WO2020158741A1

WO2020158741A1 - Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device and imaging element

Info

Publication number: WO2020158741A1
Application number: PCT/JP2020/003004
Authority: WO
Inventors: 潤壱田邊; 俊治久保山
Original assignee: 住友ベークライト株式会社
Priority date: 2019-01-31
Filing date: 2020-01-28
Publication date: 2020-08-06
Also published as: CN113366029A; JP7052900B2; JP2021120741A; CN113366029B; TW202035486A; JPWO2020158741A1; KR20210121169A

Abstract

The invention provides a photosensitive resin composition containing a polymer having a first structural unit represented by general formula (1), and having an acid value of 70 to 300 mg KOH/g and a double bond equivalent of 100 to 500 g/mol. In addition, the invention provides a polymer having a first structural unit represented by general formula (1), and having an acid value of 70 to 300 mg KOH/g and a double bond equivalent of 100 to 500 g/mol. In general formula (1), R^D represents a group containing a polymeric carbon-carbon double bond.

Description

Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device and image sensor

The present invention relates to a photosensitive resin composition, a polymer, a pattern, a color filter, a black matrix, a display device and an image sensor.

A display device (liquid crystal display or the like) and an image pickup device (CCD, CMOS or the like) usually include a color filter and a black matrix.
A photosensitive resin composition is often used for forming a color filter or a black matrix. Specifically, a photosensitive resin film is formed on a substrate by a photocurable photosensitive resin composition, and the film is exposed and developed to form a pattern such as a color filter or a black matrix on the substrate. It

Patent Document 1 discloses that an acid group, a polymerizable unsaturated group and a block isocyanato group are contained in the molecule, an acid value is 20 to 300 mgKOH/g, and an unsaturated group equivalent is 100 to 4,000 g/mol. And a curable polymer having a block isocyanato group equivalent of 400 to 6,000 g/mol is described. It is also described that a color filter is formed using this curable polymer.

Patent Document 2 describes that a black matrix is formed by using a binder resin having a weight average molecular weight of 1000 to 6000, an acid value of 80 to 200 mgKOH/g, and an ethylenically unsaturated bond equivalent of 500 or less. ..

Patent Document 3 discloses a copolymer obtained by radically polymerizing an ethylenically unsaturated monomer having a carboxyl group and having a formula weight of 70 to 120, and an ethylenically unsaturated monomer containing a carboxyl group-containing ethylenically unsaturated monomer. A photosensitive resin obtained by reacting 0.2 to 0.9 mol of an epoxy group in an epoxy group-containing ethylenically unsaturated monomer with 1 mol of a carboxyl group is described. Further, a photosensitive composition containing the photosensitive resin is described. Further, it is described that a color filter is formed using this photosensitive composition.
In Patent Document 3, it is described that the acid value of the photosensitive resin is preferably 20 to 200 mgKOH/g. In addition, the double bond equivalent of the photosensitive resin is preferably described as 300 to 1000.

Patent Document 4 discloses that a carboxyl group-containing polymer represented by a specific general formula is reacted with (i) a compound having a group reactive with carboxylic acid and an ethylenically unsaturated group, or (ii) reacted with carboxylic acid. An alkali-soluble resin obtained by reacting a compound having a group with a silicon-based functional group, and a photosensitive resin composition containing the alkali-soluble resin are described. Further, it is described that a color filter is formed using this photosensitive resin composition.
Patent Document 4 describes that the acid value of the alkali-soluble resin is preferably 25 to 100 mgKOH/g and the ethylenically unsaturated group equivalent is preferably 50 to 400.

International Publication No. 2014/141731 JP, 2005-197619, A JP, 2011-33951, A JP, 2007-264433, A

When a pattern is formed by using a photosensitive resin composition, particularly a negative photosensitive resin composition, the photocurability of the exposed area (that is, sensitivity) and the solubility of the unexposed area in a developing solution The tendency (developability) tends to have a trade-off relationship.
In particular, recently, with the background of further complication and miniaturization of liquid crystal display devices and solid-state imaging devices, it has been required to achieve both high sensitivity and high developability.

The present inventors have conducted a study this time with the aim of providing a photosensitive resin composition having both sensitivity and developability.

The present inventors have completed the inventions provided below as a result of intensive studies.

According to the present invention, the following is provided.

1.
A photosensitive resin composition comprising a polymer having a first structural unit represented by the following general formula (1), an acid value of 70 to 300 mgKOH/g, and a double bond equivalent of 100 to 500 g/mol. ..

In the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.
2.
1. The photosensitive resin composition according to,
The photosensitive resin composition, wherein the first structural unit includes a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds.
3.
1. Or 2. The photosensitive resin composition according to,
The first structural unit is a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds, and a structure in which R ^D is a group containing only one polymerizable carbon-carbon double bond. A photosensitive resin composition comprising a unit.
4.
1. ~3. The photosensitive resin composition according to any one of
The photosensitive resin composition, wherein the polymer further contains a second structural unit represented by the following formula (MA).

5.
1. ~ 4. The photosensitive resin composition according to any one of
The photosensitive resin composition, wherein the polymer further contains a structural unit having a cyclic hydrocarbon skeleton.
6.
1. ~ 5. The photosensitive resin composition according to any one of
The photosensitive resin composition, wherein the ratio of the first structural unit in all structural units of the polymer is 10 to 40 mol %.
7.
1. ~6. The photosensitive resin composition according to any one of
The photosensitive resin composition, wherein the polymer has a weight average molecular weight of 6,000 to 25,000.
8.
1. ~ 7. The photosensitive resin composition according to any one of
A photosensitive resin composition further containing a colorant.
9.
1. ~ 7. The photosensitive resin composition according to any one of
Further, a photosensitive resin composition containing a light shielding agent.
10.
A polymer having the first structural unit represented by the following general formula (1), having an acid value of 70 to 300 mgKOH/g, and having a double bond equivalent of 100 to 500 g/mol.

In the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.
11.
10. The polymer according to
The first structural unit is a polymer containing a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds.
12.
10. Or 11. The polymer according to
The first structural unit is a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds, and a structure in which R ^D is a group containing only one polymerizable carbon-carbon double bond. A polymer containing units.
13.
10. ~12. The photosensitive resin composition according to any one of
Further, a polymer containing a second structural unit represented by the following formula (MA).

14.
10. ~13. The polymer of any one of:
Further, a polymer containing a structural unit having a cyclic hydrocarbon skeleton.
15.
10. ~14. The polymer of any one of:
A polymer in which the ratio of the first structural unit in all structural units is 10 to 40 mol %.
16.
10. ~15. The polymer of any one of:
A polymer having a weight average molecular weight of 6,000 to 25,000.
17.
1. ~ 7. A pattern obtained by using the photosensitive resin composition according to any one of 1.
18.
8. A color filter obtained by using the photosensitive resin composition as described in 1.
19.
18. A display device including the color filter according to item 1.
20.
18. An image sensor including the color filter according to item 1.
21.
9. A black matrix obtained by using the photosensitive resin composition as described in 1.
22.
21. A display device comprising the black matrix described in 1.
23.
21. An image sensor including the black matrix according to item 1.

According to the present invention, a photosensitive resin composition having both sensitivity and developability is provided. Further, a polymer suitable for producing such a photosensitive resin composition is provided.

The above-mentioned object, other objects, features and advantages will be further clarified by the preferred embodiments described below and the following drawings accompanying it.

It is a figure (cross section) which shows typically an example of the structure of a liquid crystal display and/or a solid-state image sensing device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In all the drawings, the same reference numerals are given to the same components, and the description will be appropriately omitted.
In order to avoid complication, when there are a plurality of the same constituent elements in the same drawing, only one of them may be given a reference numeral, and all may not be given a reference numeral.
The drawings are for illustration purposes only. The shapes and dimensional ratios of the respective members in the drawings do not necessarily correspond to actual articles.

In the present specification, the "double bond" of "double bond equivalent" means a polymerizable carbon-carbon double bond.
In the present specification, the term “substantially” indicates a range including a manufacturing tolerance, a variation in assembly, and the like, unless otherwise specified.
In the present specification, the notation “a to b” in the description of the numerical range means a or more and b or less unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less".

In the description of a group (atomic group) in the present specification, a description not indicating whether it is substituted or unsubstituted includes both a group having no substituent and a group having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The expression "(meth)acrylic" in the present specification represents a concept including both acrylic and methacrylic. The same applies to similar notations such as “(meth)acrylate”.
Unless otherwise specified, the term "organic group" in the present specification means an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, “monovalent organic group” refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment has the first structural unit represented by the following general formula (1), has an acid value of 70 to 300 mgKOH/g, and has a double bond equivalent of 100 to 500 g/mol. Including a polymer that is
In the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.

By manufacturing a photosensitive resin composition using the above-mentioned polymer, a photosensitive resin composition having both sensitivity and developability can be obtained. The reason can be explained as follows.
The present invention is not limitedly interpreted by the following description.

The structural unit represented by the general formula (1) contains “both” of a group containing a polymerizable carbon-carbon double bond (R ^D in the general formula) and a carboxy group in one structural unit. I'm out.
Since the polymerizable group and the carboxy group are in the same structural unit, it is easy to design both the amount of the polymerizable group and the amount of the carboxy group in the polymer to be large values (other than (meth)acrylic resin etc. It is thought that such a design is difficult with the resin of. This is advantageous in that it enhances the developability as well as the sensitivity.

By designing the acid value of the polymer as a whole to 70 to 300 mgKOH/g and the double bond equivalent weight to 100 to 500 g/mol, both sensitivity and developability can be achieved at a high level.
That is, when the acid value of the polymer is 70 mgKOH/g or more, good developability can be obtained. Further, when the double bond equivalent is 500 g/mol or less, the sensitivity of the composition can be increased.

If the acid value is too large, the exposed portion is likely to be dissolved during development with an alkaline developer, and the exposure amount required for photocuring may be increased, or the pattern shape may be insufficient. There is. Therefore, in this embodiment, the upper limit of the acid value is 300 mgKOH/g.
If the double bond equivalent is too small (that is, if the density of double bonds in the polymer is too high), unexposed areas and low-exposed areas tend to be difficult to dissolve during development with an alkaline developer. However, a residual film tends to be generated during development. Further, if the double bond equivalent is too small, the molecular weight is excessively increased due to crosslinking, and there is a concern that the solubility may be excessively lowered. Therefore, in this embodiment, the lower limit of the double bond equivalent is 100 g/mol.

The acid value of the polymer is 70 to 300 mgKOH/g, preferably 80 to 200 mgKOH/g.
The double bond equivalent weight of the polymer is 100 to 500 g/mol, preferably 200 to 470 g/mol.
By adjusting the acid value and/or double bond equivalent of the polymer, it is possible to achieve both higher sensitivity and developability at a higher level.

Just in case, the acid value and the double bond equivalent can be obtained by measuring the spectrum. For example, it can be determined by the following procedure (more specifically, see the example).
(1) From the ¹ H-NMR chart of the polymer, the area (integral value) of the peak corresponding to the hydrogen atom of the carboxy group and the hydrogen atom near the polymerizable carbon-carbon double bond is determined.
(2) From the area of the peak derived from the standard substance, the area determined in (1) is determined to determine the amount of carboxy group and the amount of carbon-carbon double bond.
(3) The amount of the carboxy group obtained in (2) is converted into an acid value (mgKOH/g). Further, the amount of the polymerizable carbon-carbon double bond obtained in (2) is converted into the double bond equivalent (g/mol).

Properly designing the ratio of the structural unit represented by the general formula (1) in the polymer, the structure of R ^{D in} the general formula (1), the number of polymerizable carbon-carbon double bonds contained in R ^D , and the like. Thus, the acid value and double bond equivalent of the polymer can be set to appropriate values.

The components that can be contained in the photosensitive resin composition of the present embodiment will be described below.

(polymer)
As described above, the photosensitive resin composition of the present embodiment has the first structural unit represented by the general formula (1), has an acid value of 70 to 300 mgKOH/g, and has a double bond equivalent of 100. Includes polymers that are ˜500 g/mol. In the general formula (1), R ^D can be any group as long as it is a group containing a polymerizable carbon-carbon double bond.

-First Structural Unit The first structural unit preferably contains a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds. In other words, part or all of R ^D of the structural unit represented by the general formula (1) in the polymer is preferably a group containing two or more polymerizable carbon-carbon double bonds.
When R ^D contains two or more polymerizable carbon-carbon double bonds, the number of polymerizable carbon-carbon double bonds in R ^D is preferably 2 to 6, more preferably 2 to 5, and further preferably It is 3 to 5. By adjusting the number of polymerizable double bonds contained in R ^D , both sensitivity and developability can be made compatible at a higher level.

When R ^D contains two or more polymerizable carbon-carbon double bonds, preferably at least one (more preferably all) of the two or more polymerizable double bonds is present at the end of R ^D. With such a structure, the polymerizable double bond easily reacts with the active chemical species generated from the photopolymerization initiator. Therefore, the sensitivity can be further improved.

When R ^D contains two or more polymerizable carbon-carbon double bonds, by way of example, R ^D contains two or more (meth)acryloyl groups. More specifically, R ^D comprises 2-6, preferably 2-5, more preferably 3-5 (meth)acryloyl groups. In order to further improve the sensitivity, the (meth)acryloyl group is preferably an acryloyl group. This is because the acryloyl group not substituted with a methyl group is more likely to react with the active chemical species generated from the photopolymerization initiator than the methacryloyl group.

When R ^D contains two or more (meth)acryloyl groups, R ^D can be, for example, a group represented by the following general formula (1b) or (1c).

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

R is preferably a hydrogen atom from the viewpoint of further improving the sensitivity (ease of polymerization).
k may be 2 or 3, but is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

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

When X ¹ is a group represented by —Z—X— (Z is —O— or —OCO—, and X is an alkylene group having 1 to 6 carbon atoms), an alkylene group having 1 to 6 carbon atoms. May be linear or branched.
The alkylene group having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably —CH ₂ —CH ₂ —( Ethylene group) or —CH ₂ —CH(CH ₃ )—.

When X ¹ ′ is an alkylene group having 1 to 6 carbon atoms, its specific embodiment is the same as X ¹ .
^'If is a group represented by the -X'-Z'-, X' X 1 specific aspect is the same as the above X.

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

In the general formula (1c),
k, R, X ¹ and X ² have the same meanings as R, k, X ¹ and X ² in formula (1b), and a plurality of Rs may be the same or different from each other. X ^1's may be the same or different from each other,
X ³ is a divalent organic group having 1 to 6 carbon atoms,
X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,
X ⁶ is a divalent organic group having 1 to 6 carbon atoms.

Specific aspects and preferable aspects of R, k, X ¹ and X ² are the same as those described in the general formula (1b).
Examples of the divalent organic group having 1 to 6 carbon atoms of X ³ and X ⁶ include a group in which 2 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. You can The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon.
Examples of the divalent organic group having 1 to 6 carbon atoms for X ⁴ and X ⁵ include a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

The first structural unit is a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds, and a structural unit in which R ^D is a group containing only one polymerizable carbon-carbon double bond. It is preferable to include and. In other words, preferably, R ^D in some of the structural units represented by the general formula (1) in the polymer is a group containing two or more polymerizable carbon-carbon double bonds. Of the structural units represented by the general formula (1) in the polymer, R ^D in the remaining structural units is a group containing only one polymerizable carbon-carbon double bond.
By designing the polymer in this way, it becomes easier to obtain better developability while increasing the sensitivity.

Specific embodiments of “a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds” are as described above (in the general formula (1), R ^D is the general formula (1b). ) Or (1c) and the like).

In the “structural unit in which R ^D is a group containing a polymerizable carbon-carbon double bond having only one”, the polymerizable double bond is preferably present at the end of R ^D. Moreover, ^RD contains one (meth)acryloyl group as one aspect|mode. From the viewpoint of further improving the sensitivity, the (meth)acryloyl group is preferably an acryloyl group. More specifically, R ^D can be a group represented by general formula (2a) below.

In formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group.
The total carbon number of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10.

As the divalent organic group for X ¹⁰ , for example, an alkylene group is preferable. A part of —CH ₂ — in this alkylene group may be an ether group (—O—). The alkylene group may be linear or branched, but is preferably linear.

The divalent organic group for X ¹⁰ is more preferably a linear alkylene group having 3 to 6 carbon atoms in total. X ¹⁰ carbon atoms (corresponding to the "length" of X ¹⁰⁾ to the appropriate selection, comprising a group represented by the general formula (2a) is likely even to participate in the curing reaction. Therefore, the sensitivity can be further increased.

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

The proportion of the first structural unit in all the structural units of the polymer is preferably 10 to 40 mol%, more preferably 15 to 35 mol%.
The polymer is, as a first structural unit, R ^D is 2 or more polymerizable carbon - carbon double bond - a structural unit is a group containing a carbon double bond polymerizable carbon of R ^D is only one When both structural units that are groups are included, the molar ratio of the former to the latter is preferably 5:95 to 50:50, more preferably 10:90 to 40:60. By appropriately adjusting this ratio, it is easy to achieve both high sensitivity and developability.
Here, the molar ratio of the former to the latter can be determined as follows, for example.
In the polymer, the former amount is X ₁ (mol/g), the latter amount is X ₂ (mol/g), the amount of carboxyl group is C (mol/g), and the amount of polymerizable carbon-carbon double bond. Is D (mol/g). The former is assumed to contain n polymerizable carbon-carbon double bonds.
Both the former and the latter have one carboxyl group. Therefore, it can be written that X ₁ +X ₂ =C (assuming that the polymer contains no other structural unit containing a carboxyl group).
Further, regarding the amount of the polymerizable carbon-carbon double bond, it can be written that n·X ₁ +X ₂ =D (assuming that the polymer contains no other structural unit containing the polymerizable double bond).
C and D can be known from the peak area obtained by NMR measurement. Further, n is determined by the chemical structure of the raw material. Therefore, by solving these two mathematical expressions as simultaneous equations for unknowns X ₁ and X ₂ , the former:latter molar ratio can be obtained.
Furthermore, from the sum of X ₁ and X _2, the number of moles (mol/g) of each structural unit contained in the raw material polymer (described later), and the molecular weight of a monomer that is a base of each structural unit contained in the raw material polymer, The ratio of the first structural unit (or the total of the plural first structural units, if any) in all the structural units of the polymer can be determined.

-Second structural unit The polymer preferably further contains a second structural unit represented by the following formula (MA).
The second structural unit can be opened by an alkaline developer. It is considered that when the ring is opened, two carboxyl groups are generated, and therefore the developability is further improved.

When the polymer includes the structural unit represented by the formula (MA), the proportion of the structural unit represented by the formula (MA) in all the structural units of the polymer is preferably 1 to 25 mol%, more preferably 3 to It is 20 mol%.

-Solubility adjusting structural unit The polymer may include one or more of the structural units represented by the following general formula (a2-1), (a2-2) or (a2-3). By including such a structural unit in the polymer, it is possible to adjust the solubility in developing property and the solubility in organic solvent.
In formulas (a2-1) and (a2-2), R ₁₄ , R ₁₅ and R ₁₆ are each independently an organic group having 1 to 30 carbon atoms.

The organic group having 1 to 30 carbon atoms which constitutes R ₁₄ , R ₁₅ and R ₁₆ may include any one or more of O, N, S, P and Si in its structure. Further, the organic groups forming R ₁₄ , R ₁₅ and R ₁₆ may be those containing no acidic functional group. This makes it easy to control the acid value.

Examples of the organic group constituting R ₁₄ , R ₁₅ and R ₁₆ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group and a heterocyclic group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group and a heptyl group. , Octyl group, nonyl group, decyl group and the like.
Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group and the like.
Examples of the alkynyl group include an ethynyl group and the like.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaryl group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

In these alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, and heterocyclic group, one or more hydrogen atoms may be substituted with a halogen atom. Halogen atoms include fluorine, chlorine, bromine, and iodine. Of these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.

-Structural unit having a cyclic hydrocarbon skeleton The polymer preferably contains a structural unit having a cyclic hydrocarbon skeleton. Due to the rigid structure of the cyclic hydrocarbon skeleton, for example, the heat resistance and mechanical properties of the cured film when the photosensitive resin composition is cured can be improved.

A structural unit having a cyclic hydrocarbon skeleton, for example, is derived from the following monomers.

Cycloolefin monomer. Specifically, norbornene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5- Butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4) -Pentenyl)-2-norbornene, 5-ethylidene-2norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, and other monomers having a norbornene skeleton or norbornadiene skeleton.

A monomer having an indene skeleton or an acenaphthylene skeleton, such as indene, 2-methylindene, 3-methylindene, and acenaphthylene.
1,5,9-cyclododecatriene, cis-trans-trans-1,5,9-cyclododecatriene, trans-trans-trans-1,5,9-cyclododecatriene, trans-cis-cis-1, Monomers having a triene structure, such as 5,9-cyclododecatriene and cis-cis-cis-1,5,9-cyclododecatriene.
Monomers having a styrene skeleton such as styrene, vinyltoluene, hydroxystyrene, acetoxystyrene, α-methylstyrene.

N-cycloalkylmaleimides such as N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-norbornylmaleimide, N-cyclohexylmethylmaleimide and N-cyclopentylmethylmaleimide.
N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide ..

The structural unit having a cyclic hydrocarbon skeleton is preferably a structural unit derived from a cyclic olefin monomer, and more preferably a structural unit derived from a monomer having a norbornene skeleton or a norbornadiene skeleton. More specifically, the structural unit having a cyclic hydrocarbon skeleton is preferably represented by the following general formula (NB).

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

Examples of the organic group having 1 to 30 carbon atoms represented by R ¹ , R ² , R ³ and R ^{4 in} the general formula (NB) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group and an alkaryl group. , A cycloalkyl group, an alkoxy group, a heterocyclic group, a carboxyl group and the like.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, Examples thereof include an octyl group, a nonyl group and a decyl group.
Examples of the alkenyl group include allyl group, pentenyl group, vinyl group and the like.
Examples of the alkynyl group include ethynyl group and the like.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaryl group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group. , N-hexyloxy group and the like.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

As R ¹ , R ² , R ³ and R ⁴ in the general formula (NB), hydrogen or an alkyl group is preferable, and hydrogen is more preferable.
The hydrogen atom in the organic group having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ may be substituted with any atomic group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group or the like. More specifically, a fluorinated alkyl group or the like may be selected as the organic group having 1 to 30 carbon atoms for R ¹ , R ² , R ³ and R ⁴ .
In general formula (NB), a ₁ is preferably 0 or 1, and more preferably 0.

When the polymer contains structural units having a cyclic hydrocarbon skeleton, the amount thereof is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and further preferably 40 to 60 mol% in the total structural units of the polymer. By appropriately adjusting this ratio, it is easy to obtain additional effects (for example, improvement of heat resistance and improvement of mechanical properties when forming a cured film) while achieving both sensitivity and developability.
Incidentally, from the viewpoint of overall performance and cost, the polymer is different from the first structural unit as an essential structural unit, and the second structural unit as an optional structural unit and a structural unit having a cyclic hydrocarbon skeleton. It is preferable that the "other structural unit" is not included, or even if it is included in a small amount. Specifically, the ratio of "other structural units" in the polymer is preferably 0 to 20 mol%, more preferably 0 to 10 mol%.

The weight average molecular weight of the polymer is preferably 6,000 to 25,000, more preferably 7,000 to 20,000. By appropriately adjusting the weight average molecular weight, the solubility in an alkali developing solution, the solubility in an organic solvent and the like can be appropriately adjusted.
The dispersity of the polymer (weight average molecular weight Mw/number average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and further preferably 1.0 to 3.0. .. By properly adjusting the dispersity, the physical properties of the polymer can be made uniform, which is preferable.
These values can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The polymer may be produced (synthesized) by any method. For example,
A preparatory step of preparing a raw material polymer containing at least the structural unit represented by the above formula (MA);
The polymer can be produced by the reaction step of reacting the raw material polymer with a compound having a hydroxy group and a polymerizable carbon-carbon double bond in the presence of a basic catalyst.

The method for producing (synthesizing) a polymer by the above-mentioned preparation step and reaction step will be described more specifically below. The description will be given by exemplifying the synthesis of a polymer containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (NB), but this loses the generality of the polymer production method. Not a thing. For example, a polymer containing a structural unit represented by the general formula (1) and a structural unit (copolymerization unit) other than the general formula (NB) can be synthesized by a procedure similar to the following description.

Preparation Step The raw material polymer can be obtained, for example, by polymerizing (addition polymerization) a monomer represented by the following general formula (NB-m) and maleic anhydride.
The definitions of R ¹ , R ² , R ³ and R ⁴ and a _{1 in} the general formula (NB-m) are the same as those in the general formula (NB). The same applies to the preferred embodiment.

Examples of the monomer represented by the general formula (NB-m) include bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5- Examples thereof include methyl norbornene-2-carboxylate, 5-norbornene-2,3-dicarboxylic acid anhydride and norbornadiene.
In the polymerization, the monomer represented by the general formula (NB-m) may be used alone or in combination of two or more kinds.

The method of polymerization is not limited, but radical polymerization using a radical polymerization initiator is preferred.
As the polymerization initiator, for example, an azo compound, an organic peroxide or the like can be used.
Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl-2,2′-azobis(2-methylpropionate), 1,1′-azobis(cyclohexanecarbonitrile) (ABCN) and the like. Can be mentioned.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).
About a polymerization initiator, you may use only 1 type and may use it in combination of 2 or more type.

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

The monomer represented by the general formula (NB-m), maleic anhydride and a polymerization initiator are dissolved in a solvent and charged in a reaction vessel, and then heated to promote addition polymerization. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the general formula (NB-m) to maleic anhydride when charged in a 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.
The "raw material polymer" can be obtained by the steps described above.
The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer and the like. It is typically a random or alternating copolymer (maleic anhydride is generally known as a monomer with strong alternating copolymerization).

After synthesizing the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and remaining polymerization initiator may be performed.
Specifically, the organic layer containing the synthesized raw material polymer and the low molecular weight component is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, this solution is mixed with a poor solvent such as methanol to precipitate the monomer. The purity of the raw material polymer can be increased by filtering this precipitate and drying it.

-Reaction Step By reacting the raw material polymer obtained in the preparatory step with a compound having a hydroxy group and a polymerizable carbon-carbon double bond in the presence of a basic catalyst, the formula (MA ) The structural unit is opened. Thereby, the structural unit represented by the general formula (1) is formed.

More specifically, first, a polymer solution in which a raw material polymer is dissolved in an appropriate organic solvent is prepared.
Examples of organic solvents that can be used here include single solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF), or mixed solvents. Can be mentioned. Of course, the solvent is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

Next, a compound having a hydroxy group and a polymerizable carbon-carbon double bond is added to this polymer solution. In addition, a basic catalyst is added. Then, they are appropriately mixed to form a uniform solution.

Examples of the compound having a hydroxy group and a polymerizable carbon-carbon double bond include a compound containing one or more (meth)acryloyl groups and a hydroxy group.
By using a compound (polyfunctional compound) containing two or more (meth)acryloyl groups and a hydroxy group, a polymerizable carbon-carbon double bond having R ^D of 2 or more in the general formula (1) is used in the polymer. A structural unit which is a group containing can be introduced.
On the other hand, by using a compound (monofunctional compound) containing a (meth)acryloyl group of only 1 and a hydroxy group, a polymerizable carbon-carbon dicarboxylic acid in which R ^D is only 1 in the general formula (1) is used in the polymer. A structural unit, which is a group containing a heavy bond, can be introduced.
By using both of these polyfunctional compounds and monofunctional compounds, as a first structure unit, R ^D is 2 or more polymerizable carbon - a structural unit is a group containing a carbon double bond, R ^D is only one Both structural units, which are groups containing polymerizable carbon-carbon double bonds, can be introduced into the polymer. However, in terms of steric hindrance, a monofunctional compound tends to react with a polymer more easily than a polyfunctional compound, so in the reaction step, the monofunctional compound is not charged into the reaction system from the beginning, but “addition” is added. Preferably.

As the "compound containing two or more (meth)acryloyl groups and a hydroxy group", specifically, a compound represented by the following general formula (1b-m) or a compound represented by the following general formula (1c-m) Compounds can be mentioned.
Definitions and specific embodiments of the general formula (1b-m) in ^{^{k, R, X 1, X}} 1 ' and ^{X 2} are the same as in the general formula (1b).
The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ^{6 in} the general formula (1c-m) are the same as those in the general formula (1c).

As compounds containing two or more (meth)acryloyl groups and a hydroxy group, compounds that can be preferably used are shown below. In addition, it is also possible to use a compound in which some or all of the acryloyl groups of the compounds shown below are (meth)acryloyl groups (or vice versa).

On the other hand, examples of the "compound containing only one (meth)acryloyl group and a hydroxy group" include compounds represented by the following general formula (2a-m).
In general formula (2a-m), the definitions and specific embodiments of X ¹⁰ and R are the same as in general formula (2a).

Specific examples of the compound represented by the general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, and 2 -Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalic acid, etc. You can

After the reaction step, the reaction is stopped by diluting the reaction solution with an organic solvent and/or adding an acid for neutralizing the basic catalyst.
A polymer can be obtained by the above steps.

For reference, in the reaction step, by appropriately adjusting the amount of the compound having a hydroxy group and a polymerizable carbon-carbon double bond, the maleic anhydride structure in the raw material polymer is not all ring-opened, The structure of formula (MA) will be contained in the conventional polymer.
In the reaction step, the maleic anhydride structure in the raw material polymer is reacted with water, alcohol, or another appropriate substance to give a compound represented by the general formula (a2-1), (a2-2) or (a2-3). The structural unit represented by can be introduced into the polymer.

　In order to remove unnecessary components other than the desired polymer, it is preferable to perform the following steps as appropriate.

First, the reaction solution diluted with an organic solvent and added with an acid (for example, formic acid) is vigorously stirred for at least 3 minutes with a separating funnel. The mixture is allowed to stand for 30 minutes or longer to separate an organic phase and an aqueous phase, and the aqueous phase is removed. In this way an organic solution of the polymer is obtained.

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

(Photopolymerization initiator)
The photosensitive resin composition of the present embodiment preferably contains a photopolymerization initiator.
Any photopolymerization initiator can be used as long as the component generated by light irradiation reacts with the polymerizable double bond contained in the structural unit of the general formula (1) of the polymer. The photopolymerization initiator can be, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, or the like.
The photopolymerization initiator typically generates active chemical species upon irradiation with ultraviolet light, more specifically g-line or i-line.

From the viewpoint of further increasing the sensitivity, the photopolymerization initiator is preferably a photoradical polymerization initiator.
The photoradical polymerization initiator is not particularly limited, and known ones can be appropriately used. For example, the following can be mentioned.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl 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-methylpropionyl)benzyl]phenyl}- 2-Methylpropan-1-one, 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- Alkylphenone compounds such as butanone-1,2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

Benzophenone compounds such as benzophenone, 4,4′-bis(dimethylamino)benzophenone and 2-carboxybenzophenone.
Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutylate.
Thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone.

2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 Halomethylated triazine compounds such as -ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarboquinylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine ..
2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxa Halomethylated oxadiazole compounds such as diazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1, Biimidazole compounds such as 2'-biimidazole.
1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole- 3-yl] oxime ester compounds such as ethanone oxime.
A titanocene-based compound such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
Benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.
Acridine compounds such as 9-phenylacridine.

The photosensitive resin composition may include only one type of photopolymerization initiator, or may include two or more types thereof.
The amount of the photopolymerization initiator used is, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer.

(solvent)
The photosensitive resin composition of this embodiment typically contains a solvent. As a result, a uniform photosensitive resin film can be formed on the surface of various substrates.
An organic solvent is preferably used as the solvent. Specifically, one or more 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-methylpyrrolidone (NMP), methyl- Mention may be made of n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.

The amount of solvent used is not particularly limited. For example, it is used in such an amount that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

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

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

Specific examples of the cross-linking agent include the following.

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol Di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate , Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide Addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane tetra(meth)acrylate, propylene oxide addition pentaerythritol tetra (Meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra Polyfunctional (meth)acrylates such as (meth)acrylate and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate.

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditril Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Multifunctional vinyl ethers such as added dipentaerythritol hexavinyl ether.

2-Vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, (meth)acrylic acid 4 -Vinyloxybutyl, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, ( Vinyl ether group-containing (meth) such as p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate Acrylic esters.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether.

Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate.
Multifunctional (meth)acryloyl such as tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate Group-containing isocyanurates.
Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate.
Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Polyfunctional urethane (meth)acrylates obtained in.
Polyfunctional aromatic vinyls such as divinylbenzene.

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

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

(Colorant)
The photosensitive resin composition of this embodiment may contain a colorant. When the composition contains a colorant, it can be preferably used as a material for forming a color filter of a display device or an image pickup device.
As the colorant, various pigments or dyes can be used.

As the pigment, an organic pigment or an inorganic pigment can be used.
Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. Pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, dye lake pigments and the like can be used.
Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium, chrome vermillion, nickel titanium, chromium titanium) , Yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigment, aluminum pigment, bronze pigment, etc.), fluorescent pigment ( Zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108 and JP-A-2008-50599 can be used.

As the colorant (particularly pigment), one having an appropriate average particle diameter can be used depending on the purpose and application. Especially when transparency such as a color filter is required, a small average particle diameter of 0.1 μm or less is preferable. On the other hand, when the hiding property of paints is required, a large average particle size 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 and the like, depending on the purpose and use.

When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant or two or more types of colorant.
When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose and application, but from the viewpoint of compatibility between the color density and the dispersion stability of the colorant, the nonvolatile content of the photosensitive resin composition It is preferably from 3 to 70% by mass, more preferably from 5 to 60% by mass, and further preferably from 10 to 50% by mass, based on the entire components (components excluding the solvent).

(Shading agent)
The photosensitive resin composition of this embodiment may include a light shielding agent. When the composition contains a light-shielding agent, it can be preferably used as a material for forming a black matrix of a display device or an image pickup device.
As the light-shielding agent, a known light-shielding agent 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 shielding agent.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and application, but from the viewpoint of compatibility between the light-shielding performance and the dispersion stability of the light-shielding agent, the nonvolatile content of the photosensitive resin composition It is preferably from 3 to 70% by mass, more preferably from 5 to 60% by mass, and further preferably from 10 to 50% by mass, based on the entire components (components excluding the solvent).

(Other ingredients)
The photosensitive resin composition of the present embodiment may contain components other than the above depending on various purposes and required characteristics.
Examples of components that may be included include fillers, binder resins other than the above polymers, polyfunctional (meth)acrylate compounds, acid generators, heat resistance improvers, development aids, plasticizers, polymerization inhibitors, and ultraviolet absorbers. Antioxidants, matting agents, defoaming agents, leveling agents, surfactants, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, silane coupling agents, polyhydric phenol compounds, etc. To be

<Pattern, color filter, black matrix, display device, image sensor, and method for manufacturing display device or image sensor>
A film can be formed by using the above-mentioned photosensitive resin composition, and the film can be exposed and developed to form a pattern. This pattern is applied to, for example, a color filter or a black matrix. Specifically, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. A black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light shielding agent. Then, a display device (typically a liquid crystal display device) or an imaging device (typically a solid-state imaging device) including a color filter and/or a black matrix can be manufactured.

A typical procedure for forming a pattern is explained below.

-Formation of photosensitive resin film For example, the photosensitive resin composition of the present embodiment is applied onto an arbitrary substrate and dried as necessary. Thereby, first, a photosensitive resin film is obtained.

The substrate is not particularly limited. For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper clad laminate, etc. can be mentioned.
The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed on the surface. The substrate may be surface treated to improve adhesion.
The method for applying the photosensitive resin composition is not particularly limited. The coating can be performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

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

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

-Exposure Exposure is typically performed by exposing the photosensitive resin film to actinic rays through a suitable photomask.
Examples of actinic rays include X-rays, electron rays, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably a g-line, h-line or i-line of a mercury lamp, and particularly preferably i-line. Further, two or more light rays may be mixed and used. As the exposure device, a contact aligner, a mirror projection or a stepper is preferable.
The light amount of exposure may be appropriately adjusted depending on the amount of the photopolymerization initiator in the photosensitive resin film, the film thickness of the photosensitive resin film, and the like. The exposure light amount is, for example, about 100 to 500 mJ/cm ² .

After exposure, the photosensitive resin film may be heated again if necessary (post-exposure heating: Post Exposure Bake). The heating temperature here is, for example, 70 to 150° C., preferably 90 to 120° C. The heating time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By heating after exposure, the polymerization reaction by the active species generated from the photopolymerization initiator is promoted, and the curing reaction is further promoted. That is, it is possible to further increase the sensitivity in terms of process.

-Development By developing the exposed photosensitive resin film with a suitable developing solution, a pattern can be obtained and a substrate having a pattern can be manufactured.
In the developing step, development can be carried out by using a suitable developing solution, for example, a method such as a dipping method, a paddle method or a rotary spray method. By the development, the exposed portion (in the case of positive type) or the unexposed portion (in the case of negative type) of the photosensitive resin film is eluted and removed to obtain a pattern. When the photosensitive resin composition of this embodiment is used, a negative pattern is usually obtained.

The developer that can be used is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used.
Specific examples of the alkaline aqueous solution include (i) an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine, and triethanolamine, (iii) Examples thereof include aqueous solutions of quaternary ammonium hydroxide such as tetramethylammonium hydroxide and 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, ether solvents such as propylene glycol monomethyl ether, and the like.
The developer may contain a water-soluble organic solvent such as methanol or ethanol, or an additive such as a surfactant.

In the present embodiment, it is preferable to use an alkaline aqueous solution as the developing solution, and it is more preferable to use an aqueous solution of tetramethylammonium hydroxide or sodium carbonate.
The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

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

Alternatively, the obtained pattern may be heated to be sufficiently cured. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, more preferably 200 to 250°C. The heating time is not particularly limited, but is within a range of 15 to 300 minutes, for example. This heat treatment can be performed using a hot plate, an oven, a temperature rising oven that can set a temperature program, or the like. The atmosphere gas used for the heat treatment may be air or an inert gas such as nitrogen or argon. Moreover, you may heat under reduced pressure.

By the above process, it is possible to obtain a pattern/manufacture a substrate having a pattern. More specifically, a color filter can be obtained using a photosensitive resin composition containing a colorant. Further, a black matrix can be obtained by using a photosensitive resin composition containing a light shielding agent. Further, a display device (typically a liquid crystal display device) or an image pickup device (typically a solid-state image pickup device) including a color filter and/or a black matrix can be manufactured.

An example of the structure of a display device and/or an image sensor including a color filter and/or a black matrix is schematically shown in FIG.
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 usually made of a material that transmits light. For example, it is made of any one of glass, polyester, polycarbonate, polyolefin, polysulfone, and a polymer of cyclic olefin.
The substrate 10 may have been subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like.
The substrate 10 is made of glass, for example.

The black matrix 11 is usually a cured product of a photosensitive resin composition containing a light shielding agent.
The color filter 12 usually has three colors of red, green and blue. The color filter 12 is usually a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.

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

The compounds used in the examples may be represented by the following abbreviations or trade names.
MA: maleic anhydride NB: 2-norbornene MEK: methyl ethyl ketone BHEA: 2-hydroxyethyl acrylate 4-HBA: 4-hydroxybutyl acrylate

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

A-TMM-3LM-N: a mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatographic measurement is about 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

<Synthesis of raw material polymer>
First, a raw material polymer containing a maleic anhydride structural unit and a 2-norbornene structural unit was synthesized. Details are shown below.

(Raw polymer 1)
In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, maleic anhydride 353.02 g (3.6 mol), 2-norbornene 338.94 g (3.6 mol) and dimethyl-2,2'-azobis 33.16 g (0.144 mol) of (2-methylpropionate) was weighed in. These were dissolved in a mixed solvent composed of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.
Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated with stirring at a temperature of 65° C. for 1.5 hours, and then at 80° C. for 6 hours to give maleic anhydride. And 2-norbornene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 851.99.9 g of methanol to precipitate a white solid. The resulting white solid was vacuum dried at a temperature of 120° C. to obtain 607.5 g of a polymer (raw material polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. ..
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 7,000, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.82. there were.

(Raw polymer 2)
In a reaction vessel of appropriate size equipped with a stirrer and cooling tube, maleic anhydride 353.02 g (3.6 mol), 2-norbornene 338.94 g (3.6 mol), and dimethyl-2,2'-azobis 33.16 g (0.144 mol) of (2-methylpropionate) was weighed in. These were dissolved in a mixed solvent consisting of MEK2654.9 g and toluene 113.0 g to prepare a solution.
Nitrogen was bubbled through the solution for 30 minutes to remove oxygen, and then the solution was heated with stirring at a temperature of 65° C. for 1.5 hours and then at 80° C. for 6 hours to give maleic anhydride. And 2-norbornene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 13972.1 g of methanol to reprecipitate a white solid. By vacuum-drying the obtained white solid at a temperature of 120° C., 569.1 g of a polymer (raw material polymer 2) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride was obtained.
As a result of GPC measurement of the obtained polymer, the weight average molecular weight Mw was 4,300, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.59.

<Synthesis of polymer (ring opening of structural unit derived from MA of raw material polymer)>
(Comparative Synthesis Example 1)
A polymer in which a structural unit derived from MA of raw material polymer 1 (hereinafter, also simply referred to as “MA unit”) was opened with a trifunctional acrylate having a hydroxyl group was prepared. The details will be described below.
First, 64.15 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 96.85 g of A-TMM-3L (the amount added as the mixture of the above two kinds, the same applies below) was added, and then 9.00 g (0.089 mol) of triethylamine was added, and the temperature was adjusted to 70 A reaction solution was prepared by reacting at 6°C for 6 hours.

The aqueous phase was removed from the reaction solution by treating the prepared reaction solution with a formic acid aqueous solution. Then, the polymer was purified by the following procedure.
-Reprecipitate the polymer with excess toluene.
The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
The operation of washing the above-mentioned polymer powder after washing twice with an excess amount of water was performed three times.

From the above, 23.39 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L.

(Comparative Synthesis Example 2)
A polymer was prepared by ring-opening the MA unit of the raw material polymer 1 only with a hydroxyl group-containing monofunctional acrylate. The details will be described below.
First, 55.50 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 22.65 g (0.195 mol) of BHEA was added, then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. ..
The aqueous phase was removed from the reaction solution by treating the obtained reaction solution with an aqueous formic acid solution. Then, the solution was poured into a large amount of pure water to precipitate a polymer. The obtained polymer was collected by filtration and washed with pure water.
As a result, 27.21 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened only with BHEA.

(Comparative Synthesis Example 3)
A polymer was prepared by ring-opening the MA unit of the raw material polymer 1 only with a hydroxyl group-containing monofunctional acrylate. The details will be described below.
First, 55.5 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 28.11 g (0.195 mol) of 4-HBA was added, then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 6 hours to give a reaction solution. It was made.
The aqueous phase was removed from the reaction solution by treating the obtained reaction solution with an aqueous formic acid solution. Then, the solution was poured into a large amount of pure water to precipitate a polymer. The obtained polymer was collected by filtration and washed with pure water.
As a result, 26.54 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the starting polymer with 4-HBA was obtained.

(Synthesis example 1)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, 67.72 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 58.12 g of A-TMM-3L was added, and then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 22.21 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 2)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, MEK 49.41g was added with respect to the raw material polymer 1 30g (0.156mol of MA conversion), and the solution was produced. Next, to this solution, 19.37 g of A-TMM-3L was added, and then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 22.53 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 3)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, MEK 49.51g was added with respect to the raw material polymer 1 30g (0.156mol of MA conversion), and the solution was produced. Next, to this solution, 19.37 g of A-TMM-3L was added, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As described above, 22.10 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 4)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, 49.86 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 19.37 g of A-TMM-3L was added, and then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at 70° C. for 2 hours. After that, 28.13 g (0.195 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 24.64 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and 4-HBA.

(Synthesis example 5)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, 47.35 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 19.37 g of A-TMM-3L was added, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 28.13 g (0.195 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 25.77 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and 4-HBA.

(Synthesis example 6)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a hydroxyl group-containing pentafunctional acrylate and a hydroxyl group-containing monofunctional acrylate. The details will be described below.
First, 71.03 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 43.78 g of A-9550 was added, and then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added to the reaction solution and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 25.51 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-9550 and BHEA.

(Synthesis example 7)
A polymer was prepared by opening the MA unit of the raw material polymer 2 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, 49.41 g of MEK was added to 30 g of the raw material polymer 2 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 19.37 g of A-TMM-3LM-N was added, and then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 21.11 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 8)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, 50.60 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 7.75 g of A-TMM-3LM-N was added to this solution, and then 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 20.66 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3LM-N and BHEA.

(Synthesis example 9)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, MEK (46.60 g) was added to the raw material polymer 1 (30 g, 0.156 mol in terms of MA) to prepare a solution. Then, to this solution, 7.75 g of A-TMM-3L was added, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 21.22 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 10)
A polymer was prepared by opening the MA unit of the raw material polymer 1 with a trifunctional acrylate containing a hydroxyl group and a monofunctional acrylate containing a hydroxyl group. The details will be described below.
First, 54.13 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 29.06 g of A-TMM-3LM-N was added, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 2 hours. After that, 22.65 g (0.195 mol) of BHEA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was purified using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like, as in Comparative Synthesis Example 1.
As a result, 24.54 g of a polymer was obtained in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3LM-N and BHEA.

<GPC measurement>
For each polymer, the weight average molecular weight and the dispersity (weight average molecular weight/number average molecular weight) were determined by GPC measurement using polystyrene as a standard substance.
The disappearance of the peaks of the acrylate compounds (BHEA, 4-HBA, A-TMM-3L, A-TMM-3LM-N, A-9550) was confirmed by GPC measurement. That is, in the polymers of each synthesis example and comparative synthesis example, it is confirmed that the MA unit of the raw material polymer and the unreacted acrylate and the acrylate compound that does not react with the MA unit (acrylate not containing a hydroxyl group) are sufficiently removed. confirmed.

<NMR measurement of polymer>
¹ H-NMR measurement was performed on the polymers of each synthesis example and comparative synthesis example.
¹ H-NMR measurement Based on the integrated value of the 4 H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate as an internal standard, the H peak (around 12.4 ppm) of the polymer carboxyl group (—COOH). The amount of carboxyl groups was determined from the integrated value of. Then, the acid value (mgKOH/g) was calculated from the amount.
The larger the acid value, the larger the amount of carboxyl groups per unit mass of the polymer.

Similarly, based on the integrated value of the 4H peak of the phenyl group of dimethyl terephthalate (around 8.1 ppm), the 3H peak of the acryloyl moiety (CH ₂ ═CH—COO—) in the polymer (6. The amount of C=C double bond was obtained from the integrated value of (about 2 ppm), and the double bond equivalent (C=polymer mass per mol of C double bond, g/mol) was calculated from the amount.
The smaller the value of the double bond equivalent, the larger the amount of C=C double bond per unit mass of the polymer.

Table 1 shows the acrylate compound used in the synthesis, the weight average molecular weight of the polymer, the dispersity, the acid value, and the double bond equivalent of the polymers of each synthesis example and comparative synthesis example.

In addition, among the first structural unit, R ^D is 2 or more polymerizable carbon - the ratio of the structural unit is a group containing a carbon double bond, of the first structural unit, polymerizable R ^D is only one The ratio of structural units that are groups containing carbon-carbon double bonds (ratio in the total structural units of the polymer) is also shown in Table 1. These ratios are obtained by solving the “simultaneous equations” as described above, assuming that the ratio of the norbornene structural unit:maleic anhydride structural unit in the starting polymer 1 or 2 is 50:50 (molar ratio). I asked.
Note that in each polymer, the sum of these two ratios is less than 50 mol %. From this, it can be said that all of the maleic anhydride structural units in the polymer do not undergo ring opening, and some of them remain the structure represented by the formula (MA).

Here, from the values of the acid value and double bond equivalent of the polymers of Synthesis Examples, the polymers of Synthesis Examples 1 to 10 have the structural unit represented by the general formula (1) and R ^D is 2 or more. It is supported to include those that are groups containing a polymerizable carbon-carbon double bond. This will be described below.

Consider the ring opening of the MA unit in the starting polymer with a compound having a hydroxy group and a polymerizable carbon-carbon double bond.
When a compound having one molecule of a hydroxy group and a polymerizable carbon-carbon double bond opens one MA unit, one carboxyl group is generated as in the general formula (1).
Here, when the compound having a hydroxy group and a polymerizable carbon-carbon double bond is a monofunctional compound such as BHEA or 4-HBA, the number of C═C double bonds introduced is one. is there. That is, the ring-opening of one MA unit increases the number of carboxyl groups and the number of C=C double bonds by one.

On the other hand, when the compound having a hydroxy group and a polymerizable carbon-carbon double bond is a polyfunctional compound such as A-TMM-3L or A-9550, the carboxyl group is converted to a carboxyl group by ring opening of one MA unit. One, the C=C double bond increases by "2 or more".

Then, in two or more kinds of polymers having the same acid value (that is, the same amount of ring-opening of MA unit), the polymer obtained by ring-opening the MA unit with the polyfunctional compound is the monofunctional compound with the MA unit. The double bond equivalent is smaller than that of the polymer obtained by ring-opening.

Based on this, the above table is confirmed.
The acid values of the polymers of Synthesis Examples 1 to 10 (corresponding to the amount of carboxy groups produced by ring opening) are the same as those of the polymers of Comparative Synthesis Examples 2 and 3 (MA units of which are ring-opened with only a monofunctional compound). Same or smaller than the price. Nevertheless, the double bond equivalents of the polymers of Synthesis Examples 1-10 tend to be smaller than that of the polymers of Comparative Synthesis Examples 2 and 3 (ie the amount of C=C double bonds per unit mass of polymer). There are many). This indicates that the polymers of Synthesis Examples 1 to 10 have structures derived from polyfunctional compounds such as A-TMM-3L and A-9550 introduced therein.

From the synthetic procedure, it is clear that a structure derived from a polyfunctional compound such as A-TMM-3L or A-9550 is introduced into the raw material polymer. The relationship of the bond equivalent also supports the introduction of the structure derived from the polyfunctional compound.

<Evaluation>
[Development property evaluation] (polymer dissolution rate in TMAH aqueous solution)
The polymers of each synthesis example and comparative synthesis example were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid content concentration of 30% by mass.
Then, the solution was spin-coated on the wafer, PGMEA was dried, and prebaked at a temperature of 100° C. for 2 minutes to prepare a resin film having a thickness of about 2 μm.
This resin film, together with the wafer, was immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern disappeared, and dividing the film thickness by the time.

The developability was evaluated according to the following criteria.
Good (good): Dissolution rate of 500 nm/s or more Poor (bad): Dissolution rate of less than 500 nm/s

[Sensitivity evaluation] (2.0 mass% sodium carbonate aqueous solution)
First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration was 30% by mass.
Polymer (Synthesis Examples 1 to 10 or Comparative Synthesis Examples 1 to 3): 100 parts by mass Polyfunctional acrylate (dipentaerythritol oxaacrylate): 50 parts by mass Photopolymerization initiator (BASF Ingacure OXE01) : 5 parts by mass-Adhesion auxiliary agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass-Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

The obtained resin composition was spin-coated on a HMDS (Hexamethyldisilane)-treated 3 inch silicon wafer and baked on a hot plate at 100° C. for 120 seconds to give a thin film having a thickness of about 3.0 μm (±0.3 μm). I got A.
This thin film A was exposed to g+h+i rays with an exposure dose of 100 mJ/cm ^{2 using} a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. through a photomask having a gradation of a light blocking rate of 1 to 100%.
After the exposure, the thin film was developed (dipping the whole wafer) with a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds to obtain a thin film B exposed and developed at each exposure amount of 1 to 100 mJ/cm ² . ..

From the film thicknesses of the thin film A and the thin film B obtained by the above method, the residual film rate was calculated by the following formula.
Remaining film ratio (%)=(film thickness of thin film B at each exposure amount/film thickness of thin film A)×100
Then, the exposure amount at which the residual film ratio was 95% or more was evaluated as the sensitivity of each photosensitive resin composition according to the following criteria.
◎ (very good sensitivity): 20 mJ/cm ² or less ○ (good sensitivity): 21 to 50 mJ/cm ²
X (poor sensitivity): 51 mJ/cm ² or more

[Developability evaluation] (Addition: dissolution rate of polymer in Na ₂ CO ₃ aqueous solution)
In order to investigate the adaptability to various development processes, the developability when an aqueous sodium carbonate solution was used as the developer was also evaluated.
Specifically, among the photosensitive resin compositions prepared in the above [Sensitivity evaluation], the composition using any one of Synthesis Examples 1 to 10 was used as a developing solution containing 2.0% by mass of carbonic acid. Using a sodium aqueous solution, a resin film was prepared and the dissolution rate was measured in the same manner as in the above [Evaluation of developability]. And the following criteria evaluated.
◯ (good): Dissolution rate of 50 nm/s or more × (bad): Dissolution rate of less than 50 nm/s

The evaluation results are summarized below.

As shown in Table 2, in the evaluation using the polymers of Synthesis Examples 1 to 10, both the developability and the sensitivity were good. That is, both sensitivity and developability could be made compatible.
In particular, the developability was good not only when using the TMAH developer but also when using the sodium carbonate developer. It can be read that the photosensitive resin composition or polymer of the present embodiment has good solubility in various types of developing solutions.

On the other hand, in the evaluation using the polymer of Comparative Synthesis Example 1, the developability was poor. Despite the relatively large amount of polymerizable carbon-carbon double bond contained in the polymer (double bond equivalent: 286 g/mol), the acid value was small as less than 70 mgKOH/g, so sufficient development was performed. It is thought that the sex was not obtained.
Moreover, in the evaluation using the polymers of Comparative Synthesis Examples 2 and 3, the sensitivity was poor. It is considered that the double bonds with the density required for the sensitivity enhancement were not present in the polymer.

<Production of color filter>
Pigment dispersion NX-061 (manufactured by Dainichiseika Kogyo KK, green) was added to the photosensitive resin composition prepared in [Sensitivity evaluation] containing the polymer of Synthesis Example 1 in an appropriate amount for coloring. A photosensitive resin composition was prepared. A green color filter could be formed by forming a film on the substrate and performing exposure, alkali development treatment and the like.
Further, as the pigment dispersion liquid, NX-053 (blue), NX-032 (red) manufactured by the same company was used instead of NX-061, and a blue or red color filter could be formed.
By the way, these color filters had sufficient resistance to high temperatures that could be exposed during the device manufacturing process. It is believed that this is related to the fact that the polymer contains structural units having a cyclic hydrocarbon skeleton.

<Production of black matrix>
Black photosensitive material obtained by adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Kogyo Co., Ltd.) to the photosensitive resin composition prepared in [Sensitivity evaluation] containing the polymer of Synthesis Example 1. A resin composition was prepared. A black matrix could be formed by forming a film on the substrate and performing exposure, alkali development treatment and the like.
Incidentally, this black matrix had sufficient resistance to the high temperatures that can be exposed during the device manufacturing process. It is believed that this is related to the fact that the polymer contains structural units having a cyclic hydrocarbon skeleton.

This application claims the priority right based on Japanese Patent Application No. 2019-015715 filed on January 31, 2019, and incorporates all the disclosure thereof.

Claims

A photosensitive resin composition comprising a polymer having a first structural unit represented by the following general formula (1), an acid value of 70 to 300 mgKOH/g, and a double bond equivalent of 100 to 500 g/mol. ..

In the general formula (1), R D is a group containing a polymerizable carbon-carbon double bond.
The photosensitive resin composition according to claim 1, wherein
The photosensitive resin composition, wherein the first structural unit includes a structural unit in which R D is a group containing two or more polymerizable carbon-carbon double bonds.
The photosensitive resin composition according to claim 1 or 2, wherein
The first structural unit is a structural unit in which R D is a group containing two or more polymerizable carbon-carbon double bonds, and a structure in which R D is a group containing only one polymerizable carbon-carbon double bond. A photosensitive resin composition comprising a unit.
The photosensitive resin composition according to any one of claims 1 to 3,
The photosensitive resin composition, wherein the polymer further contains a second structural unit represented by the following formula (MA).
The photosensitive resin composition according to any one of claims 1 to 4, wherein:
The photosensitive resin composition, wherein the polymer further contains a structural unit having a cyclic hydrocarbon skeleton.
The photosensitive resin composition according to any one of claims 1 to 5, wherein
The photosensitive resin composition, wherein the ratio of the first structural unit in all structural units of the polymer is 10 to 40 mol %.
The photosensitive resin composition according to any one of claims 1 to 6, wherein:
The photosensitive resin composition, wherein the polymer has a weight average molecular weight of 6,000 to 25,000.
The photosensitive resin composition according to any one of claims 1 to 7,
A photosensitive resin composition further containing a colorant.
The photosensitive resin composition according to any one of claims 1 to 7,
Further, a photosensitive resin composition containing a light shielding agent.
A polymer having the first structural unit represented by the following general formula (1), having an acid value of 70 to 300 mgKOH/g, and having a double bond equivalent of 100 to 500 g/mol.

In the general formula (1), R D is a group containing a polymerizable carbon-carbon double bond.
The polymer according to claim 10, wherein
The first structural unit is a polymer containing a structural unit in which R D is a group containing two or more polymerizable carbon-carbon double bonds.
The polymer according to claim 10 or 11, wherein
The first structural unit is a structural unit in which R D is a group containing two or more polymerizable carbon-carbon double bonds, and a structure in which R D is a group containing only one polymerizable carbon-carbon double bond. A polymer containing units.
The photosensitive resin composition according to any one of claims 10 to 12,
Further, a polymer containing a second structural unit represented by the following formula (MA).
The polymer according to any one of claims 10 to 13, wherein
Further, a polymer containing a structural unit having a cyclic hydrocarbon skeleton.
The polymer according to any one of claims 10 to 14, wherein
A polymer in which the ratio of the first structural unit in all structural units is 10 to 40 mol %.
The polymer according to any one of claims 10 to 15, wherein
A polymer having a weight average molecular weight of 6,000 to 25,000.
A pattern obtained using the photosensitive resin composition according to any one of claims 1 to 7.
A color filter obtained by using the photosensitive resin composition according to claim 8.
A display device comprising the color filter according to claim 18.
An image pickup device comprising the color filter according to claim 18.
A black matrix obtained by using the photosensitive resin composition according to claim 9.
A display device comprising the black matrix according to claim 21.
An image pickup device comprising the black matrix according to claim 21.