having 2 or more (meth) acryloyl groups is preferably a group having 2 to 6 (meth) acryloyl groups, and more preferably a group having 3 to 5 (meth) acryloyl groups. By optimally setting R^pThe number of (meth) acryloyl groups contained can further improve the sensitivity of the polymer P containing the same in the exposure treatment. Further, it is easy to more highly balance the sensitivity and alkali solubility of the polymer P. In addition, the heat resistance of the polymer P can be improved.

R^pPreferably a group represented by formula (1b) or a group represented by formula (1 c). By using such a group, the above-described various effects tend to be easily obtained.

R in the formula (1)^pPreferably a group represented by formula (1b), a group represented by formula (1c) or a group represented by formula (1 d). By using such a group, the above-described various effects tend to be easily obtained.

In formula (1 b):

k is 2 or 3.

R is a hydrogen atom or a methyl group, and R's may be the same or different.

X¹A single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by-Z-X- (Z is-O-or-OCO-, X is an alkylene group having 1 to 6 carbon atoms), and a plurality of X¹Which may be the same or different from each other,

X¹' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by-X ' -Z ' (X ' is an alkylene group having 1 to 6 carbon atoms, and Z ' is-O-or-COO-).

X²Is a C1-12 organic group having a valence of k + 1.

R is preferably a hydrogen atom from the viewpoint of further improving sensitivity (easiness of polymerization) or the like.

k may be 2 or 3, but is preferably 3 from the viewpoint of further improving the availability or sensitivity of the raw material.

When X is present¹When the alkylene group has 1 to 6 carbon atoms, the alkylene group may be linear or branched.

When X is¹When it is an alkylene group having 1 to 6 carbon atoms, X¹Preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably-CH₂- (methylene).

When X is present¹A carbon atom of X in the case where the group is represented by-Z-X- (Z is-O-or-OCO-, and X is an alkylene group having 1 to 6 carbon atoms)The alkylene group having a sub-number of 1 to 6 may be linear or branched.

The alkylene group having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably-CH₂-CH₂- (ethylene) or-CH₂-CH(CH₃)-。

When X is present¹' when it is an alkylene group having 1 to 6 carbon atoms, as a specific embodiment, with X¹The same is true.

When X is present¹When the 'is a group represented by-X' -Z '-, the specific embodiment of X' is the same as that of X described above.

As X²The (c 1-c 12) k +1 valent organic group includes any group obtained by removing k +1 hydrogen atoms from any organic compound. The "arbitrary organic compound" herein is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less.

X²For 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, the group is a group obtained by removing k +1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon herein may contain an oxygen atom (for example, an ether bond, a hydroxyl group, or the like). Also, the hydrocarbon is preferably a saturated hydrocarbon.

As another mode, X²May be a group having a cyclic structure. Examples of the cyclic structure-containing group include an alicyclic structure-containing group, a heterocyclic structure-containing group (for example, an isocyanuric acid structure), and the like.

In formula (1 c):

k、R、X¹and X²Respectively react with R, k and X in the formula (1b)¹And X²Synonymously, a plurality of R may be the same or different from each other, and a plurality of X¹May be the same as or different from each other.

X³Is a C1-6 organic group with a valence of 2.

X⁴And X⁵Each independently represents a single bond or a C1-6 organic group having a valence of 2.

X⁶Is a C1-6 organic group with a valence of 2.

With respect to R, k, X¹And X²The specific embodiment, preferable embodiment and the like of (3) are the same as those described in the general formula (1 b).

As X³And X⁶Examples of the C1-6 organic group having a valence of 2 include groups obtained by removing 2 hydrogen atoms from a C1-6 linear or branched hydrocarbon. The hydrocarbon herein may contain an oxygen atom (for example, an ether bond, a hydroxyl group, or the like). Also, the hydrocarbon is preferably a saturated hydrocarbon.

As X⁴And X⁵Examples of the organic group having a valence of 2 and having 1 to 6 carbon atoms include a straight-chain or branched alkylene group. The number of carbon atoms of the linear or branched alkylene group is preferably 1 to 3.

In formula (1 d):

n is an integer of 2 to 5, preferably 2 or 3.

The specific embodiment, preferable embodiment and the like of R are the same as those described in the general formula (1 b).

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

In the structural unit represented by the formula (2), R^SIs a group containing only 1 (meth) acryloyl group. In one embodiment, the polymer P may contain "a structural unit of formula (2) containing only 1 acryloyl group" in addition to "a structural unit of formula (1) containing 2 or more (meth) acryloyl groups". When the polymer P contains these 2 kinds of structural units, both sensitivity and developability can be more highly achieved. Especially in the generalIn designing a photosensitive resin composition, when the sensitivity is to be improved and the curability is to be improved, curing proceeds excessively and the developability tends to be poor, while when the developability is to be improved, curing tends to be insufficient, and therefore, it is preferable that the polymer P contains a structural unit represented by formula (1) and a structural unit represented by formula (2) in combination, whereby both the sensitivity and the developability can be satisfied in a good balance.

R^SFor example, a group represented by the following formula (2 a).

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

In the formula (2a), X¹⁰Is an organic group with a valence of 2, and R is a hydrogen atom or a methyl group.

X¹⁰The total carbon number of (2) is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10.

As X¹⁰The organic group having a valence of 2 in (1) is preferably an alkylene group, for example. -CH as part of the alkylene group₂-may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

As X¹⁰The organic group having a valence of 2 in (c) is more preferably a linear alkylene group having 3 to 6 carbon atoms in total. By appropriate selection of X¹⁰Number of carbon atoms (X)¹⁰The chain length of (3), the structural unit represented by the formula (2) easily participates in the crosslinking reaction, and the sensitivity can be improved.

X¹⁰The 2-valent organic group (e.g., alkylene group) of (a) may be substituted with an arbitrary substituent. Examples of the substituent include an alkyl groupAryl, alkoxy, aryloxy, and the like.

And, X¹⁰The 2-valent organic group in (1) may be any group other than an alkylene group. For example, the compound may be a 2-valent group formed by connecting 1 or 2 or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxyl groups, and the like.

When the polymer P contains the structural unit represented by the formula (2), the proportion of the structural unit represented by the formula (2) in all the structural units of the polymer P is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

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

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

The weight average molecular weight Mw of the polymer P is, for example, 1000 to 20000, preferably 2000 to 18000, more preferably 3000 to 14000, and further preferably 3000 to 12000. The sensitivity or solubility in an alkali developing solution can be adjusted by appropriately adjusting the weight average molecular weight.

The degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer P is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0. The degree of dispersion is preferably adjusted to make the physical properties of the polymer P uniform. In addition, these values can be obtained by Gel Permeation Chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer P is preferably 150 to 250 ℃, and more preferably 170 to 230 ℃. The polymer P has a relatively high glass transition temperature by mainly containing a structural unit represented by the formula (NB). This is preferable in terms of stable existence of a pattern formed on a substrate in manufacturing a liquid crystal display device or a solid-state imaging element. The glass transition temperature can be determined by, for example, Differential Thermal Analysis (DTA).

(Compound having 2 or more (meth) acryloyl groups (polyfunctional (meth) acrylic acid Compound))

The resin composition of the present embodiment contains a compound having 2 or more (meth) acryloyl groups. By containing such a compound, the alkali solubility of the resin composition is improved, yellowing of the resin composition is reduced, and a cured product having excellent transparency can be obtained. The polyfunctional (meth) acrylic compound is preferably 3 to 9 functional groups, and more preferably 3 to 6 functional groups. By blending such a (meth) acrylic compound having the number of functional groups in the resin composition, the sensitivity of the obtained resin composition can be improved.

Examples of the compound having 2 or more (meth) acryloyl groups (referred to as "polyfunctional (meth) acrylic compound" in the present specification) used in the resin composition of the present embodiment include, but are not limited to, compounds represented by the following formula (1b-p), compounds represented by the formula (1c-p), and compounds represented by the formula (1 d-p). K, R, X in the formula (1b-p)¹、X¹' and X²The definition and the specific mode of (3) are the same as those in the above formula (1 b). And k, R, X in the formula (1c-p)¹、X²、X³、X⁴、X⁵And X⁶The definition and the specific mode of (3) are the same as those in the above formula (1 c). Y in the formula (1b-p), (1c-p) and (1d-p) is a hydrogen atom or a (meth) acryloyl group or a combination of these. In the formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3. R in the formula (1d-p) is the same as in the above formula (1 d).

Specific examples of the polyfunctional (meth) acrylic compound represented by the formula (1b-p) include, but are not limited to, the following compounds. In the following compounds, Y represents a hydrogen atom, a (meth) acryloyl group, or a combination of these.

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

X：--CH₂-CH₂-O--，a+b+c：4～8

X：--CH₂-CH₂-0--，a+b+c+d+e+f：6～12

(Compound having 1 (meth) acryloyl group)

The resin composition of the present embodiment may contain a compound having 1 (meth) acryloyl group (referred to as a "monofunctional (meth) acrylic compound" in the present specification). By containing the monofunctional (meth) acrylic compound, the alkali solubility of the obtained resin composition is improved and further yellowing is reduced.

As a book blockExamples of the monofunctional (meth) acrylic compound used in the resin composition of the embodiment include compounds represented by the following formula (2 a-m). In the formula (2a-m), with respect to X¹⁰And R is as defined for formula (2 a).

Specific examples of the compound represented by the 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, and 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

In the resin composition of the present embodiment, the polyfunctional (meth) acrylic compound is blended in an amount such that, for example, a peak area derived from the polyfunctional (meth) acrylic compound in a Gel Permeation Chromatography (GPC) chart of the resin composition is 5 to 150% with respect to a peak area of the polymer P. The lower limit of the peak area derived from the polyfunctional (meth) acrylic compound to the peak area of the polymer P is preferably 10% or more, more preferably 20% or more, further preferably 30% or more, further preferably 40% or more, and particularly preferably 50% or more. The upper limit value of the peak area derived from the polyfunctional (meth) acrylic compound to the peak area of the polymer P is preferably 140% or less, more preferably 135% or less, further preferably 130% or less, further preferably 125% or less, and particularly preferably 120% or less. By blending the polyfunctional (meth) acrylic compound in the above range, the obtained resin composition has excellent alkali solubility.

When the monofunctional (meth) acrylic compound is blended with the resin composition of the present embodiment, the amount thereof is, for example, 5 to 60% of the peak area derived from the monofunctional (meth) acrylic compound relative to the peak area of the polymer P in a Gel Permeation Chromatography (GPC) chart of the resin composition. The lower limit of the peak area derived from the monofunctional (meth) acrylic compound to the peak area of the polymer P is preferably 7% or more, more preferably 9% or more, and still more preferably 10% or more. The upper limit value of the peak area derived from the monofunctional (meth) acrylic compound to the peak area of the polymer P is preferably 55% or less, more preferably 50% or less, and still more preferably 45% or less. By blending the monofunctional (meth) acrylic compound in the above range, the obtained resin composition has excellent alkali solubility and improved heat discoloration resistance.

By providing the above-described structure for the resin composition of the present embodiment, the alkali dissolution rate can be set to, for example, 250nm/s or more, and preferably 280nm/s or more.

The resin composition of the present embodiment typically contains an organic solvent, and is provided as a liquid or varnish. As the organic solvent, 1 or 2 or more kinds of ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, and the like can be used.

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ -butyrolactone, N-methylpyrrolidone, and cyclohexanone. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The amount of the organic solvent used is not particularly limited, and is used in an amount such that the concentration of the nonvolatile component is, for example, 10 to 70 mass%, preferably 15 to 60 mass%.

(production of Polymer P)

Here, a method for producing the polymer P will be described.

The polymer P can be produced (synthesized) by any method. The polymer P can be produced, for example, by the following steps: a step (I): preparing a base polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA); and a step (II): a step of reacting the base polymer obtained in the step (I) with a compound having a hydroxyl group and 2 or more (meth) acryloyl groups (hereinafter referred to as a "polyfunctional (meth) acrylic monomer") in the presence of a basic catalyst to prepare a polymer P containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), and optionally a structural unit represented by the formula (MA).

When the polymer P further contains a structural unit represented by formula (2), it can be produced by the following steps: in the step (II), the raw material polymer obtained in the step (I), the polyfunctional (meth) acrylic monomer, and the compound having a hydroxyl group and 1 (meth) acryloyl group (hereinafter referred to as "monofunctional (meth) acrylic monomer") are reacted in the presence of a basic catalyst to prepare the polymer P containing the structural unit represented by the formula (NB), the structural unit represented by the formula (1), the structural unit represented by the formula (2), and optionally, the structural unit represented by the formula (MA).

When the polymer P further contains a structural unit represented by the formula (3), a polymer containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1) and/or a structural unit represented by the formula (2), and a structural unit represented by the formula (MA) is prepared in the step (II), and then the polymer is treated with water in the presence of an alkali catalyst (step (III)).

When the polymer P contains a sulfide group, such a polymer P can be produced by using a base polymer having a sulfide group introduced thereto in the step (II). Specifically, the thioether group-containing base polymer can be obtained by producing a base polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (MA), and a thioether group in step (I). The production of the base polymer having a thioether group introduced therein will be described in detail below.

When both a polyfunctional (meth) acrylic monomer and a monofunctional (meth) acrylic monomer are used in step (II), it is preferable that the polyfunctional (meth) acrylic monomer is first reacted with the base polymer, and then the monofunctional (meth) acrylic monomer is reacted with the obtained reaction mixture.

(Process (I))

In the step (I), a raw material containing a structural unit represented by the formula (NB) and a structural unit represented by the formula (MA) is preparedThe polymer process comprises: and a step of obtaining a target base polymer by polymerizing (addition-polymerizing) the monomer represented by formula (NBm) and maleic anhydride. R in formula (NBm)¹、R²、R³And R⁴And a₁Is as defined for formula (NB). The same applies to the preferred embodiment.

When a base polymer having a sulfide group introduced thereto is prepared in step (I), such a base polymer can be produced by polymerizing (addition-polymerizing) the monomer represented by formula (NBm) and maleic anhydride in the presence of a thiol group-containing compound. The thioether group introduced into the obtained base polymer is a group derived from a thiol group possessed by the thiol group-containing compound.

Examples of the monomer represented by the formula (NBm) include norbornene, norbornadiene (norbomadiene), bicyclo [2.2.1] -hept-2-ene (conventional name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, norbornene derivatives thereof, and the like, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, 5-norbornene-2, 3-dicarboxylic anhydride and the like. In the polymerization, only 1 monomer represented by formula (NBm) may be used, or 2 or more monomers may be used in combination.

As the thiol group-containing compound used for producing the base polymer having a sulfide group introduced therein, a thiol group-containing compound having 2 or more thiol groups, in other words, 2 or more functional groups, and more preferably 3 to 6 functional thiol group-containing compounds is used. By using such a thiol group-containing compound, the sensitivity of the obtained polymer P can be improved.

Specific examples of the thiol group-containing compound include compounds represented by the following formulas (s-1) to (s-20), but are not limited thereto. The thiol group-containing compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The method for polymerizing the monomer represented by formula (NBm) and maleic anhydride is not limited, but is preferably a radical polymerization using a radical polymerization initiator. As the polymerization initiator, for example, azo compounds, organic peroxides, and the like can be used.

Specific examples of the azo compound include Azobisisobutyronitrile (AIBN), dimethyl 2,2 '-azobis (2-methylpropionate), and 1,1' -azobis (cyclohexanecarbonitrile) (ABCN).

Examples of the organic peroxide include hydrogen peroxide, di (t-butyl) peroxide (DTBP), Benzoyl Peroxide (BPO), and Methyl Ethyl Ketone Peroxide (MEKP).

The polymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

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

The synthesis of the base polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) can be carried out by the following treatment: the monomer represented by formula (NBm), maleic anhydride, and a polymerization initiator are dissolved in a solvent, and the solution is charged into a reaction vessel, followed by heating to perform addition polymerization. The heating temperature is 50-80 deg.C, and the heating time is 5-20 hours.

The molar ratio of the monomer represented by formula (NBm) to maleic anhydride when charged into the reaction vessel is preferably 0.5:1 to 1: 0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1: 1.

Through such a step, a "base polymer" can be obtained.

The base polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, and the like. Typically a random copolymer or an alternating copolymer. Further, maleic anhydride is generally known as a monomer having a strong alternating copolymerizability.

The synthesis of the thioether-group-introduced base polymer containing the structural unit represented by formula (NB), the structural unit represented by formula (MA), and a thioether group is carried out by: the monomer represented by formula (NBm), maleic anhydride, and a polymerization initiator are dissolved in a solvent, and the solution is charged into a reaction vessel, and then heated, and addition polymerization is performed while adding dropwise the thiol group-containing compound. The heating temperature is 50 to 80 ℃ for example, and the heating time is 5 to 20 hours for example.

From the viewpoint of controlling the content of a thioether group in the raw material polymer having a thioether group introduced therein and the molecular weight of the raw material polymer, the amount of the thiol group-containing compound to be charged is preferably 0.5 to 10 mol%, particularly preferably 1 to 8 mol%, and further preferably 2 to 6 mol%, based on the total molar amount of the monomer represented by formula (NBm) and maleic anhydride charged at the time of charging into the reaction vessel.

After the synthesis of the base polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be performed.

Specifically, the organic phase containing the synthesized base polymer and low-molecular-weight components is concentrated, and then mixed with an organic solvent such as Tetrahydrofuran (THF) to obtain a solution. Then, the solution is mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried, whereby the purity of the raw polymer can be improved.

The polymer P of the present embodiment is produced in the following steps (II) and (III) using the base polymer obtained in step (I). In the following description, a case where a base polymer composed of a structural unit represented by formula (NB) and a structural unit represented by formula (MA) is used as the base polymer obtained in step (I) is described, but even in the case where a base polymer having a thioether group introduced therein is used, the same method can be used, and the polymer P obtained in this case contains a thioether group.

(Process (II))

When the structural unit represented by formula (1) and the monofunctional (meth) acrylic monomer are used, the structural unit represented by formula (2) is formed to obtain the polymer P containing the structural unit represented by formula (NB), the structural unit represented by formula (1), and the structural unit represented by formula (2) (when the monofunctional (meth) acrylic monomer is used), and the structural unit represented by formula (MA) is contained as the case may be.

More specifically, first, a solution is prepared by dissolving a raw material polymer in an appropriate 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), or the like can be used, but the organic solvent is not limited thereto, and various organic solvents used for synthesis of organic compounds or polymers can be used.

Next, a polyfunctional (meth) acrylic monomer is added to the above solution. Further adding a basic catalyst. Then, the solution is appropriately mixed to prepare a uniform solution, thereby obtaining a polymer containing at least the structural unit of formula (NB) and the structural unit of formula (1) (step (II-i)).

Examples of the polyfunctional (meth) acrylic monomer that can be used herein include compounds represented by the above formula (1b-p), compounds represented by the formula (1c-p), and compounds represented by the formula (1d-p) in which Y is a hydrogen atom.

Next, a monofunctional (meth) acrylic monomer is reacted with the polymer obtained in step (II-i) in the presence of a basic catalyst, whereby a polymer containing at least the structural unit of formula (NB), the structural unit of formula (1), and the structural unit of formula (2) can be obtained (step (II-II)).

Either of the step (II-i) and the step (II-II) may be carried out, but it is preferable to carry out the step (II-i). When both the step (II-i) and the step (II-II) are carried out, the step (II-II) is preferably carried out after the step (II-i).

(step (III))

When the step (III) is carried out, a step of treating the polymer obtained in the step (II) with water in the presence of a basic catalyst is used. By the step (III), the structural unit represented by the formula (MA) contained in the polymer obtained in the step (II) is ring-opened to form the structural unit represented by the formula (3), and thereby the polymer P containing the structural unit represented by the formula (NB), the structural unit represented by the formula (1) and/or the structural unit represented by the formula (2) and the structural unit represented by the formula (3) can be produced. When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit represented by formula (MA) remains without being ring-opened, polymer P contains the structural unit represented by formula (MA) in addition to the structural units represented by formula (NB), formula (1) and formula (2) (in the case of using a monofunctional (meth) acrylic monomer in step (II)) and formula (3).

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

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

(production of resin composition)

The resin composition of the present embodiment can be produced by mixing the above components by a known method. The resin composition of the present embodiment is used as a resin material of a photosensitive resin composition described below.

(photosensitive resin composition)

The photosensitive resin composition of the present embodiment contains the polymer P, a compound having 2 or more (meth) acryloyl groups (polyfunctional (meth) acrylic compound), and a photosensitizer. That is, the photosensitive resin composition of the present embodiment contains the resin composition of the present embodiment and a photosensitizer. Hereinafter, each component will be described.

The polymer P and the polyfunctional (meth) acrylic compound used in the photosensitive resin composition of the present embodiment are the same as described above.

As the photosensitizer used in the photosensitive resin composition of the present embodiment, a photo radical polymerization initiator can be mentioned. As the photo radical polymerization initiator, known compounds can be used, and examples thereof include 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [ 4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like, Alkylphenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholinophenyl ] -1-butanone; benzophenone-based compounds such as benzophenone, 4' -bis (dimethylamino) benzophenone, and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone and 2, 4-diethylthioxanthone; halomethylated triazine compounds such as 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, and 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5- (2 '-benzofuranyl) -1,3, 4-oxadiazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) vinyl ] -1,3, 4-oxadiazole, and 2-trichloromethyl-5-furanyl-1, 3, 4-oxadiazole; biimidazole compounds such as 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, and 2,2 '-bis (2,4, 6-trichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole; oxime ester compounds such as 1, 2-octanedione, 1- [ 4- (phenylthio) -2- (O-benzoyloxime) ], ethanone, and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime); titanocene-based compounds such as bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; benzoate-based compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine, and the like. The photo radical polymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The photo radical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, based on 1000 parts by mass of the polymer P.

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

In one embodiment, the photosensitive resin composition may contain a colorant. The colorant can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state imaging element. As the colorant, various pigments or dyes can be used.

As the pigment, an organic pigment or an inorganic pigment can be used.

As the organic pigment, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinoline yellow (quinophthalone) pigments, metal complex pigments, diketopyrrolopyrrole pigments, dibenzopyran (Xanthene) pigments, pyrromene pigments, dye lake pigments, and the like can be used.

As the inorganic pigment, there can be used white/extender pigments (titanium oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (chrome yellow, cadmium-based, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, lead red, ultramarine, iron blue, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), brightening material pigments (pearl pigment, aluminum pigment, bronze pigment, etc.), fluorescent pigments (zinc sulfide, strontium aluminate, etc.).

As the dye, for example, known dyes described in Japanese patent application laid-open Nos. 2003-270428, 9-171108, 2008-50599 and the like can be used.

When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only 1 kind of colorant, or may contain 2 or more kinds.

The colorant (particularly, pigment) can be used having an appropriate average particle diameter according to the purpose or application, and when transparency such as a color filter is particularly required, a small average particle diameter of 0.1 μm or less is preferable, and when opacity of a coating material or the like is required, a large average particle diameter of 0.5 μm or more is preferable.

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, or the like, depending on the purpose or application.

When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose or use, but from the viewpoint of satisfying both the coloring concentration and the dispersion stability of the colorant, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 50% by mass, based on the entire nonvolatile components (components other than the solvent) of the photosensitive resin composition.

In one embodiment, the photosensitive resin composition may contain a light-shading agent. The composition containing the light-shading agent can be preferably used as a material for forming a black matrix of a liquid crystal display device or a solid-state imaging element.

As the light-shading agent, known light-shading agents can be used without particular limitation. For example, black pigments such as carbon black, bone black, graphite, iron black, and titanium black can be used as the light-shading agent.

When the photosensitive resin composition contains a light-shading agent, the photosensitive resin composition may contain only 1 light-shading agent, or may contain 2 or more light-shading agents.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose or use, but from the viewpoint of achieving both light-shielding performance and dispersion stability of the light-shielding agent, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass, based on the entire nonvolatile components (components other than the solvent) of the photosensitive resin composition.

The photosensitive resin composition typically contains a solvent. As the solvent, an organic solvent can be preferably used. Specifically, 1 or 2 or more kinds of ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, and the like can be used.

Examples of the solvent include Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), Gamma Butyrolactone (GBL), N-methyl pyrrolidone (NMP), methyl N-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof.

The amount of the solvent used is not particularly limited, and is used in an amount such that the concentration of the nonvolatile component is, for example, 10 to 70 mass%, preferably 15 to 60 mass%.

In one embodiment, the photosensitive resin composition may contain a crosslinking agent.

The crosslinking agent is not particularly limited as long as it can crosslink (can chemically bond) the polymer by the action of an active chemical species generated from the photopolymerization initiator.

The crosslinking agent may be chemically bonded to the polymer, or may react with each other to form a bond.

The crosslinking agent is preferably, for example, a polyfunctional compound having 2 or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth) acrylic compound having 2 or more (meth) acryloyl groups in one molecule (however, the crosslinking agent does not correspond to the polymer). From the viewpoint of uniform curability, further improvement in sensitivity, and the like, it is preferable to use a crosslinking agent having a crosslinkable group of the same type as the crosslinkable group (polymerizable double bond) of the polymer.

The upper limit of the number of functional groups (number of polymerizable double bonds) per molecule of the crosslinking agent is not particularly limited, and is, for example, 8 or less, preferably 6 or less.

Specific examples of the crosslinking agent include the following.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexane dimethanol 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, glycerol 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 ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol tri (ethylene glycol tri (meth) acrylate, propylene glycol tri (ethylene glycol tri (meth) acrylate, propylene glycol tri (meth) acrylate, propylene glycol tri (ethylene glycol tri (meth) acrylate, propylene glycol tetra (meth) acrylate, propylene glycol tri (ethylene glycol tri (acrylate, propylene glycol tri (meth) acrylate, propylene glycol tetra (meth) acrylate, polyfunctional (meth) acrylates such as ethylene oxide-pentaerythritol tetra (meth) acrylate, ethylene oxide-dipentaerythritol hexa (meth) acrylate, propylene oxide-trimethylolpropane tri (meth) acrylate, propylene oxide-ditrimethylolpropane tetra (meth) acrylate, propylene oxide-pentaerythritol tetra (meth) acrylate, propylene oxide-dipentaerythritol hexa (meth) acrylate, epsilon-caprolactone-trimethylolpropane tri (meth) acrylate, epsilon-caprolactone-ditrimethylolpropane tetra (meth) acrylate, epsilon-caprolactone-pentaerythritol tetra (meth) acrylate, and epsilon-caprolactone-dipentaerythritol hexa (meth) acrylate.

Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol a alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol 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, and ethylene oxide-added dipentaerythritol hexavinyl ether.

2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, (meth) acrylic acid esters having a vinyl ether group such as 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexyl methyl (meth) acrylate, p-vinyloxymethylphenyl methyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, and 2- (vinyloxyethoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate.

Polyfunctional allyl ethers such as 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, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether.

Allyl group-containing (meth) acrylates such as allyl (meth) acrylate.

Isocyanurates containing a polyfunctional (meth) acryloyl group, such as tris (acryloyloxyethyl) isocyanurate, tris (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tris (acryloyloxyethyl) isocyanurate, and alkylene oxide-added tris (methacryloyloxyethyl) isocyanurate.

Isocyanurates containing polyfunctional allyl groups, such as triallyl isocyanurate.

Polyfunctional amine ester (meth) acrylates obtained by reacting polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate with hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Polyfunctional aromatic vinyl compounds such as divinylbenzene.

Among them, preferable are 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, and hexafunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only 1 kind of crosslinking agent, or may contain 2 or more kinds. When the photosensitive resin composition contains a crosslinking agent, the amount thereof may be appropriately set according to the purpose or use. For example, the amount of the crosslinking agent is usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, based on 100 parts by mass of the polymer P.

The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymers, an acid generator, a heat resistance improver, a development aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, a surfactant, an antistatic agent, a dispersant, a lubricant, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyvalent phenol compound, depending on the purpose or required characteristics.

(film, color filter, black matrix, liquid crystal display device, and solid-state imaging element)

A film with a pattern can be obtained by forming a film using the photosensitive resin composition and exposing and developing the film to form a pattern. The film is suitable for color filters, black matrices, or the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Further, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-shading agent. Then, a liquid crystal display device or a solid-state imaging device including a color filter or a black matrix can be manufactured.

Typical steps for forming a pattern will be described.

(formation of photosensitive resin film)

For example, the photosensitive resin composition is coated on an arbitrary substrate and dried as necessary, thereby obtaining a photosensitive resin film first.

The substrate of the coating composition is not particularly limited. Examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate.

The substrate may be a raw substrate or a substrate having electrodes or elements formed on the surface thereof. In order to improve the adhesion, a surface treatment may be performed.

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

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

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

(Exposure)

The exposure is typically performed by irradiating an active light ray to the photosensitive resin film through an appropriate mask.

Examples of the active light include X-rays, electron beams, ultraviolet rays, and visible rays. The wavelength is preferably 200 to 500 nm. The light source is preferably g-ray, h-ray or i-ray of a mercury lamp, and particularly preferably i-ray from the viewpoint of pattern resolution or operability. Further, 2 or more light beams may be mixed and used. As the exposure device, a contact aligner, a mirror projection aligner, or a stepper is preferable.

The amount of light to be exposed may be appropriately adjusted depending on the amount of the photosensitizer in the photosensitive resin film, and may be, for example, 100 to 500mJ/cm²Left and right.

After the Exposure, the photosensitive resin film may be heated again as necessary (Post Exposure heating). The temperature is, for example, 70 to 150 ℃, preferably 90 to 120 ℃. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By heating after exposure, a reaction based on radicals generated from the photo radical polymerization initiator is promoted, and the curing reaction is further promoted.

(development)

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

In the developing step, development can be performed using an appropriate developer by a method such as a dipping method, a spin coating and dipping method, or a spin coating and spraying method. By the 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.

The developer that can be used is not particularly limited. For example, an aqueous alkali solution or an organic solvent can be used.

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

Specific examples of the organic solvent 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.

The developer may be added with a water-soluble organic solvent such as methanol or ethanol, or a surfactant.

In the present embodiment, as the developer, an aqueous alkali solution is preferably used, and more preferably, tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution is used.

The concentration of the aqueous alkali solution is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass.

Through the above steps, a pattern can be obtained/a substrate having a pattern can be manufactured, but various processes can be performed after development.

For example, after the development, the pattern and the substrate may be cleaned with a rinse liquid. Examples of the rinse liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The obtained pattern can be sufficiently cured by heating. The heating temperature is typically 150 to 400 ℃, preferably 160 to 300 ℃, and more preferably 200 to 250 ℃. The heating time is not particularly limited, and is, for example, in the range of 15 to 300 minutes. The heat treatment can be performed by a hot plate, an oven, a temperature-raising oven capable of setting a temperature program, or the like. The atmosphere gas used in the heat treatment may be air or an inert gas such as nitrogen or argon. Further, heating may be performed under reduced pressure.

Fig. 1 schematically shows an example of a configuration of a liquid crystal display device and/or a solid-state imaging element including a color filter and/or a black matrix.

A black matrix 11 and a color filter 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 through which light passes, and is made of, for example, polyester, polycarbonate, polyolefin, polysulfone, or a polymer of cyclic olefin, in addition to glass. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like as necessary.

The substrate 10 is preferably made of glass.

The black matrix 11 is made of, for example, a cured product of a photosensitive resin composition containing a light-shading agent.

As the color filter 12, three colors of red, green, and blue are generally present. The color filter 12 is formed of a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

While the embodiments of the present invention have been described above, these are merely illustrative of the present invention and various configurations other than the above can be adopted. The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range in which the object of the present invention can be achieved are included in the present invention.

[ examples ]

The embodiments of the present invention will be described in detail with reference to examples and comparative examples. The present invention is not limited to the examples.

With respect to the compounds used in examples, the following abbreviations or trade names are sometimes indicated.

MA: maleic anhydride.

NB: 2-norbornene.

MEK: methyl ethyl ketone.

4-HBA: 4-hydroxybutyl acrylate.

A-TMM-3 LM-N: the amount of the left compound in the following 2 compound mixtures was about 57% based on the gas chromatography measurement (manufactured by Shin-Nakamura Chemical co., Ltd.).

A-9550: the amount of the compound on the left side in the mixture was about 50% estimated from the hydroxyl value of the following mixture of 2 compounds (manufactured by Shin-Nakamura Chemical co., Ltd.).

VISCOAT # 802: a mixture of tripentaerythritol acrylate, mono-and dipentaerythritol acrylate, and polypentaerythritol acrylate represented by the following formula (manufactured by Osaka Organic Chemical Industry co., Ltd.).

n＝1：10-20％。

n＝2：55-65％。

n＝3：5-15％。

< Synthesis of base Polymer >

(Synthesis of base Polymer 1)

588.36g (6.0 mol) of maleic anhydride, 564.90g (6.0 mol) of 2-norbornene and 55.26g (0.24 mol) of dimethyl 2,2' -azobis (2-methylpropionate) were metered and charged into a reaction vessel having an appropriate size and equipped with a stirrer and a cooling tube. These were dissolved in a mixed solvent composed of 1716.8g of methyl ethyl ketone and 188.3g of toluene to prepare a solution.

Nitrogen was passed through the solution for 30 minutes to remove oxygen, and then the solution was heated at 65 ℃ for 1.5 hours with stirring, and then further heated at 80 ℃ for 6 hours to polymerize maleic anhydride and 2-norbornene, thereby producing a polymerization solution.

The polymerization solution obtained in the above was dropwise added to 14230.2g of methanol, thereby precipitating a white solid. The obtained white solid was further washed with 3557.5g of methanol and then vacuum-dried at 120 ℃ to obtain 1027.2g of a polymer (base polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride.

The obtained polymer was measured by Gel Permeation Chromatography (GPC), and as a result, the weight average molecular weight Mw was 7236 and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.83.

(Synthesis of base Polymer 2)

602.56g (451.92 g, 4.8mol in terms of 2-norbornene), maleic anhydride (MAN, 470.69g, 4.8mol) and 2281.74g of Methyl Ethyl Ketone (MEK) were put into a reaction vessel equipped with a stirrer, a cooling tube and a dropping funnel, and stirred and dissolved. Then, the temperature was raised after removing the dissolved oxygen in the system by nitrogen bubbling, and when the internal temperature reached 80 ℃, a solution prepared by dissolving dimethyl 2,2' -azobisisobutyrate (product name: V-601, 44.21g, 0.19mol, manufactured by Wako Pure Chemical Industries, Ltd.) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP (thiol-containing compound of the above formula (s-2)) in MEK 193.4g was added over 1 hour. Thereafter, the reaction mixture was further reacted at 80 ℃ for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained in the above was dropwise added to 3686.4g of methanol, thereby precipitating a white solid. The obtained white solid was further washed with 3686.4g of methanol and then vacuum-dried at 120 ℃ to obtain 910.1g of a polymer (base polymer 2) containing a structural unit derived from 2-norbornene, a structural unit derived from maleic anhydride and a sulfide group.

The obtained polymer was measured by Gel Permeation Chromatography (GPC), and as a result, the weight average molecular weight Mw was 3500 and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.62.

< preparation of resin composition >

A resin composition containing the polymer P and a polyfunctional (meth) acrylic compound was produced by the following method.

Preparation example 1

A polymer P1 was produced in which the MA unit of the base polymer 1 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water. The following description will be made in detail.

First, 99.71g of MEK was added to 160.00 g (0.312 mol in terms of MA) of the base polymer to prepare a solution. Then, 38.75g of A-TMM-3LM-N, followed by 18.00g (0.178 mol) of triethylamine, was added to the solution, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 56.27g (0.390 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

Next, without post-treatment of the obtained reaction solution, 6.00g (0.333 mol) of water was added to the reaction solution, and the reaction was carried out at 70 ℃ for 0.5 hour.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following procedure.

Reprecipitation of the polymer with an excess of toluene.

The operation of washing the polymer powder obtained by reprecipitation with excess toluene was repeated 2 times.

The polymer powder after washing 2 times was washed 3 times with an excess of water.

The reaction product obtained was dried at 40 ℃ for 12 hours.

As a result, P160.20 g of a polymer obtained by ring-opening of the structural unit derived from maleic anhydride in the base polymer with A-TMM-3LM-N, 4-HBA and water was obtained.

(preparation example 2)

A resin mixture containing a polymer P2 in which the MA unit of the base polymer 1 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the following procedure, followed by solvent substitution.

Liquid-liquid extraction: the reaction solution was diluted with MEK, followed by treatment with water, whereby an aqueous phase was removed from the reaction solution, and then the same operation was further performed 1 time.

Solvent displacement: the obtained reaction mixture was subjected to solvent removal under reduced pressure and at 50 ℃ using a rotary evaporator. It was confirmed that the solid content concentration of the polymer solution became 27. + -. 2% by mass in the measurement based on the heat drying type moisture, and the operation of removing the solvent was interrupted. Thereafter, PGMEA was added so that the solid content concentration became 18 mass% and mixed until uniform. By the same operation, the removal of the solvent was performed under reduced pressure and at 50 ℃, and after the solid content concentration was adjusted to 27 ± 2 mass% in the measurement based on the heat-drying type moisture meter, the operation of further adding PGMEA so that the solid content concentration became 18 mass% and mixing to become uniform was further repeated 2 times. Thereafter, an operation of removing the solvent or adding PGMEA so that the solid content concentration becomes 30 ± 3 mass% and stirring until it becomes uniform was performed. By the above operation, the solvent used in the reaction was removed, and the solvent was replaced with PGMEA.

Thus, a resin mixture (resin composition) 2 containing a polymer P2 obtained by ring-opening the structural unit derived from maleic anhydride in the base polymer with A-TMM-3LM-N, 4-HBA and water, and the residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained.

The obtained resin composition 2 was analyzed by gel permeation chromatography, and the amounts of the polymer P2, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P2 were measured. The results are shown in Table 1. The amount of the free (meth) acrylic compound is represented by the ratio (%) of the peak area of the free (meth) acrylic compound to the peak area of the polymer P in a Gel Permeation Chromatography (GPC) chart of the resin mixture.

In addition, the measurement conditions of gel permeation chromatography are as follows.

HLC-8320GPC EcoSEC from Tosoh CORPORATION (TOSOH CORPORATION) was used as a GPC measurement device. The column temperature was set to 40.0 ℃ and the pump flow rate was set to 0.350 mL/min.

Peak position (hold time)

Polymer P: a peak detected 20 minutes before (a peak having a short retention time and a large molecular weight as compared with A-TMM-3LM-N and 4-HBA).

A-TMM-3 LM-N: a total of 2 peaks in 20.0 to 20.6 minutes and 20.6 to 21.5 minutes.

4-HBA: 21.7 to 22.4 minutes.

Measurement conditions: the analysis was performed with a differential refractive index detector (RI detector).

Preparation example 3

A resin mixture containing a polymer P3 in which the MA unit of the base polymer 1 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

Next, without post-treatment of the obtained reaction solution, 3.00g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70 ℃ for 2 hours.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 3. The obtained resin composition 3 was subjected to GPC measurement, and the amounts of the polymer P3, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P3 were measured. The results are shown in Table 1.

Preparation example 4

A resin mixture containing a polymer P4 in which the MA unit of the base polymer 1 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

First, a solution was prepared by adding 160.00 g (0.312 mol in terms of MA) of MEK 100.30g to a raw polymer. Subsequently, to the solution, 58.12g of A-TMM-3LM-N was added, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 56.27g (0.390 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 4. The obtained resin composition 4 was subjected to GPC measurement to measure the amounts of the polymer P4, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P4. The results are shown in Table 1.

Preparation example 5

A resin mixture containing a polymer P5 in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

First, 99.71g of MEK was added to 260.00 g (0.312 mol in terms of MA) of the base polymer to prepare a solution. Then, 38.75g of A-TMM-3LM-N, followed by 18.00g (0.178 mol) of triethylamine, was added to the solution, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 56.27g (0.390 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 5. The obtained resin composition 5 was subjected to GPC measurement to measure the amounts of the polymer P5, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P5. The results are shown in Table 1.

Preparation example 6

A resin mixture containing a polymer P6 in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The details will be described below.

First, MEK 100.30g was added to 260.00 g (0.312 mol in terms of MA) of a base polymer to prepare a solution. Subsequently, to the solution, 58.12g of A-TMM-3LM-N was added, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 56.27g (0.390 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 6. GPC measurement was performed on the obtained resin composition 6 to measure the amounts of the polymer P6, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P6. The results are shown in Table 1.

Preparation example 7

A resin mixture containing a polymer P7 in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The details will be described below.

First, MEK 102.43g was added to 260.00 g (0.312 mol in terms of MA) of a base polymer to prepare a solution. Subsequently, to the solution, 116.24g of A-TMM-3LM-N was added, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 56.27g (0.390 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 7. The obtained resin composition 7 was subjected to GPC measurement to measure the amounts of the polymer P7, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P7. The results are shown in Table 1.

Preparation example 8

A resin mixture containing a polymer P8 in which the MA unit of the base polymer 1 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

First, 97.74g of MEK was added to 160.00 g (0.312 mol in terms of MA) of the base polymer to prepare a solution. Subsequently, 58.12g of A-TMM-3LM-N was added to the solution, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 27.00g (0.187 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 8. The obtained resin composition 8 was subjected to GPC measurement, and the amounts of the polymer P8, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P8 were measured. The results are shown in Table 1.

Preparation example 9

A resin mixture containing a polymer P9 in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

First, 99.86g of MEK was added to 260.00 g (0.312 mol in terms of MA) of the base polymer to prepare a solution. Subsequently, to the solution, 58.12g of A-TMM-3LM-N was added, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 40.51g (0.281 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 9. The obtained resin composition 9 was subjected to GPC measurement to measure the amounts of the polymer P9, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P9. The results are shown in Table 1.

Preparation example 10

A resin mixture containing a polymer P10 in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The following description will be made in detail.

First, 100.03g of MEK was added to 260.00 g (0.312 mol in terms of MA) of the base polymer to prepare a solution. Subsequently, to the solution, 58.12g of A-TMM-3LM-N was added, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 27.00g (0.187 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 10. GPC measurement was performed on the obtained resin composition 10 to measure the amounts of the polymer P10, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P10. The results are shown in Table 1.

Preparation example 11

A polymer P11 was produced in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water. The following description will be made in detail.

First, 99.93g of MEK was added to 260.00 g (0.312 mol in terms of MA) of the base polymer to prepare a solution. Subsequently, to the solution, 77.49g of A-TMM-3LM-N was added, followed by 18.00g (0.178 mol) of triethylamine, and the mixture was reacted at 70 ℃ for 2 hours. Thereafter, 56.27g (0.390 mol) of 4-HBA was further added thereto, and the mixture was reacted at 70 ℃ for 4 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, a resin composition was obtained by performing liquid-liquid extraction and subsequent solvent substitution in the same manner as in preparation example 2. Thereafter, the resin composition was purified by the following procedure.

Reprecipitation of the polymer with an excess of toluene.

The operation of washing the polymer powder obtained by reprecipitation with an excess of toluene was repeated 2 times.

The reaction product obtained was dried at 40 ℃ for 12 hours.

As a result, P1134.35g, a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the base polymer 2, was obtained using A-TMM-3LM-N, 4-HBA and water.

Preparation example 12

A resin mixture containing a polymer P12 in which the MA unit of the base polymer 2 was ring-opened with a 3-functional (meth) acrylic compound, a monofunctional (meth) acrylic compound, and water was prepared. The details will be described below.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 12. The obtained resin composition 12 was subjected to GPC measurement to measure the amounts of the polymer P12, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P12. The results are shown in Table 1.

Preparation example 13

To resin composition 3 obtained by the same method as in production example 3, "additives" shown in table 1 were added in amounts shown in "additive amount" shown in table 1 to prepare resin composition 13. Here, the amount of the additive is set to a weight ratio with respect to the solid content (the total amount of the polymer P3 and the polyfunctional (meth) acrylic compound) of the resin composition 3.

The obtained resin composition 13 was subjected to GPC measurement to measure the amounts of the polymer P3, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P3. The results are shown in Table 1.

Peak position (hold time)

Polymer P: a peak detected 19.3 minutes before (a peak having a shorter retention time and a larger molecular weight than that of A-TMM-3LM-N, A-9550 and 4-HBA).

Polyfunctional (meth) acrylic compounds (A-TMM-3LM-N and A-9550): a total of 2 peaks in 19.3 to 19.8 minutes and 19.8 to 21.0 minutes.

4-HBA: 21.7 to 22.4 minutes.

Preparation example 14

To the resin composition 12 obtained by the same method as in production example 12, "additives" shown in table 1 were added in amounts shown in "additive amount" shown in table 1 to prepare a resin composition 14. Here, the amount of the additive is set to a weight ratio with respect to the solid content (the total amount of the polymer P12 and the polyfunctional (meth) acrylic compound) of the resin composition 12.

The obtained resin composition 14 was subjected to GPC measurement to measure the amounts of the polymer P12, the free polyfunctional (meth) acrylic compound and the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P12. The results are shown in Table 1.

Peak position (hold time)

Polymer P: the peak detected 19.5 minutes ago (peak having a shorter retention time and a larger molecular weight than VISCOAT #802, A-TMM-3LM-N and 4-HBA).

Polyfunctional (meth) acrylic compounds (A-TMM-3LM-N and VISCOAT # 802): a total of 2 peaks in 19.5 to 20.6 minutes and 20.6 to 21.5 minutes.

4-HBA: 21.7 to 22.4 minutes.

Preparation example 15

A polymer P13 was produced in which the MA unit of the base polymer 1 was ring-opened with a monofunctional (meth) acrylic compound. The following description will be made in detail.

First, MEK 18.44g was added to 110.00 g (0.052 mol in terms of MA) of the base polymer to prepare a dissolved solution. Subsequently, 9.38g (0.065 mol) of 4-HBA was added to the solution, and then 3.00g (0.030 mol) of triethylamine was added thereto, and the mixture was reacted at 70 ℃ for 6 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following procedure.

Reprecipitation of the polymer with an excess of water.

The operation of washing the polymer powder obtained by reprecipitation with an excess of water was repeated 2 times. The obtained reaction product was dried at 40 ℃ for 12 hours.

As a result, P139.5g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the base polymer with 4-HBA was obtained.

The polymer P13 thus obtained was subjected to GPC measurement to measure the weight average molecular weight and polydispersity of the polymer P13. The results are shown in Table 1.

Further, the disappearance of the peak of the monofunctional (meth) acrylic compound used was confirmed by GPC measurement of polymer P13. Thus, it was confirmed that the obtained polymer P13 contained no unreacted monofunctional (meth) acrylic compound.

Preparation example 16

A polymer P14 was produced in which the MA unit of the base polymer 2 was ring-opened with a monofunctional (meth) acrylic compound. The following description will be made in detail.

First, 18.44g of MEK was added to 210.00 g (0.052 mol in terms of MA) of the base polymer to prepare a solution. Subsequently, 9.38g (0.065 mol) of 4-HBA was added to the solution, and then 3.00g (0.030 mol) of triethylamine was added thereto, followed by reaction at 70 ℃ for 6 hours to prepare a reaction solution.

Reprecipitation of the polymer with an excess of water.

As a result, P148.7g of a polymer obtained by ring-opening of the structural unit derived from maleic anhydride in the base polymer with 4-HBA was obtained.

The weight average molecular weight and polydispersity of the polymer P14 were measured by GPC measurement of the obtained polymer P14. The results are shown in Table 1.

Further, the disappearance of the peak of the monofunctional (meth) acrylic compound used was confirmed by GPC measurement of the polymer P14. Thus, it was confirmed that the obtained polymer P14 contained no unreacted monofunctional (meth) acrylic compound.

Preparation example 17

A resin composition 17 containing a polymer P15 in which the MA unit of the base polymer 2 was ring-opened with a monofunctional (meth) acrylic compound was produced. The following description will be made in detail.

First, 18.44g of MEK was added to 210.00 g (0.052 mol in terms of MA) of the base polymer to prepare a solution. Subsequently, 9.38g (0.065 mol) of 4-HBA was added to the solution, and then 3.00g (0.030 mol) of triethylamine was added thereto, and the mixture was reacted at 70 ℃ for 6 hours to prepare a reaction solution.

The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution, thereby removing an aqueous phase from the reaction solution. Further, liquid-liquid extraction was performed by the same procedure as in preparation example 2, followed by solvent substitution to obtain a resin composition 17. The obtained resin composition 17 was subjected to GPC measurement, and the amount of the polymer P15, the free monofunctional (meth) acrylic compound contained in the composition, and the weight average molecular weight and polydispersity of the polymer P15 were measured. The results are shown in Table 1.

Table 1 below also shows the components used in each synthesis example and their loading amounts (in terms of Maleic Anhydride (MA)).

Examples 1 to 12 and comparative examples 1 to 5

In each example and each comparative example, the alkali solubility of the polymer P or the resin composition obtained in the above preparation example was evaluated. Further, a photosensitive resin composition was prepared using these polymer P or resin composition, and the properties thereof were evaluated.

< evaluation >

[ evaluation of developability ] (dissolution rate of Polymer P in alkaline developer)

The polymer P1 obtained in production example 1, the polymer P11 obtained in production example 11, the polymer P13 obtained in production example 15, and the polymer P14 obtained in production example 16 were dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) to prepare a solution having a solid content concentration of 30 mass%.

Next, the solution or the resin compositions 2 to 10, 12 to 14, 17 obtained in preparation examples 2 to 10, 12 to 14, 17 were spin-coated on a wafer, and PGMEA was dried, followed by pre-baking (pre cake) at 100 ℃ for 2 minutes to produce a resin film having a film thickness of 2 μm. + -. 0.2.

The resin film was immersed in a 2% sodium carbonate aqueous solution at a temperature of 23 c together with the wafer, and the dissolution rate of the resin film was measured.

The dissolution rate was calculated as follows: the immersed wafer was visually observed, the time until the resin film dissolved and no interference pattern was observed was measured, and the film thickness was divided by the time. The results are shown in Table 2. The alkali dissolution rate is 180nm/s or more, and the photosensitive material can be used without any problem, and the developability is good when the alkali dissolution rate is 300nm/s or more, and the developability is particularly good when the alkali dissolution rate is 500nm/s or more.

[ sensitivity evaluation 1 (exposure amount with residual film ratio of 95% or more) of photosensitive resin composition ]

First, the following components were dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) so that the total solid content concentration became 30 mass% to obtain a photosensitive resin composition.

Polymer P1 (Polymer P1 of preparation example 1), Polymer P11 (Polymer P11 of preparation example 11), Polymer P13 (Polymer P13 of preparation example 15) or Polymer P14 (Polymer P14 of preparation example 16) or resin compositions 2 to 10, 12 to 14, 17: 100 parts by mass.

(Here, the resin compositions 2 to 10, 12 to 14 and 17 were weighed so that the solid content (the total amount of the polymers P2 to P10, P12, P15 and the polyfunctional (meth) acrylic compound) was 100 parts by mass.)

Multifunctional acrylates (dipentaerythritol hexaacrylate): 50 parts by mass.

Photopolymerization initiator (manufactured by BASF, Ingacure OXE 01): 5 parts by mass.

An adhesion promoter (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by mass.

Surfactant (available from DIC Corporation, F-556): 0.5 part by mass.

The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100 ℃ for 120 seconds to obtain a film A having a thickness of 3.0 μm (+ -0.3 μm).

The film A is subjected to a mask having a gray scale of 1 to 100% light-shielding rate, and then subjected to a g + h + i ray mask aligner (PLA-501F) manufactured by Canon Inc. at a dose of 100mJ/cm²The exposure of g + h + i rays was performed.

After exposure, the film is developed in a 2.0 mass% aqueous solution of sodium carbonate at 23 ℃ for 60 seconds (together with wafer immersion), thereby obtaining a film having a thickness of 1 to 100mJ/cm²The film B was exposed and developed at each exposure.

The residual film ratio was calculated from the film thicknesses of the thin films a and B obtained by the above method by the following equation.

Residual film ratio (%) (film thickness of thin film B/film thickness of thin film a for each exposure) × 100

Then, the exposure amount at which the residual film ratio became 95% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 2. The exposure amount is 60mJ/cm when the residual film rate is more than 95%²The following can be used as a photosensitive material without any problem.

[ sensitivity evaluation 2 (residual film ratio after exposure to Low light amount) of resin composition ]

(5mJ/cm²Residual film rate of exposure amount of (2)

The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100 ℃ for 120 seconds to obtain a film A having a thickness of 3.0 μm (+ -0.3 μm).

The film A was subjected to a mask having a gray scale with a light-shielding rate of 1 to 100%, and then subjected to a g + h + i ray mask aligner (PLA-501F) made by Canon Inc. at a rate of 5mJ/cm²The exposure of g + h + i rays was performed.

After the exposure, the film was developed in a 2.0 mass% aqueous sodium carbonate solution at 23 ℃ for 60 seconds (together with wafer immersion), whereby a film B was obtained.

(10mJ/cm²Residual film ratio of exposure amount (2)

The film A is subjected to a mask having a gray scale with a light-shielding rate of 1-100%, and then subjected to a g + h + i ray mask aligner (PLA-501F) manufactured by Canon Inc. at a dose of 10mJ/cm²The exposure of g + h + i ray was performed.

The results are shown in Table 2.

The sensitivity can be considered to be good when the residual film ratio is 50% or more, and particularly good when the residual film ratio is 80% or more.

[ yellow index ]

The photosensitive resin composition prepared in the sensitivity evaluation 1 was spin-coated on EAGLE XG glass (manufactured by Corning Incorporated co., Ltd.) and baked on a hot plate at 100 ℃ for 120 seconds to obtain a film having a thickness of about 3.0 μm (± 0.1 μm).

Next, the film was aligned with a g + h + i radiation mask aligner (PLA-600F) made by Canon Inc. at 100mJ/cm²The exposure of g + h + i ray was performed.

After exposure, the film was developed in a 2.0 mass% aqueous sodium carbonate solution at 23 ℃ for 60 seconds (together with wafer immersion), thereby obtaining a film having a thickness of 100mJ/cm²The film is exposed and developed with the exposure of (1).

The film was heat treated at 230 ℃ and under air for 30 minutes. After the film was cooled at room temperature under air, the film was again heat-treated at 230 ℃ under air for 30 minutes. The same operation was repeated, and the total of 3 times of heat treatment under air was performed for 30 minutes.

The Yellowness Index (YI) of the film obtained by the above method was measured 3 times with changing the measurement site using a color difference meter CR-5 (manufactured by Konica Minolta, Inc.), and the average value thereof was taken as the value of YI. The measurement type was a transmission measurement, with 100% correction using uncoated EAGLE XG glass (manufactured by Corning Incorporated co., Ltd.) with a thickness of 0.5 mm). The results are shown in Table 2. The smaller the value of the yellow index, the better the heat discoloration resistance, and if it is 1.35 or less, it can be used as a photosensitive material without any problem.

The results of the developability evaluation and sensitivity evaluation are summarized below.

The photosensitive resin compositions of the examples had good alkali dissolution rates,therefore, the developability is excellent. The photosensitive resin composition of the example was at 10mJ/cm²The residual film ratio at the time of exposure with the exposure amount of (3) is high, in other words, curing at a low exposure amount, it can be said that sensitivity is high. Therefore, the photosensitive resin compositions of the examples had high sensitivity and low yellow index in good balance.

< production of color Filter >

A colored photosensitive resin composition was prepared by adding an appropriate amount of a pigment dispersion NX-061 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin composition prepared in examples 1 to 12.

The green color filter can be formed by forming a film on a substrate, and performing exposure, alkali development, and the like.

Further, a blue or red color filter can be formed by using NX-053 (blue), NX-032 (red) and the like manufactured by this company as a pigment dispersion liquid instead of NX-061.

< making of black matrix >

A black photosensitive resin composition was prepared by adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin compositions prepared in examples 1 to 12.

The black matrix can be formed by forming a film on a substrate, and performing exposure, alkali development, and the like.

This application claims priority based on Japanese application laid-open at 2019, 10, 16 and 2020, 1, 17 and 2020, 005974, and the disclosure of which is incorporated herein in its entirety.

Claims

1. A resin composition, wherein it comprises:

a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); and

a compound having 2 or more (meth) acryloyl groups,

in the formula (NB), R¹、R²、R³And R⁴Each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, a₁Is a number of 0, 1 or 2,

in the formula (1), R^pA group having 2 or more (meth) acryloyl groups.

2. The resin composition according to claim 1, wherein,

the polymer further contains a structural unit represented by formula (2),

in the formula (2), R^sIs a group having 1 (meth) acryloyl group.

3. The resin composition according to claim 1 or 2, wherein,

the weight average molecular weight of the polymer is 1000 or more and 20000 or less.

4. The resin composition according to any one of claims 1 to 3, wherein,

the resin composition has a Gel Permeation Chromatography (GPC) chart in which the peak area derived from the compound having 2 or more (meth) acryloyl groups is 5% or more and 150% or less relative to the peak area of the polymer.

5. The resin composition according to any one of claims 1 to 4, wherein,

the polymer further contains a structural unit represented by formula (3),

6. the resin composition according to any one of claims 1 to 5, wherein,

the polymer further contains a structural unit represented by the formula (MA),

7. the resin composition according to any one of claims 1 to 6, wherein,

the resin composition further contains a compound having 1 (meth) acryloyl group.

8. The resin composition according to claim 7, wherein,

the resin composition has a Gel Permeation Chromatography (GPC) chart in which the peak area derived from the compound having 1 (meth) acryloyl group is 5% or more and 60% or less relative to the peak area of the polymer.

9. The resin composition according to any one of claims 1 to 8, wherein,

the resin composition has an alkali dissolution rate of 250nm/s or more.

10. The resin composition according to any one of claims 1 to 9, wherein,

the resin composition further contains an organic solvent.

11. The resin composition according to claim 10, wherein,

the solvent is at least 1 selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma-butyrolactone, N-methyl pyrrolidone and cyclohexanone.

12. The resin composition according to any one of claims 1 to 11, wherein,

the resin composition is used to form a color filter or a black matrix.

13. A photosensitive resin composition, comprising:

a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1);

a compound having 2 or more (meth) acryloyl groups; and

a photosensitizer is added to the mixture of the two or more photosensitizers,

in the formula (1), R^pA group having 2 or more (meth) acryloyl groups.

14. The photosensitive resin composition according to claim 13, wherein,

the polymer further contains a structural unit represented by formula (2),

in the formula (2), R^sIs a group having 1 (meth) acryloyl group.

15. The photosensitive resin composition according to claim 13 or 14,

16. The photosensitive resin composition according to any one of claims 13 to 15,

the photosensitive resin composition has a peak area derived from the compound having 2 or more (meth) acryloyl groups in a Gel Permeation Chromatography (GPC) chart of 5% or more and 150% or less relative to a peak area of the polymer.

17. The photosensitive resin composition according to any one of claims 13 to 16,

the polymer further contains a structural unit represented by formula (3),

18. the photosensitive resin composition according to any one of claims 13 to 17, wherein,

the polymer further contains a structural unit represented by the formula (MA),

19. the photosensitive resin composition according to any one of claims 13 to 18,

the photosensitive resin composition further contains a compound having 1 (meth) acryloyl group.

20. The photosensitive resin composition according to claim 19,

the photosensitive resin composition has a peak area derived from the compound having 1 (meth) acryloyl group in a Gel Permeation Chromatography (GPC) chart of 5% or more and 60% or less relative to a peak area of the polymer.

21. A cured product formed from the photosensitive resin composition according to any one of claims 13 to 20.