JP2021120741A - Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device, and imaging element - Google Patents

Abstract

To provide a photosensitive resin composition that achieves both sensitivity and developability.SOLUTION: A photosensitive resin composition contains 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. A polymer has a first structural unit represented by general formula (1), and has 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), RD is a group containing a polymeric carbon-carbon double bond.SELECTED DRAWING: Figure 1

Description

The present invention relates to photosensitive resin compositions, polymers, patterns, color filters, black matrices, display devices and image sensors.

A display device (liquid crystal display or the like) or an image sensor (CCD, CMOS, etc.) usually includes a color filter or a black matrix.
A photosensitive resin composition is often used for forming a color filter or a black matrix. Specifically, a photosensitive resin film is formed on a substrate with 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. NS.

Patent Document 1 contains an acid group, a polymerizable unsaturated group and a blocked isocyanate group in the molecule, has an acid value of 20 to 300 mgKOH / g, and has an unsaturated group equivalent of 100 to 4,000 g / mol. There is described a curable polymer having a blocked isocyanate group equivalent of 400-6,000 g / mol. It is also described that the curable polymer is used to form a color filter.

Patent Document 2 describes that a black matrix is formed 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 describes in a copolymer obtained by radically polymerizing an ethylenically unsaturated monomer having a formula of 70 to 120 having no carboxyl group and an ethylenically unsaturated monomer containing a carboxyl group-containing ethylenically unsaturated monomer. A photosensitive resin obtained by reacting 1 mol of a carboxyl group with 0.2 to 0.9 mol of an epoxy group in an epoxy group-containing ethylenically unsaturated monomer is described. Further, a photosensitive composition containing the photosensitive resin is described. Further, it is described that a color filter is formed by using this photosensitive composition.
In Patent Document 3, the acid value of the photosensitive resin is preferably described as 20 to 200 mgKOH / g. Further, the double bond equivalent of the photosensitive resin is preferably described as 300 to 1000.

In Patent Document 4, a carboxyl group-containing polymer represented by a specific general formula is reacted with (i) a compound having a group that reacts with a carboxylic acid and an ethylenically unsaturated group, or (ii) a carboxylic acid. Described is an alkali-soluble resin obtained by reacting a compound having a group and a silicon-based functional group, and a photosensitive resin composition containing the alkali-soluble resin. Further, it is described that a color filter is formed by 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 Japanese Unexamined Patent Publication No. 2015-197619 Japanese Unexamined Patent Publication No. 2011-33951 Japanese Unexamined Patent Publication No. 2007-264433

When a pattern is formed using a photosensitive resin composition, particularly a negative photosensitive resin composition, the exposed portion is easily photocured (that is, the sensitivity) and the unexposed portion is easily dissolved in a developing solution. (Developability) tends to be in a trade-off relationship.
In particular, recently, against the background of further complexity and miniaturization of liquid crystal display devices and solid-state image sensors, it is required to achieve both sensitivity and developability at a high level.

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

As a result of diligent studies, the present inventors have completed the inventions provided below.

According to the present invention, the following are provided.

一般式（１）中、Ｒ^Ｄは、重合性炭素−炭素二重結合を含む基である。
２．
１．に記載の感光性樹脂組成物であって、
前記第一構造単位は、Ｒ^Ｄが２以上の重合性炭素−炭素二重結合を含む基である構造単位を含む、感光性樹脂組成物。
３．
１．または２．に記載の感光性樹脂組成物であって、
前記第一構造単位は、Ｒ^Ｄが２以上の重合性炭素−炭素二重結合を含む基である構造単位と、Ｒ^Ｄが１のみの重合性炭素−炭素二重結合を含む基である構造単位とを含む、感光性樹脂組成物。
４．
１．〜３．のいずれか１つに記載の感光性樹脂組成物であって、
前記ポリマーが、さらに、以下式（ＭＡ）で表される第二構造単位を含む、感光性樹脂組成物。

５．
１．〜４．のいずれか１つに記載の感光性樹脂組成物であって、
前記ポリマーが、さらに、環状炭化水素骨格を有する構造単位を含む、感光性樹脂組成物。
６．
１．〜５．のいずれか１つに記載の感光性樹脂組成物であって、
前記ポリマーの全構造単位中の前記第一構造単位の比率が、１０〜４０ｍｏｌ％である、感光性樹脂組成物。
７．
１．〜６．のいずれか１つに記載の感光性樹脂組成物であって、
前記ポリマーの重量平均分子量が、６，０００〜２５，０００である、感光性樹脂組成物。
８．
１．〜７．のいずれか１つに記載の感光性樹脂組成物であって、
さらに着色剤を含む感光性樹脂組成物。
９．
１．〜７．のいずれか１つに記載の感光性樹脂組成物であって、
さらに遮光剤を含む感光性樹脂組成物。
１０．
以下一般式（１）で表される第一構造単位を有し、酸価が７０〜３００ｍｇＫＯＨ／ｇであり、二重結合当量が１００〜５００ｇ／ｍｏｌであるポリマー。

一般式（１）中、Ｒ^Ｄは、重合性炭素−炭素二重結合を含む基である。
１１．
１０．に記載のポリマーであって、
前記第一構造単位は、Ｒ^Ｄが２以上の重合性炭素−炭素二重結合を含む基である構造単位を含むポリマー。
１２．
１０．または１１．に記載のポリマーであって、
前記第一構造単位は、Ｒ^Ｄが２以上の重合性炭素−炭素二重結合を含む基である構造単位と、Ｒ^Ｄが１のみの重合性炭素−炭素二重結合を含む基である構造単位とを含むポリマー。
１３．
１０．〜１２．のいずれか１つに記載の感光性樹脂組成物であって、
さらに、以下式（ＭＡ）で表される第二構造単位を含むポリマー。

１４．
１０．〜１３．のいずれか１つに記載のポリマーであって、
さらに、環状炭化水素骨格を有する構造単位を含むポリマー。
１５．
１０．〜１４．のいずれか１つに記載のポリマーであって、
全構造単位中の前記第一構造単位の比率が、１０〜４０ｍｏｌ％であるポリマー。
１６．
１０．〜１５．のいずれか１つに記載のポリマーであって、
重量平均分子量が、６，０００〜２５，０００であるポリマー。
１７．
１．〜７．のいずれか１つに記載の感光性樹脂組成物を用いて得られるパターン。
１８．
８．に記載の感光性樹脂組成物を用いて得られるカラーフィルタ。
１９．
１８．に記載のカラーフィルタを備える表示装置。
２０．
１８．に記載のカラーフィルタを備える撮像素子。
２１．
９．に記載の感光性樹脂組成物を用いて得られるブラックマトリクス。
２２．
２１．に記載のブラックマトリクスを備える表示装置。
２３．
２１．に記載のブラックマトリクスを備える撮像素子。 1. 1.
A photosensitive resin composition containing 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), ^RD is a group containing a polymerizable carbon-carbon double bond.
2.
1. 1. The photosensitive resin composition according to the above.
The first structural unit is a photosensitive resin composition containing a structural unit which is a group containing a polymerizable carbon-carbon double bond having an ^{RD of 2 or more.}
3. 3.
1. 1. Or 2. The photosensitive resin composition according to the above.
The first structural unit is a structural unit having a ^RD of 2 or more and containing a polymerizable carbon-carbon double bond, and a structure having an ^RD of only 1 containing a polymerizable carbon-carbon double bond. A photosensitive resin composition comprising a unit.
4.
1. 1. ~ 3. The photosensitive resin composition according to any one of the above.
A photosensitive resin composition in which the polymer further contains a second structural unit represented by the following formula (MA).

5.
1. 1. ~ 4. The photosensitive resin composition according to any one of the above.
A photosensitive resin composition, wherein the polymer further comprises a structural unit having a cyclic hydrocarbon skeleton.
6.
1. 1. ~ 5. The photosensitive resin composition according to any one of the above.
A photosensitive resin composition in which the ratio of the first structural unit to the total structural unit of the polymer is 10 to 40 mol%.
7.
1. 1. ~ 6. The photosensitive resin composition according to any one of the above.
A photosensitive resin composition having a weight average molecular weight of the polymer of 6,000 to 25,000.
8.
1. 1. ~ 7. The photosensitive resin composition according to any one of the above.
A photosensitive resin composition further containing a colorant.
9.
1. 1. ~ 7. The photosensitive resin composition according to any one of the above.
A photosensitive resin composition further containing a light-shielding agent.
10.
A polymer having a 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), ^RD is a group containing a polymerizable carbon-carbon double bond.
11.
10. The polymer described in
The first structural unit is a ^{polymer containing a structural unit in which RD} is a group containing a polymerizable carbon-carbon double bond of 2 or more.
12.
10. Or 11. The polymer described in
The first structural unit is a structural unit in which ^RD is a group containing two or more polymerizable carbon-carbon double bonds, and a structure in which ^RD is a group containing only one polymerizable carbon-carbon double bond. Polymers containing units.
13.
10. ~ 12. The photosensitive resin composition according to any one of the above.
Further, a polymer containing a second structural unit represented by the following formula (MA).

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

According to the present invention, there is provided a photosensitive resin composition having both sensitivity and developability. Also provided are polymers suitable for the production of such photosensitive resin compositions.

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

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.
In order to avoid complication, when there are a plurality of the same components in the same drawing, only one of them may be coded and all of them may not be coded.
The drawings are for illustration purposes only. The shape and dimensional ratio of each member in the drawing do not necessarily correspond to the actual article.

In the present specification, the "double bond" of the "double bond equivalent" refers to a polymerizable carbon-carbon double bond.
In the present specification, the term "abbreviation" means to include a range in consideration of manufacturing tolerances, assembly variations, etc., unless otherwise specified explicitly.
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% by mass" means "1% by mass or more and 5% by mass or less".

In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The notation "(meth) acrylic" herein represents a concept that includes both acrylic and methacryl. The same applies to similar notations such as "(meth) acrylate".
Unless otherwise specified, the term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, the "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment has a 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. Contains polymers that are.
In the general formula (1), ^RD is a group containing a polymerizable carbon-carbon double bond.

By producing a photosensitive resin composition using the above-mentioned polymer, it is possible to obtain a photosensitive resin composition having both sensitivity and developability. The reason can be explained as follows.
It should be noted that 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 (RD 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" of the amount of the polymerizable group and the amount of the carboxy group in the polymer to a large value (others such as (meth) acrylic resin). Such a design is considered difficult with the resin of.). This is convenient in that it enhances the developability while increasing the sensitivity.

By designing the acid value of the polymer as a whole to 70 to 300 mgKOH / g and the double bond equivalent to 100 to 500 g / mol, it is possible to achieve both sensitivity and developability 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 high, the exposed part is likely to dissolve during development with an alkaline developer, which may increase the amount of exposure required for photocuring or cause the pattern shape to become insufficient. There is. Therefore, in the present embodiment, the upper limit of the acid value is set to 300 mgKOH / g.
Also, if the double bond equivalent is too small (ie, the density of the double bonds in the polymer is too high), the unexposed and underexposed areas tend to be difficult to dissolve during development with an alkaline developer. , Residual film tends to be generated during development. On the other hand, if the double bond equivalent is too small, the molecular weight is excessively increased due to cross-linking, and there is a concern that the solubility is excessively lowered. Therefore, in the present embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

The acid value of the polymer is 70-300 mgKOH / g, preferably 80-200 mgKOH / g.
The double bond equivalent of the polymer is 100-500 g / mol, preferably 200-470 g / mol.
By adjusting the acid value and / or double bond equivalent of the polymer, both sensitivity and developability can be achieved at an even higher level.

As a reminder, the acid value and double bond equivalent can be determined by spectral measurement or the like. For example, it can be obtained by the following procedure (more specifically, refer to the examples).
(1) From the ¹ H-NMR chart of the polymer, the area (integrated value) of the peak corresponding to the hydrogen atom of the carboxy group and the hydrogen atom in the vicinity of the polymerizable carbon-carbon double bond is obtained.
(2) For the area obtained in (1), the amount of carboxy group and the amount of carbon-carbon double bond are obtained from the area of the peak derived from the standard substance.
(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 a double bond equivalent (g / mol).

Appropriately design the ratio of structural units represented by the general formula (1) in the polymer, the structure of ^{RD in} the general formula (1), the number of polymerizable carbon-carbon double bonds contained in ^{RD, and the like.} Therefore, the acid value and double bond equivalent of the polymer can be set to appropriate values.

The components and the like 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 ranging from ~ 500 g / mol. In the general formula (1), ^RD 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 which is a group containing a polymerizable carbon-carbon double bond having an ^{RD of 2 or more.} In other words, some or all R ^D of the structural unit represented by the general formula in the polymer (1), preferably, 2 or more polymerizable carbon - is a group containing a carbon double bond.
When the ^RD contains two or more polymerizable carbon-carbon double bonds, the number of polymerizable carbon-carbon double bonds in the ^{RD is preferably 2-6, more preferably 2-5, even more preferably.} It is 3 to 5. ^{By adjusting the number of polymerizable double bonds contained in RD} , both sensitivity and developability can be achieved at a higher level.

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

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

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

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

When X ¹ is a group represented by -Z-X- (Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), an alkylene group having 1 to 6 carbon atoms of X is used. 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, for specific embodiments thereof are 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, and more preferably 100 or less.
X ² is, for example, a group obtained by removing k + 1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing k + 1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon.
In another aspect, X ² may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure, a group containing a heterocyclic structure (for example, an isocyanuric acid structure), and the like.

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

Specific embodiments, preferred embodiments, and the like of R, k, X ¹ and X ² are the same as those described in the general formula (1b).
^{Examples of the divalent organic group having 1 to 6} carbon atoms of X ³ and X 6 include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. Can be done. 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 X ⁴ and X ^5, may be mentioned 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 ^RD is a group containing two or more polymerizable carbon-carbon double bonds and a structural unit in which ^RD is a group containing only one polymerizable carbon-carbon double bond. And are preferably included. In other words, preferably, among the structural units represented by the general formula (1) in ^{the polymer, RD} in some structural units is a group containing two or more polymerizable carbon-carbon double bonds. Among the structural units represented by the general formula (1) in ^{the polymer, RD} 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 easy to obtain better developability while increasing the sensitivity.

^{The specific embodiment of the "structural unit in which the RD} is a group containing two or more polymerizable carbon-carbon double bonds" is as described above (in the general formula (1), the ^RD is the general formula (1b). ) Or (for example, when it is a group represented by (1c)).

In the "structural unit which is a group containing a polymerizable carbon-carbon double bond having only 1 ^RD ", the polymerizable double bond is preferably present at the end of the ^RD. In addition, ^RD contains one (meth) acryloyl group as one embodiment. From the viewpoint of further improving the sensitivity, the (meth) acryloyl group is preferably an acryloyl group. More specifically, ^RD can be a group represented by the following general formula (2a).

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

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

It is more preferably a divalent organic group X ^10, the total linear alkylene group having a carbon number of 3-6. 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.

A divalent organic group of X ¹⁰ (e.g. 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 the alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group and the like.

The ratio of the first structural unit to the total structural unit of the polymer is preferably 10 to 40 mol%, more preferably 15 to 35 mol%.
Further, the polymer contains, as the first structural unit, a structural unit which is a group containing a polymerizable carbon-carbon double bond having an ^{RD of 2 or more, and a polymerizable carbon-carbon double bond having an RD} of only 1. When both of the structural units that are the groups are included, the molar ratio of the former: 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 sensitivity and developability at a higher level.
Here, the molar ratio of the former: the latter can be obtained, for example, as follows.
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). Further, 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 as X 1} + X ₂ = C (assuming that the polymer does not contain any other structural unit containing a carboxyl group).
Further, the amount of the polymerizable carbon-carbon double bond can _{be written as n · X 1} + X ₂ = D (assuming that the polymer does not contain any other structural unit containing the polymerizable double bond).
C and D can be known from the peak area obtained by NMR measurement and the like. Further, n is determined by the chemical structure of the raw material. Therefore, the former: the latter molar ratio can be obtained by solving these two equations as simultaneous equations for the unknowns X ₁ and X _2.
Further, 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), the molecular weight of the monomer which is the element of each structural unit contained in the raw material polymer, etc. The ratio of the first structural unit (if there are a plurality of first structural units, the total) can be obtained from all the structural units of the polymer.

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

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

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

The organic groups having 1 to 30 carbon atoms constituting R ₁₄ , R ₁₅ and R ₁₆ may contain any one or more of O, N, S, P and Si in the structure. Further, _{the organic groups constituting R 14} , R ₁₅ and R ₁₆ can be free of acidic functional groups. 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 alkalil 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 alkaline group include a tolyl group, a xylyl group and the like.
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, an oxetanyl group and the like.

In these alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkalinel group, cycloalkyl group, and heterocyclic group, one or more hydrogen atoms may be substituted with halogen atoms. 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 halogen atoms 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 characteristics of the cured film when the photosensitive resin composition is cured can be improved.

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

Cyclic olefin monomer. Specifically, norbornene, norbornene, bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5- Butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-methyl-4) -Pentenyl) -A monomer having a norbornene skeleton or a norbornene skeleton, such as -2-norbornene, 5-ethylidene-2 norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene.

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, A monomer having a triene structure, such as 5,9-cyclododecatriene and cis-cis-cis-1,5,9-cyclododecatriene.
Monomer having a styrene skeleton such as styrene, vinyltoluene, hydroxystyrene, acetoxystyrene, α-methylstyrene and the like.

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

As the structural unit having a cyclic hydrocarbon skeleton, a structural unit derived from a cyclic olefin monomer is preferable, and a structural unit derived from a monomer having a norbornene skeleton or a norbornadiene skeleton is more preferable. 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 independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.
a ₁ is 0, 1 or 2.

^{The organic groups having 1 to 30 carbon atoms of 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 alkalil group. , Cycloalkyl group, alkoxy group, heterocyclic group, carboxyl group and the like.

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

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

When the polymer contains a structural unit having a cyclic hydrocarbon skeleton, the amount thereof is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, based on the total structural units of the polymer. By appropriately adjusting this ratio, it is easy to obtain additional effects (for example, improvement in heat resistance and mechanical properties when a cured film is formed) while achieving both sensitivity and developability.
By the way, from the viewpoint of overall performance, cost, etc., the polymer is different from the first structural unit as an essential structural unit, the second structural unit as an arbitrary structural unit, and the structural unit having a cyclic hydrocarbon skeleton. It preferably does not contain or, if any, a small amount of "other structural units". 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 alkaline developer, 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 even more preferably 1.0 to 3.0. .. By appropriately 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 for preparing a raw material polymer containing at least the structural unit represented by the above formula (MA), and
-A polymer can be produced by a reaction step of reacting a raw material polymer with a compound having a hydroxy group and a polymerizable carbon-carbon double bond in the presence of a basic catalyst.

Hereinafter, a method for producing (synthesizing) a polymer by the above-mentioned preparation step and reaction step will be described more specifically. The description will be made by synthesizing a polymer containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (NB) as an example, but this loses the generality of the polymer production method. It's 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 also 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 of the general formula (NB-m) are the same as those of the general formula (NB). The same applies to the preferred embodiment.

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

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

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

The monomer represented by the general formula (NB-m), maleic anhydride and the polymerization initiator are dissolved in a solvent and charged into a reaction vessel, and then heated to allow the addition polymerization to proceed. 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 the reaction vessel is preferably 0.5: 1 to 1: 0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1: 1.
By the above steps, a "raw material polymer" can be obtained.
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 copolymer or an alternating copolymer (generally, maleic anhydride is known as a monomer having strong alternating copolymerization).

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

-Reaction step The formula (MA) contained in the raw material polymer is obtained 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. ) Is opened. As a result, the structural unit of the general formula (1) is formed.

More specifically, first, a polymer solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared.
Examples of the organic solvent that can be used here include single solvents or mixed solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF). 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 mixed appropriately to obtain 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 an ^{RD of 2 or more in the general formula (1) is contained in the polymer.} A structural unit that is a group containing the above can be introduced.
On the other hand, by using a compound (monofunctional compound) containing only one (meth) acryloyl group and a hydroxy group, a polymerizable carbon-carbon double having only one ^{RD in the general formula (1) is contained in the polymer.} Structural units that are groups containing double bonds can be introduced.
By using both the polyfunctional compound and the monofunctional compound, the first structural unit is a structural unit having an ^RD of 2 or more and a group containing a polymerizable carbon-carbon double bond, and an ^RD of only 1. Both with structural units that are groups containing polymerizable carbon-carbon double bonds can be introduced into the polymer. However, in terms of steric hindrance, monofunctional compounds tend to react with polymers more easily than polyfunctional compounds, so in the reaction process, monofunctional compounds are not charged into the reaction system from the beginning, but "addition". It is preferable to do so.

As "a compound containing two or more (meth) acryloyl groups and a hydroxy group", specifically, it is represented by a compound represented by the following general formula (1 bm) or a following general formula (1 cm). 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 (1 cm) are the same as those in the general formula (1c).

Compounds containing two or more (meth) acryloyl groups and a hydroxy group, which can be preferably used, are shown below. It should be noted that a compound having a part or all of the acryloyl group of the compound shown below as a (meth) acryloyl group (or vice versa) can also be used.

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 (2am).
In the general formula (2am), ^{the definitions and specific embodiments of X 10} and R are the same as those in the general formula (2a).

Specific examples of the compound represented by the general formula (2am) include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, and 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid and the like. Can be done.

After the reaction step, the reaction is stopped by diluting the reaction solution with an organic solvent and / or adding an acid to neutralize 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 completely ring-opened, and the final The structure of the formula (MA) will be included in the polymer.
Further, in the reaction step, water, alcohol, or other suitable substances are reacted with the maleic anhydride structure in the raw material polymer to cause the general formulas (a2-1), (a2-2), or (a2-3). The structural units indicated by can be introduced into the polymer.

Further, it is preferable to appropriately perform the following steps in order to remove unnecessary components other than the desired polymer.

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

To the organic solution of the obtained polymer, an excess amount of toluene is added to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is washed with toluene several more times.
Further, in order to remove formic acid and the basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (about 3 times).
A high-purity polymer can be obtained by drying the polymer powder washed with ion-exchanged water at, for example, 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 may be, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, or the like.
The photopolymerization initiator typically generates an active chemical species by irradiation with ultraviolet light, more specifically, g-ray, i-ray, or the like.

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-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4- (2) -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-Methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- 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-ethoxycarbokynylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine ..
2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole-based 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, A biimidazole-based compound such as 2'-biimidazole.
1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole- 3-Il] An oxime ester compound such as etanone oxime.
Titanocene compounds such as bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-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 contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators.
The amount of the photopolymerization initiator used is, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polymer.

(solvent)
The photosensitive resin composition of the present embodiment typically contains a solvent. As a result, a uniform photosensitive resin film can be formed on the surfaces of various substrates.
An organic solvent is preferably used as the solvent. Specifically, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent and the like can be used.

Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-. Examples thereof include n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof.

The amount of the solvent used is not particularly limited. For example, it is used in an amount such 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 the present embodiment may contain a cross-linking agent.
The cross-linking agent is not particularly limited as long as it can cross-link the polymer by the action of the active chemical species generated from the photopolymerization initiator (the one capable of chemically bonding to the polymer).
The cross-linking agent may not only chemically bond with the polymer, but may react with each other to form a bond.

The cross-linking agent is, for example, a polyfunctional compound having two or more polymerizable double bonds in one molecule, and a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups in one molecule. (However, the cross-linking agent does not correspond to the above-mentioned polymer). It is preferable to use a cross-linking agent having the same kind of cross-linking group as the cross-linking group (polymerizable double bond) of the polymer in terms of uniform curability and further improvement of sensitivity.
There is no particular upper limit on the number of functionals (the number of polymerizable double bonds) per molecule of the cross-linking agent, but it 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 Falkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane 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 trimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (Meta) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added dimethylolpropane 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, trimetyl propanetrivinyl ether, ditri Methylolpropan tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropanetrivinyl ether, ethylene oxide-added ditrimethylolpropanetetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Polyfunctional vinyl ethers such as added dipentaerythritol hexavinyl ether.

2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4 (meth) acrylate − Vinyloxybutyl, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, ( Contains vinyl ether groups (meth) such as p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate. Acrylic acid esters.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol Falkylene oxide diallyl ether, trimethyl propantriallyl ether, Ditrimethylol propanetetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol propanetriallyl ether, ethylene oxide-added ditrimethylol propanetetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether.

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

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

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

(Colorant)
The photosensitive resin composition of the present 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.
Organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. Pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, dye lake pigments and the like can be used.
Inorganic pigments include white / extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (chrome yellow, cadmium, chromium vermillion, nickel titanium, chromium titanium). , Yellow iron oxide, red iron oxide, zinc chromate, lead tan, ultramarine, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), bright material pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments ( Zinc oxide, strontium sulfide, strontium aluminate, etc.) can be used.

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

As the colorant (particularly pigment), one having an appropriate average particle size can be used depending on the purpose and application. In particular, when transparency such as a color filter is required, a small average particle size of 0.1 μm or less is preferable. On the other hand, when a concealing property such as a paint 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, etc., depending on the purpose and application.

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

(Shading agent)
The photosensitive resin composition of the present embodiment may contain 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, a black pigment such as carbon black, bone black, graphite, iron black, or titanium black can be used as a 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 achieving both light-shielding performance and dispersion stability of the light-shielding agent, the photosensitive resin composition is non-volatile. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and further preferably 10 to 50% by mass with respect to the entire component (component excluding the solvent).

(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 the components that may be contained include fillers, binder resins other than the above-mentioned polymers, polyfunctional (meth) acrylate compounds, acid generators, heat-resistant improvers, development aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, and the like. Antioxidants, matting agents, defoaming agents, leveling agents, surfactants, antistatic agents, dispersants, slip agents, surface modifiers, rocking agents, silane coupling agents, polyvalent phenol compounds, etc. Be done.

<Pattern, color filter, black matrix, display device, image sensor, and manufacturing method of display device or image sensor>
A film can be formed 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. Further, 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 image pickup device (typically a solid-state image pickup device) including a color filter and / or a black matrix can be manufactured.

A typical procedure for forming a pattern is described below.

-Formation of a photosensitive resin film For example, the photosensitive resin composition of the present embodiment is applied onto an arbitrary substrate and dried if necessary. As a result, 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, and the like can be mentioned.
The substrate may be an unprocessed substrate or a substrate on which electrodes and elements are formed on the surface. The substrate may be surface-treated to improve adhesiveness.
The method of applying the photosensitive resin composition is not particularly limited. The coating can be performed by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

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

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

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

After the exposure, the photosensitive resin film may be heated again if necessary (heating after exposure: Post Exposure Bake). The 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 from the process aspect.

-Development By developing the exposed photosensitive resin film with an appropriate developing solution, a pattern can be obtained and a substrate having the pattern can be manufactured.
In the developing step, development can be carried out using a suitable developer, for example, by a method such as a dipping method, a paddle method, or a rotary spray method. By development, the exposed portion (in the case of the positive type) or the unexposed portion (in the case of the negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained. When the photosensitive resin composition of the present 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, and (iii). Examples thereof include an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Specific examples of the organic solvent include a ketone solvent such as cyclopentanone, an ester solvent such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and an ether solvent such as propylene glycol monomethyl ether.
The developer may contain, for example, 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 a 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.

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

Further, the obtained pattern may be heated to be sufficiently cured. The heating temperature is typically 150-400 ° C, preferably 160-300 ° C, more preferably 200-250 ° C. The heating time is not particularly limited, but is, for example, in the range of 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature-increasing oven in which a temperature program can be set, or the like. The atmospheric gas for the heat treatment may be air or an inert gas such as nitrogen or argon. Further, it may be heated under reduced pressure.

By the above steps, a pattern can be obtained / a substrate having the pattern can be manufactured. More specifically, a color filter can be obtained by using a photosensitive resin composition containing a colorant. In addition, 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. Further, a protective film 13 and a transparent electrode layer 14 are provided above the black matrix 11 and the color filter 12.
The substrate 10 is usually made of a material that allows light to pass through. For example, it is composed of any of glass, polyester, polycarbonate, polyolefin, polysulfone, a polymer of cyclic olefin, and the like.
The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical solution treatment, or the like.
The substrate 10 is made of, for example, glass.

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

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved 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 examples.

The compounds used in the examples may be indicated by the following abbreviations or trade names.
-MA: Maleic anhydride-NB: 2-Norbornene-MEK: Methyl ethyl ketone-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 chromatograph measurement is about 55% (manufactured by Shin-Nakamura Chemical Industry 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 chromatograph measurement is about 57% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

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

<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 material polymer 1)
Maleic anhydride 353.02 g (3.6 mol), 2-norbornene 338.94 g (3.6 mol) and dimethyl-2,2'-azobis in an appropriately sized reaction vessel equipped with a stirrer and condenser. 33.16 g (0.144 mol) of (2-methylpropionate) was weighed and added. These were dissolved in a mixed solvent consisting of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.
The solution is aerated with nitrogen for 30 minutes to remove oxygen, then heated at a temperature of 65 ° C. for 1.5 hours with stirring, and then heated at 80 ° C. for 6 hours to obtain maleic anhydride. And 2-norbornene were polymerized to prepare a polymerization solution.
The polymerization solution obtained above was added dropwise to 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum dried at a temperature of 120 ° C. to obtain 607.5 g of a polymer (raw material polymer 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 7000, and the degree of polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.82. there were.

(Raw material polymer 2)
Maleic anhydride 353.02 g (3.6 mol), 2-norbornene 338.94 g (3.6 mol) and dimethyl-2,2'-azobis in an appropriately sized reaction vessel equipped with a stirrer and condenser. 33.16 g (0.144 mol) of (2-methylpropionate) was weighed and added. These were dissolved in a mixed solvent consisting of 2654.9 g of MEK and 113.0 g of toluene to prepare a solution.
The solution is aerated with nitrogen for 30 minutes to remove oxygen, then heated at a temperature of 65 ° C. for 1.5 hours with stirring, and then heated at 80 ° C. for 6 hours to obtain 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 the white solid. The obtained white solid was vacuum-dried at a temperature of 120 ° C. to obtain 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.
As a result of GPC measurement of the obtained polymer, the weight average molecular weight Mw was 4300, and the degree of 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 obtained by ring-opening the MA-derived structural unit of the raw material polymer 1 (hereinafter, also simply referred to as “MA unit”) with a hydroxyl group-containing trifunctional acrylate was prepared. The details will be described below.
First, 64.15 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 96.85 g of A-TMM-3L (addition amount as the above-mentioned two kinds mixture, the same applies hereinafter) was added to this solution, and then 9.00 g (0.089 mol) of triethylamine was added, and the temperature was 70. The reaction was carried out at ° C. for 6 hours to prepare a reaction solution.

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

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

(Comparative Synthesis Example 2)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened only with a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 55.50 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Then, 22.65 g (0.195 mol) of BHEA was added to this solution, 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 solution of formic acid. Then, the solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration and further washed with pure water.
As described above, 27.21 g of the polymer was obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer only with BHEA.

(Comparative Synthesis Example 3)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened only with a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 55.5 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Then, 28.11 g (0.195 mol) of 4-HBA was added to this solution, 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. Made.
The aqueous phase was removed from the reaction solution by treating the obtained reaction solution with an aqueous solution of formic acid. Then, the solution was poured into a large amount of pure water to precipitate the polymer. The obtained polymer was collected by filtration and further washed with pure water.
From the above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with 4-HBA to obtain 26.54 g of the polymer.

(Synthesis Example 1)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 67.72 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Then, 58.12 g of A-TMM-3L was added to this solution, 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 in the same manner as in Comparative Synthesis Example 1.
From the above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and BHEA to obtain 22.21 g of the polymer.

(Synthesis Example 2)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 49.41 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, 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 in the same manner as in Comparative Synthesis Example 1.
As described above, 22.53 g of the polymer was obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA.

(Synthesis Example 3)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 49.51 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, and then 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 in the same manner as in Comparative Synthesis Example 1.
As described above, 22.10 g of the polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA was obtained.

(Synthesis Example 4)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 49.86 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, 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, 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 in the same manner as in Comparative Synthesis Example 1.
As described above, 24.64 g of the polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and 4-HBA was obtained.

(Synthesis Example 5)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 47.35 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, and then 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 in the same manner as in Comparative Synthesis Example 1.
From the above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3L and 4-HBA to obtain 25.77 g of the polymer.

(Synthesis Example 6)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing pentafunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 71.03 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 43.78 g of A-9550 was added to this solution, 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 the mixture was 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 in the same manner as in Comparative Synthesis Example 1.
From the above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-9550 and BHEA to obtain 25.51 g of the polymer.

(Synthesis Example 7)
A polymer in which the MA unit of the raw material polymer 2 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 49.41 g of MEK was added to 230 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3LM-N was added to this solution, 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 in the same manner as in Comparative Synthesis Example 1.
As described above, 21.11 g of the polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA was obtained.

(Synthesis Example 8)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 50.60 g of MEK was added to 130 g of the raw material polymer (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, 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 in the same manner as in Comparative Synthesis Example 1.
From the above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3LM-N and BHEA to obtain 20.66 g of the polymer.

(Synthesis Example 9)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 46.60 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 7.75 g of A-TMM-3L was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 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 in the same manner as in Comparative Synthesis Example 1.
As described above, 21.22 g of the polymer was obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA.

(Synthesis Example 10)
A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. The details will be described below.
First, 54.13 g of MEK was added to 130 g of the raw material polymer (0.156 mol in terms of MA) to prepare a solution. Next, 29.06 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 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 in the same manner as in Comparative Synthesis Example 1.
From the above, the structural unit derived from maleic anhydride in the raw material polymer was ring-opened with A-TMM-3LM-N and BHEA to obtain 24.54 g of the polymer.

<GPC measurement>
For each polymer, the weight average molecular weight and the degree of dispersion (weight average molecular weight / number average molecular weight) were determined by GPC measurement using polystyrene as a standard substance.
By GPC measurement, the disappearance of the peak of the acrylate compound (BHEA, 4-HBA, A-TMM-3L, A-TMM-3LM-N, A-9550) was confirmed. That is, in the polymers of each synthetic example and the comparative synthetic example, the acrylate that has not reacted with the MA unit of the raw material polymer and the acrylate compound that does not react with the MA unit in the first place (acrylate that does not contain a hydroxyl group) are sufficiently removed. confirmed.

<NMR measurement of polymer>
^{1 1} H-NMR measurement was carried out for the polymers of each synthetic example and comparative synthetic example.
¹ H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer based on the integrated value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, which is the standard in 1 H-NMR measurement. The amount of carboxyl group was obtained 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 polymer unit mass.

Similarly, based on the integrated value of the peak of 4H phenyl group of dimethyl terephthalate (around 8.1 ppm), a peak of 3H acryloyl moieties in the polymer _{(CH 2 = CH-COO-)} (6. The amount of C = C double bond was determined from the integrated value (around 2 ppm), and the double bond equivalent (polymer mass per 1 mol of C = 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 bonds per polymer unit mass.

Table 1 summarizes 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 for the polymers of each synthetic example and the comparative synthetic example.

In addition, the ratio of the structural unit which is a group containing a polymerizable carbon-carbon double bond having an ^RD of 2 or more in the first structural unit and ^{the polymerizable property of the first structural unit having an RD} of only 1 The ratio of structural units that are groups containing carbon-carbon double bonds (ratio of polymer to all structural units) is also shown in Table 1. These ratios are determined by solving the "simultaneous equations" as described above, assuming that the ratio of norbornene structural units: maleic anhydride structural units in the raw material polymer 1 or 2 is 50:50 (molar ratio). I asked.
As a reminder, for each polymer, the sum of these two ratios is less than 50 mol%. From this, it can be said that not all of the maleic anhydride structural units in the polymer are ring-opened, and some of them remain in the structure represented by the formula (MA).

Here, from the numerical values of the acid value and the double bond equivalent of the polymer of the synthetic example, the polymers of the synthetic examples 1 to 10 are structural units represented by the general formula (1) and have an ^RD of 2 or more. It is supported that it contains a group containing a polymerizable carbon-carbon double bond. This will be described below.

Consider ring opening of MA units in a raw material polymer by 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. be. That is, the ring opening of one MA unit increases one carboxyl group and one C = C double bond.

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 can be changed by ring-opening of one MA unit. One, the C = C double bond increases by "2 or more".

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

Based on this, check the above table.
The acid value of the polymers of Synthesis Examples 1 to 10 (corresponding to the amount of carboxy group produced by ring opening) is the acid of the polymers of Comparative Synthesis Examples 2 and 3 (the MA unit is ring-opened only by the monofunctional compound). Similar to or less than the value. Nevertheless, the double bond equivalents of the polymers of Synthesis Examples 1-10 tend to be smaller than those of the polymers of Comparative Synthesis Examples 2 and 3 (ie, the amount of C = C double bonds per polymer unit mass). There are many). This indicates that the polymers of Synthesis Examples 1 to 10 have a structure derived from a polyfunctional compound such as A-TMM-3L or A-9550.

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, but as described above, it is double with the acid value. The bond equivalent relationship also supports the introduction of structures derived from polyfunctional compounds.

<Evaluation>
[Developability evaluation] (Solution rate of polymer 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.
Next, the above solution was spin-coated on the wafer, PGMEA was dried, and prebaked at a temperature of 100 ° C. for 2 minutes to prepare a resin film having a film thickness of about 2 μm.
This resin film was immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at a temperature of 23 ° C. together with the wafer, and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern disappearing, and dividing the film thickness by that time.

The quality of developability was judged according to the following criteria.
○ (Good): Dissolution rate 500 nm / s or more × (Bad): Dissolution rate less than 500 nm / s

[Sensitivity evaluation] (2.0 mass% sodium carbonate aqueous solution)
First, a photosensitive resin composition in which the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) was obtained 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 xaacrylate): 50 parts by mass-Photopolymerization initiator (BASF, Industry OXE01) : 5 parts by mass, adhesion aid (manufactured by Shinetsu Chemical Industry Co., Ltd., KBM-403): 1 part by mass, surfactant (manufactured by DIC Co., Ltd., F-556): 0.5 parts by mass

The obtained resin composition was rotationally coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane) and baked on a hot plate at 100 ° C. for 120 seconds to form a thin film having a thickness of about 3.0 μm (± 0.3 μm). I got A.
The thin film A was exposed to g + h + i lines at an exposure amount of ^{100 mJ / cm 2} with a Canon g + h + i line mask aligner (PLA-501F) via a photomask having a gradation of 1 to 100% of shading rate.
After the exposure, the thin film was developed (immersed together with the wafer) at 23 ° C. for 60 seconds in a 2.0 mass% sodium carbonate aqueous solution 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 films A and B obtained by the above method, the residual film ratio was calculated from the following formula.
Residual film ratio (%) = (thin film thickness of thin film B / film thickness of thin film A at each exposure amount) × 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): 21-50 mJ / cm ²
× (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 explore 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], a composition using any one of Synthesis Examples 1 to 10 as a polymer is used as a developing solution of 2.0% by mass carbonate. Using an aqueous sodium solution, the resin film was prepared and the dissolution rate was measured in the same manner as in the above [Evaluation of developability]. Then, it was evaluated according to the following criteria.
○ (Good): Dissolution rate 50 nm / s or more × (Bad): Dissolution rate 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 performance were good. That is, it was possible to achieve both sensitivity and developability.
In particular, the developability was good not only when the TMAH developer was used but also when the sodium carbonate developer was used. It can be seen that the photosensitive resin composition or polymer of the present embodiment has good solubility in various kinds of developing solutions.

On the other hand, in the evaluation using the polymer of Comparative Synthesis Example 1, the developability was poor. Although a relatively large amount of polymerizable carbon-carbon double bond was contained in the polymer (double bond equivalent: 286 g / mol), the acid value was as small as less than 70 mgKOH / g, so that sufficient development was sufficient. It is probable 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 bond having the density required for high sensitivity was not present in the polymer.

<Making color filters>
Of the photosensitive resin compositions prepared in [Sensitivity Evaluation], those containing the polymer of Synthesis Example 1 are further colored by adding an appropriate amount of pigment dispersion liquid NX-061 (manufactured by Dainichiseika Kogyo Co., Ltd., green). A photosensitive resin composition was prepared. A green color filter could be formed by forming a film on a substrate and performing exposure, alkali development treatment, and the like.
Further, as the pigment dispersion liquid, NX-053 (blue), NX-032 (red) or the like manufactured by the same company could be used instead of NX-061 to form a blue or red color filter.
By the way, these color filters have sufficient resistance to high temperatures that can be exposed in the device manufacturing process. This is believed to be related to the fact that the polymer contains structural units with a cyclic hydrocarbon backbone.

<Making a black matrix>
Of the photosensitive resin compositions prepared in [Sensitivity Evaluation], a black photosensitive resin composition containing the polymer of Synthesis Example 1 was further added with an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Kogyo Co., Ltd.). A sex resin composition was prepared. A black matrix could be formed by forming a film on a substrate and performing exposure, alkali development treatment, and the like.
By the way, this black matrix had sufficient resistance to high temperatures that could be exposed during the device fabrication process. This is believed to be related to the fact that the polymer contains structural units with a cyclic hydrocarbon backbone.

This application claims priority on the basis of Japanese Application Japanese Patent Application No. 2019-015715 filed on January 31, 2019, and incorporates all of its disclosures herein.

Claims (23)

A photosensitive resin composition containing 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), ^RD is a group containing a polymerizable carbon-carbon double bond. The photosensitive resin composition according to claim 1.
The first structural unit is a photosensitive resin composition containing a structural unit which is a group containing a polymerizable carbon-carbon double bond having an ^{RD of 2 or more.} The photosensitive resin composition according to claim 1 or 2.
The first structural unit is a structural unit having a ^RD of 2 or more and containing a polymerizable carbon-carbon double bond, and a structure having an ^RD of only 1 containing a 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.
A photosensitive resin composition in which 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.
A photosensitive resin composition, wherein the polymer further comprises a structural unit having a cyclic hydrocarbon skeleton. The photosensitive resin composition according to any one of claims 1 to 5.
A photosensitive resin composition in which the ratio of the first structural unit to the total structural unit of the polymer is 10 to 40 mol%. The photosensitive resin composition according to any one of claims 1 to 6.
A photosensitive resin composition having a weight average molecular weight of the polymer 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.
A photosensitive resin composition further containing a light-shielding agent. A polymer having a 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), ^RD is a group containing a polymerizable carbon-carbon double bond. The polymer according to claim 10.
The first structural unit is a ^{polymer containing a structural unit in which RD} is a group containing a polymerizable carbon-carbon double bond of 2 or more. The polymer according to claim 10 or 11.
The first structural unit is a structural unit in which ^RD is a group containing two or more polymerizable carbon-carbon double bonds, and a structure in which ^RD is a group containing only one polymerizable carbon-carbon double bond. Polymers 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.
Further, a polymer containing a structural unit having a cyclic hydrocarbon skeleton. The polymer according to any one of claims 10 to 14.
A polymer in which the ratio of the first structural unit to all structural units is 10 to 40 mol%. The polymer according to any one of claims 10 to 15.
A polymer having a weight average molecular weight of 6,000 to 25,000. A pattern obtained by 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 including the color filter according to claim 18. An image pickup device including 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.

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