JP2021063222A - Polymer, method for producing polymer, photosensitive resin composition, and cured product - Google Patents

Abstract

To provide a polymer for being used in a photosensitive resin composition which has good sensitivity, has high alkali solubility and is excellent in developability, and a method for producing the same.SOLUTION: A copolymer composed of a structural unit represented by formula (NB) and a maleic acid anhydride structural unit is reacted with a compound having a hydroxyl group and a (meth)acryloyl group in the presence of a basic catalyst, and a polymer having a structural unit by ester exchange with the maleic acid anhydride structural unit and a structural unit by a hydrolyzable group of the maleic acid anhydride structural unit site is obtained.SELECTED DRAWING: None

Description

The present invention relates to a polymer, a method for producing the polymer, a photosensitive resin composition containing the polymer, and a cured product formed from the photosensitive resin composition. More specifically, the present invention relates to a polymer used for producing a color filter or a black matrix, a method for producing the polymer, and an application thereof.

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

International Publication No. 2012/147706

As the photosensitive resin composition for forming a color filter or a black matrix, a resin having a property of being cured by causing a polymerization reaction by light is used. A color filter or a black matrix is produced by patterning a photosensitive resin composition by exposure and development and then curing the photosensitive resin composition. In photosensitive resin compositions, "higher sensitivity" seems to be a general issue, but with the increasing complexity and widespread use of display devices and imaging devices, higher levels of high sensitivity are required. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the higher the productivity can be improved. Further, the photosensitive resin composition is required to have excellent processability in photolithography using an alkaline developer.

By improving the polymer used in the photosensitive resin composition, the present inventors can obtain a photosensitive resin composition having good sensitivity, high alkali solubility, and thus excellent developability. This led to the present invention.

According to the present invention, the structural unit represented by the formula (NB), the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structural unit represented by the formula (3). A polymer containing the above is provided.

（式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１〜３０の有機基であり、ａ_１は０、１または２である。）

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

（式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基である。）

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

（式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基である。）

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

Further, according to the present invention, the structural unit represented by the formula (NB), the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the structure represented by the formula (3). A method of producing a polymer containing units,
A polymer precursor containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (MA). The first step of preparation and
A method for producing a polymer is provided, which comprises a second step of treating the polymer precursor with water in the presence of a catalyst.

（式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１〜３０の有機基であり、ａ_１は０、１または２である。）

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

（式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基である。）

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

（式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基である。）

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

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

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

According to the present invention, there is provided a polymer used for producing a photosensitive resin composition having good sensitivity and excellent developability.

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. ^{13 is a 13} C-NMR chart of the polymer P13 obtained in Example 13. ^{13 is} a 13 C-NMR chart of polymer P14 obtained in Example 14.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate. All drawings are for illustration purposes only. The shape and dimensional ratio of each member in the drawing do not necessarily correspond to the actual article. In the present specification, the notation "a to b" in the description of the numerical range means a or more and b or less unless otherwise specified. For example, "1 to 5 mol%" means "1 mol% or more and 5 mol% or less".

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

The notation "(meth) acrylic" herein represents a concept that includes both acrylic and methacrylic. The same applies to similar notations such as "(meth) acrylate".
In particular, the “(meth) acryloyl group” in the present specification refers to _{an acryloyl group represented by −C (= O) −CH = CH 2} and −C (= O) −C (CH ₃ ) = CH _2. Represents a concept including the methacryloyl group represented by.

(Polymer P)
The polymer of the present embodiment (hereinafter referred to as "polymer P") is a structural unit represented by the formula (NB), a structural unit represented by the formula (1), a structural unit represented by the formula (2), and the like. And the structural unit represented by the formula (3). It should be noted that these structural units typically constitute the main chain of the polymer P.

式（ＮＢ）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１〜３０の有機基であり、ａ_１は０、１または２である。

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

式（１）中、Ｒ^ｐは、２以上の（メタ）アクリロイル基を有する基である。

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

式（２）中、Ｒ^ｓは、１つの（メタ）アクリロイル基を有する基である。

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

Since the polymer P contains a structural unit represented by the formula (1) and a structural unit represented by the formula (2), the photosensitive resin composition containing the structural unit is excellent when subjected to a photolithography method. Has high sensitivity. It is considered that this is because the curing reaction (polymerization reaction) is promoted by the (meth) acryloyl group contained in the structural units represented by the formulas (1) and (2). Further, the polymer P has high alkali solubility by containing the structural unit represented by the formula (3). As a result, the photosensitive resin composition containing the polymer P has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developing solution. Moreover, the structural unit represented by the formula (NB) is chemically robust. Therefore, the polymer P containing this as a part of the structural unit has a small weight loss and is stable with respect to heating when manufacturing a liquid crystal display device or a solid-state image sensor.

The polymer P of the present embodiment may contain a structural unit represented by the formula (MA) in addition to the structural unit described above. The structural unit represented by the formula (MA) is ring-opened with an alkaline developer to generate two carboxyl groups. Therefore, the polymer P has excellent developability. When the polymer P contains a structural unit represented by the formula (MA), the structural unit represented by the formula (MA) in all the structural units of the polymer P is preferably 3 to 40 mol%, more preferably. , 10-30 mol%.

In the structural unit represented by the formula (NB) constituting the polymer P, the organic group having 1 to 30 carbon atoms which can constitute ^{R 1 to} R ^{4 is a substituted or unsubstituted, linear or branched carbon.} Alkyl of the number 1 to 30 can be mentioned, and more specifically, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaline group, a cycloalkyl group, an alkoxy group, a heterocyclic group and a carboxyl group. And so on.

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.

In formula ^{(NB), R 1, R} 2, preferably a hydrogen or an alkyl group as ^{R 3} and ^{R 4,} 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 with arbitrary atomic groups.} 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 formula (NB), _{a 1} is preferably 0 or 1, more preferably 0.

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

In the structural unit represented by the formula (1) constituting the polymer P, R ^p is not particularly limited as long as it is a group containing two or more (meth) acryloyl groups, but has 2 to 6 (meth) acryloyl groups. It is more preferably a group containing, and even more preferably a group containing 3 to 5 (meth) acryloyl groups. By optimizing the number of (meth) acryloyl groups contained in R ^p, the sensitivity of the polymer P containing them can be further increased. In addition, it becomes easier to achieve both sensitivity and developability at a higher level. Further, the heat resistance can be improved.
From the viewpoint of further improving the sensitivity, it is preferable that ^{R p} contains two or more acryloyl groups (groups represented by −C (= O) -CH = CH _{2) in terms of steric hindrance and the like.} ..

式（１ｂ）中、
ｋは２または３であり、
Ｒは水素原子またはメチル基であり、複数のＲは同じでも異なっていてもよく、
Ｘ^１は単結合、炭素数１〜６のアルキレン基または−Ｚ−Ｘ−で表される基（Ｚは−Ｏ−または−ＯＣＯ−であり、Ｘは炭素数１〜６のアルキレン基である）であり、複数存在するＸ^１は同一であっても異なっていてもよく、
Ｘ^１'は単結合、炭素数１〜６のアルキレン基または−Ｘ'−Ｚ'−で表される基（Ｘ'は炭素数１〜６のアルキレン基であり、Ｚ'は−Ｏ−または−ＣＯＯ−である）であり、
Ｘ^２は炭素数１〜１２のｋ＋１価の有機基である。 R ^p is preferably a group represented by the formula (1b), a group represented by the formula (1c), or a group represented by the formula (1d). With such a group, it tends to be easy to obtain the above-mentioned various effects.

In equation (1b),
k is 2 or 3
R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different.
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms. ), And 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-, and X is an alkylene group having 1 to 6 carbon atoms), X has 1 to 6 carbon atoms. The alkylene group may be linear or branched.
The alkylene group having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably −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 equation (1c),
k, R, X ¹ and X ^{2 are synonymous with R, k, X 1} and X ² in equation (1b), respectively, and a plurality of Rs may be the same or different from each other, 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.

式（１ｄ）中、ｎは、２〜５の整数であり、好ましくは、２または３である。
Ｒの具体的態様、好ましい態様などについては、一般式（１ｂ）で説明したものと同様である。

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

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

In the structural unit represented by the formula (2) constituting the polymer P, ^RS is a group containing only one (meth) acryloyl group. The polymer P contains both the structural unit of the formula (1) containing two or more (meth) acryloyl groups and the structural unit of the formula (2) containing only one acryloyl group to improve sensitivity and developability. It can be more highly compatible. In particular, in the design of a normal photosensitive resin composition, when the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while an attempt is made to improve the developability. In some cases, curing tends to be insufficient, but the polymer P of the present embodiment has both sensitivity and developability in a good balance.

^{More specifically, RS} is a group represented by the following formula (2a).

式（２ａ）において、Ｘ^１０は２価の有機基であり、Ｒは水素原子またはメチル基である。
Ｘ^１０の総炭素数は、好ましくは１〜３０、より好ましくは１〜２０である、さらに好ましくは１〜１０である。
式（２ａ）において、Ｘ^１０は２価の有機基であり、Ｒは水素原子またはメチル基である。
Ｘ^１０の総炭素数は、好ましくは１〜３０、より好ましくは１〜２０である、さらに好ましくは１〜１０である。
Ｘ^１０の２価の有機基としては、例えばアルキレン基が好ましい。このアルキレン基中の一部の−ＣＨ_２−はエーテル基（−Ｏ−）となっていてもよい。アルキレン基は、直鎖状でも分枝状でもよいが、直鎖状であることがより好ましい。

In 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.
In 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. The number of carbon atoms in X ¹⁰ (the chain length of X ¹⁰⁾ by appropriately selecting, more likely to participate in the structural units crosslinking reaction represented by formula (2), it is possible to increase the sensitivity.

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 proportion of the structural unit represented by the formula (2) in the total structural units of the polymer P is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.
Further, in the polymer P of the present embodiment, the total content of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is based on all the structural units of the polymer P. It is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 10 to 40 mol%.

The polymer P of the present embodiment contains a structural unit represented by the formula (3). As a result, the polymer P has excellent solubility in an alkaline developer, and thus has excellent developability.

The proportion of the structural unit represented by the formula (3) in the total structural units of the polymer P is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

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

The weight average molecular weight Mw of the polymer P of the present embodiment is preferably 1000 to 80,000, more preferably 2000 to 40,000, and even more preferably 3000 to 30000. By appropriately adjusting the weight average molecular weight, the sensitivity and the solubility in an alkaline developer can be adjusted.
The dispersity of the polymer P of the present embodiment (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. It is 0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the polymer P can be made uniform, which is preferable.
These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer P of the present embodiment is preferably 150 to 250 ° C, more preferably 170 to 230 ° C. The polymer P of the present embodiment tends to have a high glass transition temperature mainly because it contains a structural unit of the formula (NB). This is preferable in that the pattern formed on the substrate can be stably present in the manufacture of the liquid crystal display device and the solid-state image sensor. The glass transition temperature can be determined by, for example, differential thermal analysis (DTA).

By providing the above configuration, the polymer P of the present embodiment can have an alkali dissolution rate of 150 nm / s or more, preferably 180 nm / s or more, and more preferably 200 nm / s or more. s or more. The upper limit is not particularly limited, but may be, for example, 500 nm / s or less. In the specification of the present application, the alkali dissolution rate is a value measured under the following conditions.
(Method for Measuring Alkali Dissolution Rate) Polymer P is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid content concentration of 30% by mass. Next, the obtained polymer solution is spin-coated on a wafer, PGMEA is dried, and prebaked at a temperature of 100 ° C. for 2 minutes to prepare a resin film having a film thickness of 2 μm ± 0.2. The resin film is immersed in a 2.0 mass% sodium carbonate aqueous solution at a temperature of 23 ° C. together with the wafer. By visually observing the immersed wafer and measuring the time until the resin film dissolves and the interference pattern disappears, the film thickness before immersion (2 μm ± 0.2) is divided by that time to make the alkali. Calculate the dissolution rate (μm / sec).

(Manufacturing method of polymer P)
The polymer P of the present embodiment can be produced (synthesized) by any method. The polymer P of this embodiment is
(I) The structural unit represented by the above formula (NB), the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), and the above formula (MA). The first step of preparing a polymer precursor containing the represented structural unit (hereinafter referred to as "polymer precursor P'"), and
(II) The polymer precursor obtained in the first step is produced by the second step of treating with water in the presence of a catalyst. According to the second step, the structural unit represented by the above formula (NB), the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), and the above formula ( A polymer P containing a structural unit represented by 3) and optionally a structural unit represented by the above formula (MA) is produced.

Hereinafter, a method for producing (synthesizing) the polymer of the present embodiment by these steps will be described.
The first step (I) of preparing the polymer precursor is
A step of preparing a raw material polymer containing a structural unit represented by the formula (IB) and a structural unit represented by the formula (MA), and
(I-ii) The raw material polymer obtained in step (I-i) and a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as "polyfunctional (meth) acrylic compound"). Is reacted in the presence of a basic catalyst, and contains the structural unit represented by the formula (NB), the structural unit represented by the formula (MA), and the structural unit represented by the formula (1). And the process of preparing the polymer precursor of
(I-iii) A compound having a first polymer precursor obtained in the step (I-iii), a hydroxyl group and one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylic compound”). ) In the presence of a basic catalyst, the structural unit represented by the formula (NB), the structural unit represented by the formula (MA), the structural unit represented by the formula (1), and the formula. It is preferable to include a step of preparing a second polymer precursor containing the structural unit represented by (2). Here, the second polymer precursor obtained in the step (I-iii) corresponds to the polymer precursor P'described in the above step (I).

(Step (I-i))
In the step (Ii), the step of preparing the raw material polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) is the monomer represented by the formula (NBm). And maleic anhydride are polymerized (addition polymerization). The definitions of R ¹ , R ² , R ³ and R ⁴ and a _{1 in} the formula (NBm) are the same as those in the formula (NB). The same applies to the preferred embodiment.

Examples of the monomer represented by the formula (NBm) include norbornene, norbornene, 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 -Methyl norbornene-2-carboxylate, 5-norbornene-2,3-dicarboxylic acid anhydride and the like can be mentioned. At the time of polymerization, only one type of monomer represented by the formula (NBm) may be used, or two or more types may be used in combination.

The method of polymerization is not limited, but radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, or the like can be used.
Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis (2-methylpropionate), and 1,1'-azobis (cyclohexanecarbonitrile) (ABCN). Can be mentioned.
Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), methyl ethyl ketone peroxide (MEKP) and the like.
As the polymerization initiator, only one 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 synthesis of the raw material polymer is carried out by dissolving the monomer represented by the formula (NBm), maleic anhydride and the polymerization initiator in a solvent, charging the reaction vessel, and then heating to proceed the addition polymerization. .. The heating temperature is, for example, 50 to 80 ° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the formula (NBm) to maleic anhydride when charged in the reaction vessel is preferably 0.5: 1 to 1: 0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1: 1.
By such a step, a "raw material polymer" can be obtained.
The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer and the like. It is typically a random copolymer or an alternating copolymer. In addition, maleic anhydride is generally known as a monomer having strong alternating copolymerizability.

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

(Step (I-ii))
The structure represented by the formula (MA) contained in the raw material polymer is formed by reacting the raw material polymer obtained in the step (Ii) with the polyfunctional (meth) acrylic compound in the presence of a basic catalyst. A part of the unit is opened to form a structural unit represented by the formula (1), and the structural unit represented by the formula (NB), the structural unit represented by the formula (MA), and the structural unit represented by the formula (MA) are formed. A first polymer precursor containing the structural unit represented by) is obtained.

More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. As the organic solvent, a single solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) or the like or a mixed solvent can be used. However, various organic solvents used in the synthesis of organic compounds and polymers can be used.

Next, a polyfunctional (meth) acrylic compound is added to the above solution. In addition, a basic catalyst is added. Then, the solutions are mixed appropriately to obtain a uniform solution.

Examples of the polyfunctional (meth) acrylic compound include a compound represented by the formula (1 bm), a compound represented by the formula (1 cm), and a compound represented by the formula (1 dm). be able to. Definitions and embodiments of formula (1b-m) in ^{k, R, X 1, X} 1 ' and ^{X 2} are the same as those in the above-mentioned formula (1b). Further, the definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ^{6 in} the formula (1 cm) are the same as those in the above formula (1c). Further, the definitions of n and R in the formula (1dm) are the same as those in the above formula (1d).

Specific examples of the polyfunctional (meth) acrylic compound represented by the formula (1bm) include, but are not limited to, the following compounds.

Specific examples of the polyfunctional (meth) acrylic compound represented by the formula (1 cm) include, but are not limited to, the following compounds.

As the basic catalyst, an amine compound known in the field of organic synthesis, a nitrogen-containing heterocyclic compound and the like can be appropriately used. For example, an amine compound such as triethylamine, pyridine, or dimethylaminopyridine or a nitrogen-containing heterocyclic compound can be used as a catalyst. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass with respect to 100 parts by mass of the raw material polymer.

By heating the solution at preferably 60 to 80 ° C. for about 3 to 9 hours, a part of the structural unit of the formula (MA) contained in the raw material polymer is opened and the structural unit of the formula (1) is opened. Is formed, and a first polymer precursor containing a structural unit represented by the formula (NB), a structural unit represented by the formula (MA), and a structural unit represented by the formula (1) is produced.

(Step (I-iii))
Then, the first polymer precursor obtained in the step (I-ii) and the monofunctional (meth) acrylic compound are reacted in the presence of a basic catalyst to be contained in the first polymer precursor. A part of the structural unit represented by the formula (MA) is opened, the structural unit represented by the formula (2) is formed, and the structural unit represented by the formula (NB) is represented by the formula (MA). A second polymer precursor containing the structural unit represented by the formula (1), the structural unit represented by the formula (1), and the structural unit represented by the formula (2), that is, the polymer precursor P'is obtained.

The step (I-iii) is preferably carried out by adding a monofunctional (meth) acrylic compound to the reaction system containing the first polymer precursor obtained in the step (I-iii). From the viewpoint of steric hindrance of the reaction, the monofunctional (meth) acrylic compound tends to react more easily with the raw material polymer than the polyfunctional (meth) acrylic compound. Therefore, the step of reacting the monofunctional (meth) acrylic compound (I-iii) and the step of reacting the monofunctional (meth) acrylic compound (I-iii) are not carried out at the same time, but are carried out in this order. Is preferable. Further, the reaction between the monofunctional (meth) acrylic compound and the first polymer precursor proceeds in the presence of a basic catalyst. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (I-ii) can be used as it is. Therefore, in the step (I-iii), the first polymer precursor is isolated and purified from the reaction mixture containing the first polymer precursor obtained in the step (I-iii), or is contained in the mixture. Performed in situ by adding a monofunctional (meth) acrylic compound to the reaction mixture containing the first polymer precursor obtained in step (Ii) without neutralizing the basic catalyst. It is preferable to do so. Specifically, the reaction solution obtained by adding a monofunctional (meth) acrylic compound to the reaction mixture containing the first polymer precursor is heated at preferably 60 to 80 ° C. for about 1 to 9 hours. Then, a part of the structural unit represented by the formula (MA) contained in the first polymer precursor is opened, the structural unit represented by the formula (2) is formed, and the polymer precursor P'is generated. To do.

Examples of the monofunctional (meth) acrylic compound used in the step (I-iii) include a compound represented by the following formula (2am). In the formula (2am), ^{the definitions of X 10} and R are the same as those in the formula (2a).

Specific examples of the compound represented by the 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-hydroxyethyl-phthalic acid and the like. Can be done.

(Step (II))
By treating the polymer precursor P'obtained in the step (I-iii) with water in the presence of a catalyst, the structural unit represented by the formula (MA) contained in the polymer precursor P'is opened. The structural unit represented by the formula (3) is formed by ringing, and the structural unit represented by the formula (NB), the structural unit represented by the formula (1), and the structural unit represented by the formula (2) are formed. , And the polymer P containing the structural unit represented by the formula (3) can be produced. When a part of the structural unit represented by the formula (MA) is ring-opened and a part of the structural unit of the formula (MA) remains without opening the ring, the polymer P is represented by the formula (NB), the formula (NB). In addition to the structural units of 1), the formula (2), and the formula (3), the structural unit represented by the formula (MA) is included.

Step (II) is preferably carried out by adding water to the reaction system containing the polymer precursor P'obtained in step (I-iii). As the catalyst used in the step (II), a basic catalyst can be used, and a catalyst similar to the basic catalyst used in the above step (I-iii) or the step (I-iii) can be used. .. Specific examples of the basic catalyst include amine compounds such as triethylamine, pyridine and dimethylaminopyridine, and nitrogen-containing heterocyclic compounds.

In step (II), water was added to the reaction system containing the polymer precursor P'obtained in step (I-iii), and the obtained reaction solution was prepared at 0.25, preferably at 60 to 80 ° C. By heating for about 6 hours, the structural unit of the formula (MA) contained in the polymer precursor P'is ring-opened, and the structural unit represented by the formula (3) is produced. This reaction proceeds in the presence of a basic catalyst. As the basic catalyst, the catalyst remaining in the reaction system obtained in the step (I-iii) can be used as it is. Therefore, in step (II), the polymer precursor P'is isolated and purified from the reaction mixture containing the polymer precursor P'obtained in step (I-iii), or the basic catalyst contained in the mixture is used. It is preferably carried out in situ by adding water to the reaction mixture containing the polymer precursor P'obtained in step (I-iii) without neutralization.

After the step (II), 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 (for example, formic acid, citric acid, etc.) 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 polymer P is obtained.

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

(Photosensitive resin composition)
A photosensitive resin composition can be prepared by using the above polymer P and a photoradical polymerization initiator.
As described above, this photosensitive resin composition has excellent curability and therefore good sensitivity, and has high alkali solubility and thus has excellent developability.

The photoradical polymerization initiator that can be used is not particularly limited, and known photoradical polymerization initiators can be appropriately used.
For example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-( 2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-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, 4 , 4'-Bis (dimethylamino) benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutylate and other benzoin compounds; thioxanthone, 2-ethylthioxanthone, 2 Thioxanthone compounds such as −isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine , 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-( Halomethylated triazine compounds such as 4-ethoxycarbokynylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxa Diazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 , 4-Oxaziazole and other halomethylated oxadiazole compounds; 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-1,2'-biimidazole, etc. Biimidazole compounds; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Oxime ester compounds such as carbazole-3-yl] -1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H) -Pyrol-1-yl) -phenyl) Titanosen compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; aclydin compounds such as 9-phenylaclydin; etc. be able to.

The photosensitive resin composition may contain only one type of photoradical polymerization initiator, or may contain two or more types of photoradical polymerization initiators.
The amount of the photoradical polymerization 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 P.

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

As the pigment, an organic pigment or an inorganic pigment can be used.
Organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. Pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, dye lake pigments and the like can be used.
Inorganic pigments include white / extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chromium vermillion, nickel titanium, chromatitanium, etc.) , 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.

When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one colorant or two or more colorants.
A colorant (particularly a pigment) having an appropriate average particle size can be used depending on the purpose and application, but a small average of 0.1 μm or less is particularly required when transparency such as a color filter is required. When the particle size is preferable and other concealing properties such as paints are 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 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).

In one aspect, the photosensitive resin composition may contain a light-shielding agent. By containing a light-shielding agent, it can be preferably used as a material for forming a black matrix of a liquid crystal display device or a solid-state image sensor.
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 photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of 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).

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

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

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

In one aspect, the photosensitive resin composition can 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 acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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 about 30 to 70 parts by mass, preferably about 40 to 60 parts by mass with respect to 100 parts by mass of the polymer P.

The photosensitive resin composition can be used as a filler, a binder resin other than the above-mentioned polymers, an acid generator, a heat resistance improver, a development aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, and an oxidation, depending on various purposes and required properties. Inhibitors, matting agents, defoaming agents, leveling agents, surfactants, antistatic agents, dispersants, slip agents, surface modifiers, rocking agents, rocking aids, silane coupling agents, polyvalent phenols It may contain a component such as a compound.

(Pattern, color filter, black matrix, liquid crystal display device and solid-state 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 color filters, black matrices, and the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Further, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Then, a liquid crystal display device or a solid-state image sensor provided with a color filter and a black matrix can be manufactured.

A typical procedure for forming a pattern will be described.

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

The substrate on which the composition is applied is not particularly limited. For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper-clad laminate, and the like can be mentioned.
The substrate may be an unprocessed substrate or a substrate on which electrodes and elements are formed on the surface. It may be surface-treated to improve the adhesiveness.
The method of applying the photosensitive resin composition is not particularly limited. It can be performed by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

Drying of the photosensitive resin composition applied on the substrate is typically 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, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by adjusting the content of the solvent in the photosensitive resin composition, the coating method, and the like.

(exposure)
The exposure is typically carried out by irradiating the photosensitive resin film with an active ray through a suitable 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 photosensitizer in the photosensitive resin film and the like, and is, for example, about ^{100 to 500 mJ / cm 2.}

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

(developing)
By developing the exposed photosensitive resin film with an appropriate 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 the development, the exposed portion (in the case of the positive type) or the unexposed portion (in the case of the negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained.

The developer that can be used is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used.
Specific examples of the alkaline aqueous solution include (i) an inorganic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine and triethanolamine, and (iii). Examples thereof include an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Specific examples of the organic solvent include a ketone solvent such as cyclopentanone, an ester solvent such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and an ether solvent such as propylene glycol monomethyl ether.
A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developing solution.

In the present embodiment, it is preferable to use an alkaline aqueous solution as the developing solution, and it is more preferable to use tetramethylammonium hydroxide, sodium carbonate aqueous solution, or potassium hydroxide aqueous solution.
The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass.

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

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

An example of the structure of a liquid crystal display device and / or a solid-state 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, and is made of, for example, a polymer of polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin, or the like, in addition to glass. The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical solution treatment, or the like, if necessary.
The substrate 10 is preferably made of glass.

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

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. 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>
(Synthesis of raw material polymer 1)
588.36 g (6.0 mol) of maleic anhydride, 564.90 g (6.0 mol) of 2-norbornene and dimethyl 2,2'-in an appropriately sized reaction vessel equipped with a stirrer and a condenser. 55.26 g (0.24 mol) of azobis (2-methylpropionate) was weighed in. These were dissolved in a mixed solvent consisting of 1716.8 g of methyl ethyl ketone and 188.3 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 1423.2 g of methanol to precipitate a white solid. The obtained white solid is further washed with 3557.5 g of methanol and then vacuum dried at a temperature of 120 ° C. to provide a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (a polymer (). Raw material polymer 1) 1027.2 g was obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 7236, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.83. there were.

<Synthesis of polymer P>
Polymer P was prepared using the following method.
(Synthesis Example 1)
A polymer P1 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound was prepared. The details will be described below.
First, 99.01 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Then, 38.75 g of A-TMM-3LM-N was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 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 diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
From the above, 61.39 g of polymer P1 ring-opened with A-TMM-3LM-N and BHEA was obtained as a structural unit derived from maleic anhydride in the raw material polymer.
GPC measurement of polymer P1 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P1 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P1 had a ring-opened structure with A-TMM-3LM-N and BHEA.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P1 measured by GPC measurement.

(Synthesis Example 2)
20.00 g of the polymer P1 obtained in Synthesis Example 1 was dissolved in 46.67 g of PGMEA (propylene glycol monomethyl ether acetate) to prepare a solution. Then, 8.00 g (0.444 mol) of water was added to this solution, and the mixture was reacted at a temperature of 70 ° C. for 6 hours. The obtained reaction mixture was solvent-substituted to obtain 55.20 g (solid content concentration: 28.56% by mass) of polymer P2.
The above solvent substitution was carried out by the following procedure.
The obtained reaction mixture was subjected to solvent removal at 50 ° C. under reduced pressure by a rotary evaporator. After confirming that the polymer solution became considerably viscous, the solvent removal operation was interrupted. Then, 60.00 g of PGMEA was added and mixed until uniform. The solvent was removed at 50 ° C. under reduced pressure in the same manner. After confirming that the polymer solution became considerably viscous, the solvent removal operation was interrupted. Then, 80.00 g of PGMEA was added and mixed until uniform. The solvent was removed at 50 ° C. under reduced pressure in the same manner to prepare a solution having a solid content concentration of 30% by mass ± 2% by mass as measured by a heat-drying moisture meter. By the above operation, the water used in the reaction is removed and the solvent is replaced with PGMEA.
¹³ C-NMR measurement of polymer P2 confirmed that polymer P2 had a ring-opened structure with A-TMM-3LM-N, BHEA and water.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P2 measured by GPC measurement.

(Synthesis Example 3)
A solution was prepared by adding 99.01 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Then, 38.75 g of A-TMM-3LM-N was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 mol) of BHEA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, without post-treatment, the obtained reaction solution was added with 3.00 g (0.167 mol) of water and reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 70.52 g of polymer P3 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N, BHEA and water was obtained.
GPC measurement of the polymer P3 confirmed the disappearance of the peaks of the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P3 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ¹³ C-NMR measurement confirmed that the polymer P3 had a ring-opened structure with A-TMM-3LM-N, BHEA and water. In addition, ¹³ C-NMR measurement revealed that the polymer P3 had a higher proportion of the water-opened structure than the polymer P2.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P3 measured by GPC measurement.

(Synthesis Example 4)
A polymer P4 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound was prepared. The details will be described below.
First, 108.26 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Then, 58.12 g of A-TMM-3LM-N was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 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 diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, 65.76 g of polymer P4 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N and BHEA was obtained.
GPC measurement of the polymer P4 confirmed the disappearance of the peaks of the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P4 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P4 had a ring-opened structure with A-TMM-3LM-N and BHEA.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P4 measured by GPC measurement.

(Synthesis Example 5)
20.00 g of the polymer P4 obtained in Synthesis Example 1 was dissolved in 46.67 g of PGMEA (propylene glycol monomethyl ether acetate) to prepare a solution. Then, 8.00 g (0.444 mol) of water was added to this solution, and the mixture was reacted at a temperature of 70 ° C. for 6 hours. The obtained reaction mixture was solvent-substituted to obtain 59.35 g (solid content concentration: 28.70% by mass) of polymer P5. Solvent substitution was carried out in the same manner as in Synthesis Example 2.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P5 had a structure ring-opened with A-TMM-3LM-N, BHEA and water.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P5 measured by GPC measurement.

(Synthesis Example 6)
A solution was prepared by adding 108.26 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Then, 58.12 g of A-TMM-3LM-N was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 mol) of BHEA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, 24.00 g (1.332 mol) of water was added to the obtained reaction solution without post-treatment, and the reaction solution was reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 78.50 g of polymer P6 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N, BHEA and water was obtained.
GPC measurement of the polymer P6 confirmed the disappearance of the peaks of the polyfunctional (meth) acrylic compound and the monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P6 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P6 had a structure ring-opened with A-TMM-3LM-N, BHEA and water. In addition, ¹³ C-NMR measurement revealed that the polymer P6 had a higher proportion of the water-opened structure than the polymer P5.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P6 measured by GPC measurement.

(Synthesis Example 7)
A solution was prepared by adding 108.26 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Then, 58.12 g of A-TMM-3LM-N was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 mol) of BHEA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, without post-treatment, the obtained reaction solution was added with 6.00 g (0.333 mol) of water and reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 70.59 g of polymer P7 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N, BHEA and water was obtained.
GPC measurement of polymer P7 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P7 had a structure ring-opened with A-TMM-3LM-N, BHEA and water. In addition, ¹³ C-NMR measurement revealed that polymer P7 had a higher proportion of water-opened structures than polymer P5.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P7 measured by GPC measurement.

(Synthesis Example 8)
A polymer P8 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound was prepared. The details will be described below.
First, 99.71 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Then, 38.75 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, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, 58.17 g of polymer P8 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.
GPC measurement of polymer P8 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P1 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P8 had a structure ring-opened with A-TMM-3L and 4-HBA.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P8 measured by GPC measurement.

(Synthesis Example 9)
A solution was prepared by adding 99.71 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Then, 38.75 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, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, without post-treatment, the obtained reaction solution was added with 9.00 g (0.500 mol) of water and reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 58.56 g of polymer P9 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L, 4-HBA and water was obtained.
GPC measurement of polymer P9 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P9 had a structure ring-opened with A-TMM-3L, 4-HBA and water.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P8 measured by GPC measurement.

(Synthesis Example 10)
A polymer P10 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound was prepared. The details will be described below.
First, 114.39 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Next, 35.03 g of A-9550 was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 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 diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, 57.82 g of polymer P10 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-9550 and BHEA was obtained.
GPC measurement of polymer P10 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P10 had a ring-opened structure with A-9550 and BHEA.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P10 measured by GPC measurement.

(Synthesis Example 11)
A solution was prepared by adding 102.73 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Next, 35.03 g of A-9550 was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.31 g (0.390 mol) of BHEA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, without post-treatment, the obtained reaction solution was added with 3.00 g (0.167 mol) of water and reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 70.77 g of polymer P11 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-9550, BHEA and water was obtained.
^{It was confirmed by 13} C-NMR that the polymer P11 had a structure ring-opened with A-9550, BHEA and water.
GPC measurement of polymer P11 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ^{it was confirmed by 13} C-NMR measurement that the polymer P11 had a structure ring-opened with A-9550, BHEA and water.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P11 measured by GPC measurement.

(Synthesis Example 12)
A solution was prepared by adding 103.03 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Next, 35.03 g of A-9550 was added to this solution, and then 36.00 g (0.356 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 45.01 g (0.312 mol) of 4-HBA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, without post-treatment, the obtained reaction solution was added with 6.00 g (0.333 mol) of water and reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 70.64 g of polymer P12 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-9550, 4-HBA and water was obtained.
GPC measurement of polymer P12 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group.
Furthermore, ¹³ C-NMR measurement confirmed that the polymer P12 had a structure ring-opened with A-9550, 4-HBA and water.
Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P12 measured by GPC measurement.

(Synthesis Example 13)
A polymer P13 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth) acrylic compound and a monofunctional (meth) acrylic compound was prepared. The details will be described below.
First, 99.71 g of MEK was added to 160 g of the raw material polymer (0.312 mol in terms of MA) to prepare a solution. Then, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70 ° C. for 4 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 16 hours.
As described above, 56.44 g of polymer P13 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N and 4-HBA was obtained.
GPC measurement of polymer P13 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group. Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P13 measured by GPC measurement.
^{It was confirmed by 13} C-NMR that the polymer P13 had a structure ring-opened with A-TMM-3LM-N and 4-HBA.
Further, the structural unit (structural unit of the formula (1)) derived from the trifunctional (meth) acrylic compound (A-TMM-3LM-N) and the structure derived from the monofunctional (meth) acrylic compound (4-HBA) in the polymer P13. Amount (mole fraction) of units (structural unit of formula (2)), water-opened side chain (structural unit of formula (3), and unreacted (unopened) MA unit (structural unit of formula (MA)) , Mol%) (A, B, C, and D, respectively) were ^{calculated by 13} C-NMR integrated value analysis. The results are shown below. The ¹³ C-NMR chart is shown in FIG.
As shown in FIG. 2, the integrated values a, b, c, and d corresponding to each structure were defined as signals existing in the chemical shift in the following range, and the integrated values were measured.
a: 164.8 to 165.3 ppm
b: 165.3 to 165.6 ppm
c: 174.7 to 178.0 ppm
d: 168.0 to 174.7 ppm
From the integrated values a, b, c, and d, the molar ratios A, B, C, and D were calculated from the following formulas.
A = a / 3
B = b
C = {c- (a / 3) -b} / 2
D = {d- (a / 3) -b} / 2
Since the peak of 168.0 to 174.7 ppm in the ¹³ C-NMR chart included the peak of citric acid used in the extraction (peak top: 171.30 ppm), the integrated value d was 168.0. It was calculated by dividing the integrated value of 171.23-171.33 ppm (corresponding to the citric acid content) from the integrated value of -174.7 ppm.
The mole fraction of each structural unit was as follows.
Structural unit derived from A-TMM-3LM-N: 13.1 mol%
Structural unit derived from 4-HBA: 34.2 mol%
Water-opening side chain: 0.7 mol%
MA unit: 52.1 mol%

(Synthesis Example 14)
A solution was prepared by adding 99.71 g of MEK to 160 g of the raw material polymer (0.312 mol in terms of MA). Then, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70 ° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70 ° C. for 3.5 hours to prepare a reaction solution.
Then, without post-treatment, the obtained reaction solution was added with 9.00 g (0.500 mol) of water and reacted at 70 ° C. for 0.5 hours.
The obtained reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, the polymer was purified by the following procedure.
-The polymer was reprecipitated with an excess amount of toluene.
-The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.
-The operation of washing the polymer powder after washing twice with an excess amount of water was performed three times.
The resulting reaction product was dried at 40 ° C. for 12 hours.
As described above, 65.04 g of polymer P14 obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N, 4-HBA and water was obtained.
GPC measurement of polymer P14 confirmed the disappearance of peaks of the polyfunctional (meth) acrylic compound and monofunctional (meth) acrylic compound used. As a result, it was confirmed that the obtained polymer P7 did not contain an unreacted (meth) acrylic compound or a (meth) acrylic compound having no hydroxyl group. Table 1 shows the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer P13 measured by GPC measurement.
^{It was confirmed by 13} C-NMR that the polymer P14 had a structure ring-opened with A-TMM-3LM-N, 4-HBA and water. Further, the amount of each structural unit was calculated by the same method as in Synthesis Example 13. The results are described below. The ¹³ C-NMR chart is shown in FIG.
Since the peak of 168.0 to 174.7 ppm in the ¹³ C-NMR chart included the peak of citric acid used in the extraction (peak top: 171.34 ppm and 175.12 ppm), the integrated value d. Was calculated by dividing the integral value of 171.33 to 171.39 ppm and the integral value of 175.08 to 175.15 ppm (both corresponding to citric acid content) from the integral value of 168.0 to 174.7 ppm.
The mole fraction of each structural unit was as follows.
Structural unit derived from A-TMM-3LM-N: 14.0 mol%
Structural unit derived from 4-HBA: 35.3 mol%
Water-opening side chain: 7.0 mol%
MA unit: 43.6 mol%

^{The conditions for 13} C-NMR measurement are as follows.
(Test conditions) The measurement sample was prepared by adding a measurement solvent to the weighed sample to adjust the concentration, and then pouring a specified amount into a sample tube for NMR measurement.
-Measuring device: JEOL JNM-ECA400 superconducting FT-NMR device-Resonance frequency: 100.53 MHz
・ Measurement nucleus: ¹³ C
-Measurement method: NNE measurement (inverse gate decoupling method)
-Pulse width: 3.83 μsec
・ Pulse repetition waiting time: 30s
・ Number of integrations: 4096 times ・ Measurement temperature: Room temperature ・ Measurement solvent: DMSO-d ₆ (deuterated dimethyl sulfoxide)
-Sample concentration: 20% (w / v)

Table 1 below shows the components used in each synthesis example and the amount charged (maleic anhydride (MA) equivalent).

(Examples 1 to 7, Reference Examples 1 to 2, Comparative Examples 1 to 5)
In each Example and each Comparative Example, the alkali solubility of the polymer P obtained in the above synthetic example was evaluated. In addition, a photosensitive resin composition was prepared using these polymers P, and its performance was evaluated.

<Evaluation>
[Evaluation of developability] (Dissolution rate of polymer P in alkaline developer)
Polymers P1, P3, P4, and P6 to P14 obtained in Synthesis Example 1, Synthesis Example 3, Synthesis Example 4, and Synthesis Examples 6 to 14 are dissolved in propylene glycol monomethyl ether acetate (PGMEA) to have a solid content concentration of 30 mass by mass. % Solution was made. Since the polymers P2 and P5 obtained in Synthesis Example 2 and Synthesis Example 5 were adjusted to have a solid content concentration of 30% by mass ± 2% by mass, they were used as they were in the next operation.
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 2 μm ± 0.2.
The resin film was immersed in a 2.0 mass% sodium carbonate aqueous solution at a temperature of 23 ° C. together with the wafer, and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern disappearing, and dividing the film thickness by that time. The results are shown in Table 2. When the alkali dissolution rate is 180 nm / s or more, it can be considered that the developability is good.

[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 P (polymer P obtained in Synthesis Examples 1 to 14): 100 parts by mass (for polymers P2 and P5, the polymers P2 and P5 were weighed so that the solid content of the polymer excluding PGMEA was 100 parts by mass. .)
-Polyfunctional acrylate (dipentaerythritol hexaacrylate): 50 parts by mass-Photopolymerization initiator (BASF, Industry OXE01): 5 parts by mass-Adhesion aid (Shinetsu Chemical Industry Co., Ltd., KBM-403): 1 Parts by mass-Initiator (F-556, manufactured by DIC Corporation): 0.5 parts by mass The obtained photosensitive resin composition is filtered with a PTFE membrane filter Millex-LS (manufactured by Merck Millipore), if necessary. , The insoluble matter was removed.

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. The results are shown in Table 2. The smaller the exposure amount value at which the residual film ratio is 95% or more, the higher the sensitivity. If the exposure amount at which the residual film ratio is 95% or more is 40 mJ / cm ² or less, it can be used as a photosensitive material without any problem, and in particular ^{, if it is 25 mJ / cm 2} or less, it is considered that the sensitivity is good. Can be done.

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

The polymer P3, polymer P6, polymer P7, polymer P9, polymer P11, polymer P12 and polymer P14 are all structural units obtained by ring-opening the maleic anhydride structural unit with water in the polymer structure (formula (3). ), The alkali dissolution rate was good, and therefore the developability was excellent. Further, the polymer P3, the polymer P7, the polymer P9, the polymer P11, the polymer P12 and the polymer P14 have particularly high sensitivity, and thus the photosensitive resin composition containing these polymers has a good balance between developability and sensitivity. I was prepared.

<Making color filters>
A colored photosensitive resin composition was prepared by further adding an appropriate amount of a pigment dispersion liquid NX-061 (manufactured by Dainichiseika Kogyo Co., Ltd., green) to the photosensitive resin compositions prepared in Examples 1 to 7.
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.

<Making a black matrix>
A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion liquid NX-595 (manufactured by Dainichiseika Kogyo Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 7.
A black matrix could be formed by forming a film on a substrate and performing exposure, alkali development treatment, and the like.

10 Substrate 11 Black matrix 12 Color filter 13 Protective film 14 Transparent electrode layer

Claims (14)

A polymer containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3).

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

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

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

The polymer according to claim 1, further comprising a structural unit represented by the formula (MA).

The polymer according to claim 1 or 2, wherein the alkali dissolution rate is 150 nm / s or more. ^{R p} in the structural unit represented by the formula (1) is selected from the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d). The polymer according to any one of claims 1 to 3, which is at least one.

(In equation (1b),
k is 2 or 3
R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different.
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms. ), And 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. )

(In equation (1c),
k, R, X ¹ and X ^{2 are synonymous with R, k, X 1} and X ² in equation (1b), respectively, and a plurality of Rs may be the same or different from each other, 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. )

(In equation (1d),
n is an integer of 2-5
R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. ) ^{The polymer according to any one of claims 1 to 4, wherein R s} in the structural unit represented by the formula (2) is a group represented by the formula (2a).

(In formula (2a), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.) A polymer containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3) is produced. It ’s a method,
A polymer precursor containing a structural unit represented by the formula (NB), a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (MA). The first step of preparation and
A method for producing a polymer, which comprises a second step of treating the polymer precursor with water in the presence of a catalyst.

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

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

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

The method for producing a polymer according to claim 6, wherein the catalyst used in the second step is a basic catalyst. The method for producing a polymer according to any one of claims 6 or 7, wherein the first step and the second step are carried out in situ. The first step is
A step of preparing a raw material polymer containing a structural unit represented by the formula (NB) and a structural unit represented by the formula (MA).
The raw material polymer is reacted with a compound having a hydroxy group and two or more (meth) acryloyl groups in the presence of a basic catalyst, and the structural unit represented by the formula (NB) is represented by the formula (MA). The step of preparing a first polymer precursor containing the structural unit represented and the structural unit represented by the formula (1), and the first polymer precursor, a hydroxy group and one (meth) acryloyl group. The structural unit represented by the formula (NB), the structural unit represented by the formula (1), the structural unit represented by the formula (2), by reacting the compound having The method for producing a polymer according to any one of claims 6 to 8, further comprising the step of preparing the polymer precursor containing the structural unit represented by the formula (MA). The compound having a hydroxy group and two or more (meth) acryloyl groups is a compound represented by the formula (1 bm), a compound represented by the formula (1 cm), and a compound represented by the formula (1 dm). The method for producing a polymer according to claim 9, which is at least one selected from the represented compounds.

(In equation (1b-m),
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. a certain), X ¹ existing in plural numbers may be the same or different and
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. )

(In formula (1 cm),
k, R, X ¹ and X ^{2 are synonymous with R, k, X 1} and X ² in equation (1b-m), respectively, and a plurality of Rs may be the same or different from each other. a plurality of X ¹ may be the being the same or different,
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. )

(In equation (1 dm),
n is an integer of 2-5
R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different) The method for producing a polymer according to claim 9 or 10, wherein the compound having a hydroxy group and one (meth) acryloyl group is a compound represented by the formula (2am).

(In formula (2am), X ¹⁰ is a divalent organic group and R is a hydrogen atom or a methyl group.) The polymer according to any one of claims 1 to 5, which is used for forming a color filter or a black matrix. The polymer according to any one of claims 1 to 5 and
Including a photoradical polymerization initiator,
Photosensitive resin composition. A cured product formed from the photosensitive resin composition according to claim 13.

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