JP7585658B2 - Polymer solution, photosensitive resin composition - Google Patents

Description

The present invention relates to a polymer solution and a photosensitive resin composition.

Liquid crystal display devices and solid-state imaging devices are usually equipped with color filters and black matrices. Color filters and black matrices are configured by forming structures such as colored patterns and protective films on a substrate. Of these structures, the most common method for forming colored patterns and protective films is by photolithography using a photosensitive resin composition.

Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition that contains an alkali-soluble resin having an acidic group and two or more different polymerizable unsaturated groups at least in the side chain, a polymerizable compound, and a photopolymerization initiator. In addition, an example of Patent Document 1 describes the synthesis of a methacrylic acid/allyl methacrylate/glycidyl adduct as an alkali-soluble resin, and the preparation of a photosensitive resin composition using this.

International Publication No. 2012/147706

The photosensitive resin composition used to form color filters and black matrices uses a resin that has the property of being hardened by a polymerization reaction caused by light. Color filters and black matrices are produced by patterning the photosensitive resin composition through exposure and development, and then hardening it.

Although "high sensitivity" seems to be a common issue for photosensitive resin compositions, higher levels of sensitivity are required due to the increasing complexity and popularity of display devices and imaging devices. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, which can improve productivity. Furthermore, the cured product of the photosensitive resin composition is required to be suppressed from yellowing and to have excellent transparency and heat discoloration resistance.
In Patent Document 1, there is room for improvement in these characteristics.

The inventors discovered that by improving the polymers used in the photosensitive resin composition and the formulation of the composition, it is possible to obtain a cured resin product that has good sensitivity and is highly resistant to heat discoloration and suppresses yellowing, and thus arrived at the present invention.

（一般式（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、ａ１は０、１または２である。）

（一般式（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。）

（一般式（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。）
本発明によれば、
ポリマー溶液と、感光剤とを含む感光性樹脂組成物が提供される。 According to the present invention,
A structural unit represented by general formula (NB),
Provided is a polymer solution comprising: a polymer comprising a structural unit represented by general formula (1) and at least one structural unit selected from structural units represented by general formula (2); and a compound having a thiol group and an alkoxy group or an oligomer thereof.

(In general formula (NB), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.)

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

(In general formula (2), ^Rs is a group having one (meth)acryloyl group.)
According to the present invention,
A photosensitive resin composition is provided that includes a polymer solution and a photosensitizer.

The polymer solution of the present invention can provide a cured resin product that has good sensitivity, reduced yellowing, excellent transparency, and excellent developability. In other words, the polymer solution of the present invention can provide a cured resin product that has an excellent balance of these properties.

FIG. 1 is a diagram (cross-sectional view) illustrating a schematic example of a structure of a liquid crystal display device and/or a solid-state imaging device.

The following describes an embodiment of the present invention with reference to the drawings. In all drawings, similar components are given similar reference numerals and descriptions are omitted as appropriate. In addition, all drawings are for explanatory purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual objects. In this specification, the notation "a-b" in the explanation of a numerical range means a or more and b or less, unless otherwise specified. For example, "5-90%" means "5% or more and 90% or less."

In this specification, when a group (atomic group) is represented without specifying whether it is substituted or unsubstituted, it includes both groups that have no substituents and groups that have a substituent. For example, "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups).

In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

In particular, the term "(meth)acrylic group" in this specification represents a concept that includes an acryloyl group represented by -C(=O)-CH= _CH2 and a methacryloyl group represented by -C(=O)-C( _CH3 )= _CH2 .

The polymer solution of this embodiment is
The polymer P includes a predetermined structural unit; and a compound Q having a thiol group and an alkoxy group, or an oligomer thereof.

[Polymer P]
The polymer P of this embodiment is
A structural unit represented by the following general formula (NB):
The polymer P includes at least one structural unit selected from a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). In other words, the polymer P includes a structural unit represented by the general formula (NB) and either one or both of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). These structural units typically constitute the main chain of the polymer P.

In formula (NB), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

In general 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 P used in the polymer solution of this embodiment contains a structural unit represented by general formula (1) and/or a structural unit represented by general formula (2). In other words, the polymer P contains either one or both of the structural units represented by general formula (1) and the structural units represented by general formula (2). As a result, the photosensitive resin composition containing the polymer P has excellent sensitivity when subjected to a photolithography method. This is thought to be because the (meth)acryloyl group contained in the structural unit represented by general formula (1) or general formula (2) promotes the curing reaction (polymerization reaction). The polymer P also contains a structural unit represented by general formula (NB). This structural unit (NB) is chemically robust. Therefore, the polymer P containing this structural unit has a small weight loss when subjected to a heat treatment and is stable. Therefore, the photosensitive resin composition containing the polymer P can be suitably used for producing films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

In a preferred embodiment, polymer P contains a structural unit represented by general formula (1) or a structural unit represented by general formula (2) as an essential component, and in a more preferred embodiment, polymer P contains a structural unit represented by general formula (1) as an essential component. Since the structural unit represented by general formula (1) has at least two (meth)acryloyl groups, polymer P containing this has higher sensitivity in photolithography processing.

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

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

In the structural unit represented by general formula (NB) constituting polymer P, examples of the organic group having 1 to 30 carbon atoms which may constitute R ¹ to R ⁴ include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, more specifically, alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.
The alkynyl group includes, for example, 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 xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaryl group include a tolyl group and a xylyl group.
Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of the alkoxy group include 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, a neopentyloxy group, and an n-hexyloxy group.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.
In the structural unit represented by formula (NB), R ¹ , R ² , R ³ and R ⁴ are preferably hydrogen or an alkyl group, and more preferably hydrogen.

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 any atomic group. For example, they may be substituted with fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, a fluorinated alkyl group may be selected as the organic group having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ .
In the structural unit represented by formula (NB), a1 is preferably 0 or 1, and more preferably 0.

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

In one embodiment, it is preferable that polymer P has either or both of a structural unit represented by general formula (1), in other words, a structural unit containing two or more (meth)acryloyl groups (-C(=O)-CH=CH ₂ ), and a structural unit represented by general formula (2), because this can further improve the sensitivity of polymer P in exposure processing.

In the structural unit represented by general formula (1) which can constitute the polymer P, R ^p is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 6 (meth)acryloyl groups, and 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 it in the exposure treatment can be further increased. In addition, it becomes easier to achieve a high compatibility between the sensitivity and the alkali solubility of the polymer P. Furthermore, the heat resistance of the polymer P can be improved.
Rp is preferably a group represented by general formula (1b) or a group represented by general formula (1c). By using such a group, the above-mentioned various effects tend to be easily obtained.

In general formula (1), Rp is preferably a group represented by general formula (1b), a group represented by general formula (1c), or a group represented by general formula (1d). By using such a group, it tends to be easier to obtain the various effects described above.

In general formula (1b),
k is 2 or 3;
R is a hydrogen atom or a methyl group, and multiple R may be the same or different.

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

X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-);
^X2 is a (k+1) valent organic group having 1 to 12 carbon atoms.

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

When X ¹ is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched.
When X ¹ is an alkylene group having 1 to 6 carbon atoms, X ¹ is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2- (methylene group).

When ^X1 is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched.

The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2 _{- CH2-} (ethylene group) or _-CH2 -CH( _CH3 )-.
When X ¹ ' is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are the same as those of X1.
When X ¹ ' is a group represented by -X'-Z'-, specific embodiments of X' are the same as those of X above.

The k+1 valent organic group having 1 to 12 carbon atoms for ^X2 may be any group obtained by removing k+1 hydrogen atoms from any organic compound. The "any organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, more preferably 100 or less.

^X2 is, for example, a group in which k+1 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which k+1 hydrogen atoms have been removed 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 hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon.

In another embodiment, ^X2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

In general formula (1c),
k, R, ^X1 , and ^X2 are the same as R, k, X1, and ^X2 in formula (1b), respectively, and a plurality of R may be the same or different from each other, and a plurality of X1 may be the same or different from each other;

^X3 is a divalent organic group having 1 to 6 carbon atoms;
^X4 and ^X5 each independently represent a single bond or a divalent organic group having 1 to 6 carbon atoms;
^X6 is a divalent organic group having 1 to 6 carbon atoms.
Specific and preferred aspects of R, k, ^X1 and ^X2 are the same as those explained in relation to formula (1b).

Examples of the divalent organic group having 1 to 6 carbon atoms for ^X3 and ^X6 include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (e.g., an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon.

The divalent organic group having 1 to 6 carbon atoms for ^X4 and ^X5 may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3.
When the polymer P contains a structural unit represented by general formula (1), the proportion of the structural unit represented by general formula (1) in all structural units of the polymer P is preferably 3 to 40 mol %, more preferably 3 to 30 mol %.

In the structural unit represented by general formula (2) which can constitute the polymer P, R 1 ^S is a group containing only one (meth)acryloyl group. 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 when the developability is improved, the curing tends to be insufficient. Therefore, it is preferable that the polymer P contains either or both of the structural unit represented by general formula (1) and the structural unit represented by general formula (2), thereby achieving a good balance between both the sensitivity and the developability.
R 1 ^S is, for example, a group represented by the following general formula (2a).

In formula (2a), ^X10 is a divalent organic group, and R is a hydrogen atom or a methyl group.
The total number of carbon atoms in X ¹⁰ is preferably 1-30, more preferably 1-20, and even more preferably 1-10.
In formula (2a), ^X10 is a divalent organic group, and R is a hydrogen atom or a methyl group.
The total number of carbon atoms in X ¹⁰ is preferably 1-30, more preferably 1-20, and even more preferably 1-10.

The divalent organic group of X ¹⁰ is preferably, for example, an alkylene group. A portion 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.

The divalent organic group of X ¹⁰ is more preferably a linear alkylene group having a total carbon number of 3 to 6. By appropriately selecting the number of carbon atoms of X ¹⁰ (the chain length of X ¹⁰ ), the structural unit represented by general formula (2) becomes more likely to participate in the crosslinking reaction, and the sensitivity can be increased.

The divalent organic group (e.g., an alkylene group) of X ¹⁰ may be substituted with any substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, and an aryloxy group.

The divalent organic group of ^X10 may be any group other than an alkylene group, for example, a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

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

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

The content (ratio) of each structural unit contained in polymer P can be estimated/calculated from the amount (molar amount) of raw materials used in synthesizing the polymer, the amount of raw materials remaining after synthesis, the presence of peaks in various spectra (e.g., IR spectrum, ^1H -NMR spectrum, ^13C -NMR spectrum), the peak area, etc.

The weight average molecular weight Mw of the polymer P is, for example, 1,000 to 20,000, preferably 2,000 to 18,000, more preferably 3,000 to 14,000, and even more preferably 3,000 to 12,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and solubility in an alkaline developer.

The dispersity of polymer P (weight average molecular weight Mw/number average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of polymer P can be made uniform, which is preferable. These values can be determined by gel permeation chromatography (GPC) measurements using polystyrene as a standard substance.

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

(Thioether Group-Containing Polymer P1)
From the viewpoint of the effects of the present invention, the polymer P of this embodiment preferably contains a thioether group-containing polymer P1.
The thioether group-containing polymer P1 of this embodiment preferably has a structure represented by the following general formula (P): The structural unit A and the structural unit B in general formula (P) typically constitute the main chain of the polymer P1.

In formula (P), p, q and r respectively represent the molar contents of A, B and C in the polymer, and p+q+r=1.
p is greater than 0, and is preferably between 0.25 and 0.75.
q is greater than 0, and is preferably in the range of 0.25 to 0.75.
The value of r is 0 or more, and preferably 0 to 0.5.
p, q or r may be the same or different for each of the n structural units in [ ].
n is an integer from 1 to 6.
X is hydrogen or an organic group having 1 to 30 carbon atoms.
Y is a mono- to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a di- or higher functional thiol group-containing compound, and is bonded to the structural unit in [ ]n via a thioether group derived from the thiol group.

A contains a structural unit represented by general formula (NB).
B contains at least one structural unit selected from the structural units represented by general formula (1) and the structural units represented by general formula (2).
C contains a structural unit derived from a copolymerizable compound having a double bond.
A plurality of As, Bs or Cs may be the same or different.
In general formula (P), the order in which A, B and C are bonded is not particularly limited, and any of A, B and C may be bonded to Y.

In formula (NB), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

In general 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 thioether group-containing polymer P1 of this embodiment contains, as the structural unit B, a structural unit represented by general formula (1) and/or a structural unit represented by general formula (2). In other words, as the structural unit B, it contains either one or both of the structural unit represented by general formula (1) and the structural unit represented by general formula (2). As a result, the photosensitive resin composition containing the thioether group-containing polymer P1 has excellent sensitivity when subjected to a photolithography method.

This is believed to be because the (meth)acryloyl group contained in the structural unit represented by general formula (1) or general formula (2) promotes the curing reaction (polymerization reaction). In addition, the thioether group-containing polymer P1 contains a structural unit represented by general formula (NB) as the structural unit A. This structural unit is chemically robust. Therefore, the thioether group-containing polymer P1 containing this structural unit has a small weight loss when subjected to heat treatment and is stable. Therefore, the photosensitive resin composition containing the thioether group-containing polymer P1 can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

In a preferred embodiment, the thioether group-containing polymer P1 contains a structural unit represented by general formula (1) as an essential component. The structural unit represented by general formula (1) has at least two (meth)acryloyl groups, and therefore the (meth)acrylic resin (a) containing this has high sensitivity in photolithography processing.

In one embodiment, the thioether group-containing polymer P1 may contain, in addition to the above structural units, a structural unit B represented by the general formula (3). By containing the structural unit represented by the general formula (3), the thioether group-containing polymer P1 has high alkali solubility. As a result, the photosensitive resin composition containing the thioether group-containing polymer P1 has excellent developability when subjected to photolithography processing using an alkaline aqueous solution as a developer.

In one embodiment, the thioether group-containing polymer P1 may contain, in addition to the above structural units, a structural unit represented by the general formula (MA) as the structural unit B. The structural unit represented by the general formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the thioether group-containing polymer P1 containing this structural unit has excellent developability. When the thioether group-containing polymer P1 contains a structural unit represented by the general formula (MA), the structural unit represented by the general formula (MA) is preferably 1 to 10 mol %, more preferably 2 to 7 mol %, of all structural units of the thioether group-containing polymer P1.

In one embodiment, the thioether group-containing polymer P1 may contain a divalent structural unit C derived from a copolymerizable compound having a double bond. The structural unit C includes at least one structural unit derived from, for example, substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (cyclohexene, etc.), cyclododecatriene, tricycloundecene, dialkyl fumarates (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.), and the like.
Substituents that these monomers may have include alkyl groups, aryl groups, etc. More specifically, substituted indenes include methylindene, etc. Substituted maleimides include cyclohexylmaleimide, phenylmaleimide, etc. Substituted styrenes include methylstyrene, vinyltoluene, etc.

Among these, the structural unit C preferably includes a structural unit represented by the general formula (4) (a divalent structural unit derived from substituted or unsubstituted indene), a structural unit represented by the general formula (5) (a divalent structural unit derived from substituted or unsubstituted maleimide), a structural unit represented by the general formula (6) (a divalent structural unit derived from substituted or unsubstituted styrene), or a structural unit represented by the general formula (7) (a divalent structural unit derived from substituted or unsubstituted norbornadiene).

In general formula (4), ^R1 and ^R2 each independently represent a hydrogen atom, an alkyl group, or an aryl group. In general formula (5), ^R3 each independently represent a hydrogen atom, an alkyl group, or an aryl group. In general formula (6), ^R4 to ^R6 each independently represent a hydrogen atom, an alkyl group, or an aryl group. In general formula (7), ^R7 to ^R10 each independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

In the thioether group-containing polymer P1 represented by the above general formula (P), X is hydrogen or an organic group having from 1 to 30 carbon atoms. The organic group having from 1 to 30 carbon atoms is the same as the organic group having from 1 to 30 carbon atoms constituting R ¹ to R ⁴ described above.

In the thioether group-containing polymer P1 represented by the above general formula (P), Y is a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a thiol group-containing compound having one or more functionalities. In this embodiment, the number of functional groups is the number of thiol groups. That is, the thiol group-containing compound contains one or more thiol groups, and the organic group (i) bonds to the structural unit in [ ]n via 1 to 6 thioether groups derived from the thiol group. The organic group (i) may have a thiol group that is not involved in the bond with the structural unit in [ ]n, and the thioether group-containing polymer P1 can be obtained as a mixture of resins having n numbers (bond numbers) of 1 to 6.
The organic group (i) having 1 to 30 carbon atoms is monofunctional or more, preferably difunctional or more, more preferably trifunctional or more. The upper limit is not particularly limited, but is hexafunctional or less.
The valence of the organic group (i) having 1 to 30 carbon atoms is, from the viewpoint of the effects of the present invention, monovalent to hexavalent, preferably divalent to hexavalent, and more preferably trivalent to hexavalent.

The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P, and Si. Examples of the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, and heterocyclic groups having 1 to 6 thioether groups (-S-* (* is a bond)).

Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Examples of alkenyl groups include allyl, pentenyl, and vinyl.

Alkynyl groups include ethynyl groups.
Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.
Aralkyl groups include, for example, benzyl and phenethyl groups.
Examples of the alkaryl group include a tolyl group and a xylyl group.

Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups.
Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

Examples of the thiol group-containing compound having one or more functional groups include compounds represented by the following chemical formulas (s-1) to (s-23).

The mono- or higher functional thiol group-containing compound may be used alone or in combination of two or more.
The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms has a thioether group (-S-* (* is a bond)) derived from a thiol group of the thiol group-containing compound at its terminal, and bonds to the structural unit in [ ]n via the thioether group. The organic group (i) may have a thiol group that is not involved in the bond to the structural unit in [ ]n.

When a compound represented by the chemical formula (s-2) is used as the monofunctional or higher thiol group-containing compound, the thioether group-containing polymer P1 of this embodiment can have a structure represented by, for example, the following general formula (I).

In general formula (I), A, B, C, X, p, q, and r have the same meanings as in general formula (P). A, B, C, X, p, q, and r contained in the structural units in the four [ ] may be the same or different.

In general formula (I), the order of bonding of A, B, and C is not particularly limited, and any of A, B, and C may be bonded to the thioether group. In addition, in general formula (I), an example is shown in which the compound represented by chemical formula (s-2) is bonded to the four structural units in [ ] via thioether groups derived from the four mercapto groups, but the structure may have 1 to 3 structural units in [ ] bonded. In this embodiment, the thioether group-containing polymer P1 can be obtained as a mixture containing at least one compound having 1 to 4 structures in [ ] bonded.

The weight average molecular weight Mw of the thioether group-containing polymer P1 is, for example, 1,000 to 15,000, preferably 1,500 to 12,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 8,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and solubility in an alkaline developer.

The dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the thioether group-containing polymer P1 is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the thioether group-containing polymer P1 can be made uniform, which is preferable. These values can be determined by gel permeation chromatography (GPC) measurements using polystyrene as a standard substance.

The glass transition temperature of the thioether group-containing polymer P1 is preferably 150 to 250°C, more preferably 170 to 230°C. The thioether group-containing polymer P1 has a relatively high glass transition temperature due to the inclusion of structural units mainly represented by the general formula (NB). This is preferable in that the pattern formed on the substrate can be stable when manufacturing a liquid crystal display device or a solid-state imaging device. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

The content (ratio) of each structural unit contained in the thioether group-containing polymer P1 of the present embodiment can be estimated/calculated from the amount (molar amount) of raw materials charged during polymer synthesis, the amount of raw materials remaining after synthesis, and peak areas of various spectra (e.g., ^1H -NMR peak areas), etc.

(Method for producing polymer P)
The polymer P of this embodiment may be produced (synthesized) by any method. For example,
a preparation step of preparing a raw material polymer containing a structural unit represented by the above general formula (MA) and a structural unit represented by the above general formula (2);
A polymer P including a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) can be produced by a reaction step of reacting the raw polymer with a compound having a hydroxy group and two or more (meth)acryloyl groups in the presence of a basic catalyst.
Hereinafter, the method for producing (synthesizing) the polymer P of this embodiment through these steps will be described.

Preparation Step The raw material polymer can typically be obtained by polymerizing (addition polymerization) a monomer represented by the following general formula (NBm) with maleic anhydride.
The definitions of R ¹ , R ² , R ^{3 ,} R ⁴ and a1 in formula (NBm) are the same as those in formula (NB). The same also applies to preferred embodiments.

Examples of monomers represented by the general formula (NBm) include norbornene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride.

In the polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more kinds.
Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used.

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

Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP).
The polymerization initiator may be used alone or in combination of two or more kinds.

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

The monomer represented by the general formula (NBm), maleic anhydride, and a polymerization initiator are dissolved in a solvent and charged into a reaction vessel, which is then heated to cause 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 formula (NBm) to maleic anhydride when charged into a reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1.
Through such a process, a "raw polymer" can be obtained.

The raw polymer may be any of random copolymers, alternating copolymers, block copolymers, and periodic copolymers. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.
After synthesis of the raw polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out.

Specifically, the organic layer containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried to increase the purity of the raw polymer.

Reaction Step In the presence of a basic catalyst, the raw material polymer is reacted with a compound having a hydroxy group and two or more (meth)acryloyl groups, whereby the structural unit of general formula (MA) contained in the raw material polymer is ring-opened and the structural unit of general formula (1) is formed.
More specifically, first, a solution is prepared by dissolving a raw material polymer in an appropriate organic solvent.

As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

Next, a polyfunctional (meth)acrylic compound having a hydroxyl group is added to the above solution. A basic catalyst is then added. The solution is then mixed appropriately to obtain a homogeneous solution.

Examples of the polyfunctional (meth)acrylic compound having a hydroxy group include a compound represented by general formula (1b-m) below, a compound represented by general formula (1c-m) below, or a compound represented by general formula (1d-m) below.
The definitions and specific embodiments of k, R, X ¹ , X ¹ ' and X ² in general formula (1b-m) are the same as those in general formula (1b).
The definitions and specific embodiments of k, R, ^X1 , ^X2 , ^X3 , ^X4 , ^X5 and ^X6 in general formula (1c-m) are the same as those in general formula (1c).
The definition of n in general formula (1d-m) is the same as that in general formula (1d).

The following polyfunctional (meth)acrylic compounds having hydroxyl groups can be preferably used. Note that it is also possible to use the compounds shown below in which some or all of the acryloyl groups have been replaced with (meth)acryloyl groups (or vice versa).

As the basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as catalysts. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of the raw polymer. Note that if an excess of the basic catalyst is used, a large amount of acid is required for neutralization, which may complicate purification.

The solution is heated, preferably at 60 to 80°C, for about 3 to 9 hours to open the ring of the structural unit of general formula (MA) contained in the raw polymer and form the structural unit of general formula (1).

For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating process, the structural unit represented by the general formula (2) can be generated in the polymer P.

From the viewpoint of steric hindrance of the reaction, etc., monofunctional (meth)acrylic compounds having a hydroxyl group tend to react more easily with the raw material polymer than polyfunctional (meth)acrylic compounds having a hydroxyl group. Therefore, when generating the structural unit represented by the above-mentioned general formula (2) in the polymer P, it is preferable to add the monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system rather than to charge it in the reaction system from the beginning.
Examples of the monofunctional (meth)acrylic compound having a hydroxy group include compounds represented by the following general formula (2a-m).
In the general formula (2a-m), the definitions of ^X10 and R are the same as those in the general formula (2a).

Specific examples of the compound represented by general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.
After the reaction step, the reaction is stopped by diluting the reaction solution with an organic solvent and adding an acid to neutralize the basic catalyst.

The polymer P of this embodiment can be obtained by the above steps, but the following steps can also be carried out as appropriate to remove unnecessary components other than the desired polymer.

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

An excess amount of toluene is added to the obtained organic solution of polymer P to reprecipitate the polymer, and the polymer powder obtained by the reprecipitation is further washed several times with toluene.
The resulting organic solution of the thioether group-containing (meth)acrylic resin (a) is purified using a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the resulting organic solution of the thioether group-containing (meth)acrylic resin (a) is added to an excess amount of toluene or water to reprecipitate the polymer. The polymer powder obtained by the reprecipitation is further washed several times with toluene or water.
Furthermore, in order to remove formic acid and the basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (about 1 to 3 times).
The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more to obtain a high-purity polymer.
In the liquid-liquid extraction method, water is added to the obtained organic solution of polymer P, and the solution is vigorously stirred in a separatory funnel for at least 3 minutes. The solution is left to stand for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. Water is then added to the organic solution of the polymer after the water removal, and the solution is vigorously stirred in a separatory funnel for at least 3 minutes. The solution is left to stand for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, the steps of adding water and removing the aqueous phase may be further carried out.
The obtained organic solution of the polymer is concentrated by heating under reduced pressure using a rotary evaporator, and then the final solvent (PGMEA, etc.) is added to dilute the concentrated solution. This process is repeated to obtain a solution of polymer P dissolved in the final solvent.

<Method of producing thioether group-containing polymer P1>
The method for producing the thioether group-containing polymer P1 can be performed in the same manner as in the method for producing the polymer P described above, except that in the preparation step of preparing a raw material polymer, a raw material polymer containing a structural unit represented by the above-mentioned general formula (MA), a structural unit represented by the above-mentioned general formula (NB), and the mono- to hexavalent organic group (i) having 1 to 30 carbon atoms is prepared.

The raw polymer can be prepared by polymerizing (addition polymerizing) a monomer composition containing a monomer represented by the general formula (NBm) and maleic anhydride in the presence of the thiol group-containing compound having two or more functionalities.

The monomer composition may contain other monomers in addition to the above monomers.
The other monomer is not particularly limited as long as it is a copolymerizable compound having a double bond, and a known compound can be used, which can be polymerized with the monomer represented by the general formula (NBm) and maleic anhydride. Examples of the other monomer include substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (cyclohexene, etc.), cyclododecatriene, tricycloundecene, dialkyl fumarates (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.), and the like. In this step, the monomer represented by the general formula (2m), maleic anhydride, and, if necessary, other monomers can be polymerized (addition polymerized) in the presence of the thiol group-containing compound having one or more functional groups.

Examples of compounds containing thiol groups having one or more functionalities include, but are not limited to, compounds represented by the above chemical formulas (s-1) to (s-23). The compounds containing thiol groups having one or more functionalities may be used alone or in combination of two or more.

The synthesis of the raw polymer is carried out by dissolving the monomer represented by the general formula (NBm), maleic anhydride and a polymerization initiator in a solvent and charging the resulting solution into a reaction vessel, then heating the vessel and allowing addition polymerization to proceed while dropping in the thiol group-containing compound having one or more functional groups. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. By this process, the "raw polymer" can be obtained.

Next, in the same manner as in the above-mentioned method for producing polymer P, a reaction step is carried out in which the above-mentioned raw 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 a washing step is appropriately carried out to obtain a thioether group-containing polymer P1.

[Compound Q having a thiol group and an alkoxy group or its oligomer]
The polymer solution of this embodiment contains a polymer P and a compound Q having a thiol group and an alkoxy group or an oligomer thereof.
As the compound Q, any known compound can be used as long as it has a thiol group and an alkoxy group and the effects of the present invention can be achieved.

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

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

In this embodiment, examples of the m+n valent organic chain of L include a linear or branched alkylene group (m+n:2) having 1 to 10 carbon atoms, an m+n valent group derived from a linear or branched alkane having 1 to 20 carbon atoms, and an m+n valent group derived from a substituted or unsubstituted siloxane.

X represents a single bond or a divalent organic group which may contain a carbonyl group, a (thio)ester group or a (thio)amide group.
In this embodiment, X is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms.

Q represents a single bond, or a divalent organic group which may contain a carbonyl group, a (thio)ester group, or a (thio)amide group.
In this embodiment, Q is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms.
The molar ratio of m:n is from 1:1 to 1:8, and m+n is from 2 to 20.
The weight average molecular weight of the compound is 100 to 2,000.

Examples of compound Q include 3-mercaptopropylmethyldimethoxysilane (KBM-802, manufactured by Shin-Etsu Silicones), 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Silicones), (3-mercaptopropyl)triethoxysilane, a siloxane chain-containing multifunctional silane coupling agent (KR-519, manufactured by Shin-Etsu Silicones), and an organic chain-containing multifunctional silane coupling agent having the following structural unit.

In the above general formula, a:b (molar ratio) is 2:1 to 4:1. The weight average molecular weight is 1000 to 1500. * is a bond. Examples of the compound include X-12-1154 (manufactured by Shin-Etsu Silicones Co., Ltd.).
The compound Q or its oligomer may be used alone or in combination of two or more kinds.

In the polymer solution of this embodiment, the compound Q or its oligomer is present in an amount of 0.25 to 20% by mass, preferably 1.0 to 15% by mass, and more preferably 2.0 to 12% by mass, based on the polymer P, from the viewpoint of the effects of the present invention.

[Compound having two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound)]
The polymer solution of the present embodiment may contain a compound having two or more (meth)acryloyl groups, together with the polymer P and the compound Q or its oligomer. By containing such a compound, the alkali solubility of the polymer solution is further improved, and further yellowing of the polymer solution is further reduced, making it possible to obtain a cured product with excellent transparency.

Examples of compounds having two or more (meth)acryloyl groups (referred to as "polyfunctional (meth)acrylic compounds" in this specification) that may be used in the polymer solution of this embodiment include, but are not limited to, compounds represented by the following general formula (1b-p), compounds represented by the general formula (1c-p), and compounds represented by the general formula (1d-p).

The definitions and specific embodiments of k, R, ^X1 , ^X1 ', and ^X2 in general formula (1b-p) are the same as those in general formula (1b) above. The definitions and specific embodiments of k, R, ^X1 , ^X2 , ^X3 , ^X4 , ^X5 , and ^X6 in general formula (1c-p) are the same as those in general formula (1c) above.

In general formulae (1b-p), (1c-p) and (1d-p), Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.
The compounds in which Y is a hydrogen atom in general formula (1b-p), general formula (1c-p), and general formula (1d-p) may be unreacted monomers (i.e., compounds represented by general formula (1b-p), general formula (1c-p), and general formula (1d-p)), or may be added separately.
In formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

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

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

In the resin composition of this embodiment, the polyfunctional (meth)acrylic compound is preferably blended in an amount such that the peak area derived from the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the resin composition is 5 to 100% of the peak area of the photosensitive resin, and more preferably 10 to 90%. By blending the polyfunctional (meth)acrylic compound in the above range, the resulting resin composition has excellent alkali solubility.

[Compound having one (meth)acryloyl group]
The polymer solution of the present embodiment may contain a compound having one (meth)acryloyl group (referred to as a "monofunctional (meth)acrylic compound" in this specification) in addition to the polymer P and the compound Q or its oligomer. By containing the monofunctional (meth)acrylic compound, the alkali solubility of the resulting polymer solution is improved, and further yellowing is reduced.

Examples of the monofunctional (meth)acrylic compound that may be used in the polymer solution of the present embodiment include compounds represented by the following general formula (2a-m). The monofunctional (meth)acrylic compound may be an unreacted monomer, or may be added separately.
In the general formula (2a-m), the definitions of ^X10 and R are the same as those in the general formula (2a).

Specific examples of compounds represented by general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

When the above-mentioned polyfunctional (meth)acrylic compound is blended in the polymer solution of this embodiment, it is preferably blended in an amount such that the peak area attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is 5 to 100% of the peak area of polymer P, and more preferably 10 to 90%. By blending the polyfunctional (meth)acrylic compound in the above range, the resulting polymer solution has excellent alkali solubility.

When a monofunctional (meth)acrylic compound is blended into the polymer solution of this embodiment, the amount is preferably such that the peak area attributable to the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is 5 to 50% of the peak area of polymer P, and more preferably 10 to 35%. By blending the monofunctional (meth)acrylic compound in the above range, the resulting polymer solution has better alkali solubility.

<Polymer solution>
The polymer solution of the present embodiment contains the above-mentioned polymer P, the above-mentioned compound Q or its oligomer, and a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound added as necessary. By providing the above-mentioned configuration, the alkali dissolution rate can be, for example, 150 nm/s or more, and preferably 300 nm/s or more.

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

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more.
The amount of the organic solvent used is not particularly limited, but is used in such an amount that the concentration of the non-volatile components becomes, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

(Preparation of polymer solution)
The polymer solution of the present embodiment can be prepared by mixing the above components by a known method. The polymer solution of the present embodiment is used as a resin material for the photosensitive resin composition described below.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment comprises the above-mentioned polymer P, the above-mentioned compound Q or an oligomer thereof, and a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound added as necessary. That is, the photosensitive resin composition of the present embodiment contains the above-mentioned polymer solution (varnish, resin composition) of the present embodiment and a photosensitizer. Each component is described below. do.

[Photosensitizer]
The photosensitizer used in the photosensitive resin composition of the present embodiment includes a photoradical polymerization initiator. Known compounds can be used as the photoradical polymerization initiator, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl) alkylphenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine halomethylated triazine compounds such as 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; halomethylated oxadiazole compounds such as 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 compounds such as 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds.
The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of the polymer P.

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

In the photosensitive resin composition of this embodiment, the polyfunctional (meth)acrylic compound is preferably blended in an amount such that the peak area attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the photosensitive resin composition is 5 to 50% of the peak area of polymer P, and more preferably 10 to 35%. By blending the polyfunctional (meth)acrylic compound in the above range, the resulting photosensitive resin composition has excellent alkali solubility.

The photosensitive resin composition of this embodiment may contain, in addition to the above-mentioned polymer P, polyfunctional (meth)acrylic compound, and photosensitizer, a compound having one (meth)acryloyl group (monofunctional (meth)acrylic compound). The monofunctional (meth)acrylic compound is the same as that described above. By including the monofunctional (meth)acrylic compound, the alkali solubility of the obtained photosensitive resin composition is further improved and yellowing is reduced.

When the photosensitive resin composition of this embodiment contains a monofunctional (meth)acrylic compound, the amount of the compound is preferably such that the peak area attributable to the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the photosensitive resin composition is 5 to 50% of the peak area of polymer P, and more preferably 10 to 35%. By adding a monofunctional (meth)acrylic compound in the above range, the resulting photosensitive resin composition has excellent alkali solubility.

In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition 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.

As organic pigments, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, dye lake pigments, etc. can be used.

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

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

Colorants (particularly pigments) with an appropriate average particle size can be used depending on the purpose and application, but when transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, and when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

Depending on the purpose and application, the colorant may be surface-treated with rosin, surfactant, resin-based dispersant, pigment derivative, oxide film, silica coating, wax coating, or other treatments.

When the photosensitive resin composition contains a colorant, the amount of the colorant may be set appropriately depending on the purpose and application, but in order to achieve both coloring concentration and dispersion stability of the colorant, the amount of the colorant is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % of the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

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

As the light-shielding agent, any known light-shielding agent can be used without any particular limitation. For example, black pigments such as carbon black, bone black, graphite, iron black, and titanium black can be used as the light-shielding agent.
When the photosensitive resin composition contains a light-shielding agent, the photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agents.

When the photosensitive resin composition contains a light-blocking agent, the amount of the light-blocking agent may be set appropriately depending on the purpose and application, but in order to achieve both light-blocking performance and dispersion stability of the light-blocking agent, the amount of the light-blocking agent is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % of the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

The photosensitive resin composition typically contains a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. can be used.

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

The crosslinking agent is not particularly limited as long as it can crosslink the polymer (can chemically bond with the polymer) by the action of the activated chemical species generated from the photopolymerization initiator.
The crosslinking agent may form a bond by reacting with itself instead of only chemically bonding with the polymer.

The crosslinking agent is preferably, for example, a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not fall under the above-mentioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) of the polymer in terms of uniform curing property, further improvement of sensitivity, etc.
There is no particular upper limit to the number of functionalities (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, and preferably 6 or less.

Specific examples of the crosslinking agent include the following:
Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added Polyfunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate.

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

(Meth)acrylic acid esters containing vinyl ether groups, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate.

Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether.
Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate.

Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate.
Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate.

Polyfunctional urethane (meth)acrylates obtained by reacting 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 aromatic vinyls such as divinylbenzene.

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

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one type of crosslinking agent, or may contain two or more types. When the photosensitive resin composition contains a crosslinking agent, the amount may be appropriately set according to the purpose and application. As an example, the amount of crosslinking agent may be usually about 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, per 100 parts by mass of polymer P.

Depending on various purposes and required characteristics, the photosensitive resin composition may contain components such as fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, development aids, plasticizers, polymerization inhibitors, UV absorbers, antioxidants, matting agents, defoamers, leveling agents, surfactants, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropic aids, silane coupling agents, and polyhydric phenol compounds.

[Films, color filters, black matrices, liquid crystal display devices and solid-state imaging devices]
A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition, exposing and developing the film to form a pattern. This film is applied to color filters, black matrices, and the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Also, 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 imaging device equipped with a color filter or a black matrix can be manufactured.
A typical procedure for forming a pattern will now be described.

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

The substrate to which the composition is applied is not particularly limited, and examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate.
The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed on its surface, and may be surface-treated to improve adhesion.

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

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

The thickness of the photosensitive resin film is not particularly limited and may be adjusted as appropriate depending on the final pattern to be obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by the content of the solvent in the photosensitive resin composition and the coating method, etc.

(exposure)
Exposure is typically carried out by applying actinic rays to the photosensitive resin film through an appropriate photomask.

Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling, the light source is preferably g-rays, h-rays, or i-rays from a mercury lamp, and i-rays are particularly preferred. Two or more types of light may be used in combination. As the exposure device, a contact aligner, a mirror projection, or a stepper is preferred.
The amount of light for exposure may be appropriately adjusted depending on the amount of photosensitizer in the photosensitive resin film, and is, for example, about 100 to 500 mJ/cm ² .

After exposure, the photosensitive resin film may be heated again (Post Exposure Bake) if necessary. 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. Post exposure baking promotes the reaction caused by the radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

(developing)
The exposed photosensitive resin film can be developed with an appropriate developer to obtain a pattern, and a substrate having a pattern can be produced.

In the development step, development can be carried out using an appropriate developer, for example, by a dipping method, a paddle method, a rotary spray method, etc. By development, the exposed area (in the case of a positive type) or the unexposed area (in the case of a negative type) of the photosensitive resin film is dissolved and removed, thereby obtaining a pattern.
There is no particular limitation on the type of developer that can be used, and for example, an alkaline aqueous solution or an organic solvent can be used.

Specific examples of alkaline aqueous solutions include (i) aqueous inorganic alkaline solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous organic amine solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

Specific examples of the organic solvent include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether-based solvents such as propylene glycol monomethyl ether.
The developer may contain, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like.

In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution.
The concentration of the aqueous alkaline solution is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.
Through the above steps, a pattern can be obtained/a substrate having a pattern can be manufactured, but various treatments may be carried out after development.

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

The pattern thus obtained may be heated to sufficiently harden it. The heating temperature is typically 150 to 400° C., preferably 160 to 300° C., and more preferably 200 to 250° C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a temperature-programmable heating oven, or the like. The atmospheric gas used in the heat treatment may be air or an inert gas such as nitrogen or argon. Heating may also be performed under reduced pressure.
FIG. 1 shows a schematic diagram of an example of the structure of a liquid crystal display device and/or a solid-state imaging device that includes a color filter and/or a black matrix.

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

The substrate 10 is usually made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, a polymer of a cyclic olefin, etc. The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical treatment, etc., as necessary.
The substrate 10 is preferably made of glass.
The black matrix 11 is formed, for example, from a cured product of a photosensitive resin composition containing a light-shielding agent.

Color filters 12 usually come in three colors: red, green, and blue. The color filters 12 are made of a cured product of a photosensitive resin composition that contains a colorant corresponding to each color.

The above describes the embodiments of the present invention, but these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements that can achieve the object of the present invention are included in the present invention.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

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 PEMP: Pentaerythritol tetrakis (3-mercaptopropionate)
4-HBA: 4-hydroxybutyl acrylate PGMEA: propylene glycol monomethyl ether acetate KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-802: 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicones)
X-12-1154: Organic chain-containing multifunctional silane coupling agent (manufactured by Shin-Etsu Silicones)
KR-519: siloxane chain-containing multifunctional silane coupling agent (manufactured by Shin-Etsu Silicones)
KBM-3066: 1,6-bis(trimethoxysilyl)hexane (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-3103C: Decyltrimethoxysilane (manufactured by Shin-Etsu Silicones)
KBM-5103: 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicones)

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

<Synthesis of raw polymer>
First, a raw material polymer containing maleic anhydride structural units and 2-norbornene structural units (containing no (meth)acryloyl groups) was synthesized. The details are shown below.

(Synthesis of Raw Polymer 1)
353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene (NB), and 33.16 g (0.144 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed into a suitable sized reaction vessel equipped with a stirrer and a condenser, and dissolved in a mixed solvent of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.
Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 65° C. for 1.5 hours with stirring, and then further heated at 80° C. for 6 hours to polymerize maleic anhydride and 2-norbornene, thereby producing a polymerization solution.
The polymerization solution obtained above was added dropwise to 8,519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum-dried at a temperature of 120° C. to obtain 607.5 g of a polymer (raw polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride.
The resulting polymer had a weight average molecular weight Mw of 7,000 as measured by gel permeation chromatography (GPC), and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.82.

(Synthesis of Raw Material Polymer 2)
In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g, 4.8 mol in terms of NB), maleic anhydride (MA, 470.69 g, 4.8 mol) and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyrate dimethyl (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21 g, 0.19 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 93.82 g, 0.19 mol) dissolved in MEK 193.4 g was added over 1 hour. Then, the mixture was further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid was washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 910.1 g of a polymer (raw polymer 2) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride.
The resulting polymer had a weight average molecular weight Mw of 3,500 and a polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) of 1.62 as measured by gel permeation chromatography (GPC).

ＰＥＭＰを使用して合成した原料ポリマー２の^１３Ｃ－ＮＭＲ測定において、６２．０ｐｐｍ付近に、炭素ｂ由来のピークｂの出現を確認した。反応溶液のＧＰＣ測定で、ＰＥＭＰ単体のピークが認められず、未反応のＰＥＭＰが残っていないことから、ＰＥＭＰが原料ポリマー２中に取り込まれたことを確認した。
また、原料ポリマー２の^１３Ｃ－ＮＭＲ測定では、炭素a由来のピークａが確認されず、代わりに２８ｐｐｍ付近にチオエーテル（Ｒ－Ｓ－Ｒ'）に対応するピークｃが出現した。このピークｃの積分値はピークｂの積分値のおよそ２倍になっていることから、原料ポリマー２は下記のようなチオエーテル基を有する骨格を備えており、チオール基は消失していた。原料ポリマー２を用いて合成した実施例のポリマーも同様の骨格を備えると考えられる。

^１３Ｃ－ＮＭＲ測定の条件は以下の通りである。
（試験条件）測定サンプルは、秤量した試料に測定溶媒を加えて濃度調製した後、ＮＭＲ測定用試料管に規定分量注いで作製した。
・測定装置：日本電子ＪＮＭ－ＥＣＡ４００超伝導ＦＴ－ＮＭＲ装置
・共鳴周波数：１００．５３ＭＨｚ
・測定核：^１３Ｃ
・測定法：ＮＮＥ測定（インバースゲートデカップリング法）
・パルス幅：３．８３μｓｅｃ
・パルス繰り返し待ち時間：３０ｓ
・積算回数：４０９６回
・測定温度：室温
・測定溶媒：ＤＭＳＯ－ｄ_６（重水素化ジメチルスルホキシド）
・試料濃度：２０％（ｗ／ｖ） [Confirmation of thioether structure contained in raw polymer 2]
By ¹³ C-NMR measurement of PEMP alone represented by the following chemical formula, peak a derived from carbon a was confirmed at about 19.0 ppm, and peak b derived from carbon b was confirmed at about 62.0 ppm.

In the ^13C -NMR measurement of the raw material polymer 2 synthesized using PEMP, the appearance of peak b derived from carbon b was confirmed at about 62.0 ppm. In the GPC measurement of the reaction solution, no peak of PEMP alone was observed, and no unreacted PEMP remained, so it was confirmed that PEMP was incorporated into the raw material polymer 2.
Furthermore, in the ^13C -NMR measurement of raw polymer 2, peak a derived from carbon a was not confirmed, and instead peak c corresponding to thioether (R-S-R') appeared at about 28 ppm. Since the integral value of this peak c is about twice the integral value of peak b, raw polymer 2 has a skeleton having a thioether group as shown below, and the thiol group has disappeared. It is considered that the polymer of the example synthesized using raw polymer 2 also has a similar skeleton.

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

[Amount of sulfur in raw polymer 2]
The amount of sulfur in the obtained raw material polymer 2 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the polymer. In addition, in the GPC measurement of the reaction solution before the addition of methanol, the peak derived from PEMP disappeared, and it was confirmed that PEMP was incorporated in the polymer.
As a result of elemental analysis, the sulfur content in Raw Material Polymer 2 was found to be 2.4 wt %.
The elemental analysis method is as follows.
- Test item: Flask combustion - ion chromatography method for determining total sulfur - Test method: Flask combustion - ion chromatography method (1) Approximately 50 mg of a sample is completely burned in a sealed flask with the atmosphere replaced with oxygen.
(2) The gas produced is collected in a flask to which hydrogen peroxide absorbing liquid has already been added, and the resulting solution is adjusted to 50 ml to serve as the test liquid.
(3) The test solution and the standard solution are introduced into an ion chromatography analyzer, the concentration of sulfate ions is determined using the calibration curve method, and the amount of sulfur contained in the sample is calculated.
- Equipment used: Dionex ICS-3000 ion chromatograph

[Example 1]
<Preparation of polymer solution>
A polymer solution 1 containing a photosensitive resin 1 (polymer P) was prepared by ring-opening the MA unit of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Details will be described below.
First, 100.30 g of MEK was added to 60.00 g of raw polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the reaction was allowed to proceed for 2 hours at 70° C. The resulting 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. Liquid-liquid extraction and subsequent solvent replacement were then carried out as follows.
Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was then repeated once more.
Solvent replacement: The obtained reaction mixture was subjected to removal of the solvent at 50° C. under reduced pressure using a rotary evaporator. The solid content concentration of the polymer solution was confirmed to be 27±2% by mass as measured by a heat-drying moisture meter, and the solvent removal operation was interrupted. Thereafter, PGMEA was added so that the solid content concentration was 18% by mass, and mixed until uniform. The solvent was removed at 50° C. under reduced pressure in the same manner, and the solid content concentration was adjusted to 27±2% by mass as measured by a heat-drying moisture meter. Then, PGMEA was added so that the solid content concentration was 18% by mass, and the operation of mixing until uniform was repeated two more times. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration was 30±3% by mass, and the operation of stirring until uniform was performed. The above operations remove the solvent used in the reaction, and the solvent is replaced with PGMEA.
Subsequently, 5% by weight of KBM-803 was mixed with respect to the solid content of the polymer solution (resin composition) as compound Q. As a result, a photosensitive resin 1 in which the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N, 4-HBA, and water, and a polymer solution (resin composition) 1 containing remaining (free) A-TMM-3LM-N, remaining (free) 4-HBA, and KBM-803 as compound Q were obtained.
The obtained polymer solution 1 was analyzed by gel permeation chromatography to measure the amounts of photosensitive resin 1, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in polymer solution 1, as well as the weight average molecular weight and polydispersity of photosensitive resin 1. The results are shown in Table 1. The amount of free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the photosensitive resin in a gel permeation chromatography (GPC) chart of the resin mixture.
The measurement conditions for gel permeation chromatography are as follows.
The GPC measurement device used was an HLC-8320GPC EcoSEC manufactured by Tosoh Corporation. The column temperature was set to 40.0° C., and the pump flow rate was set to 0.350 mL/min.
・Peak position (retention time)
Photosensitive resin: Peak detected before 20 minutes (peak with shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA)
A-TMM-3LM-N: Sum of two peaks at 20.0-20.6 minutes and 20.6-21.5 minutes 4-HBA: 21.7-22.4 minutes Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[Alkaline dissolution rate of polymer solution]
Polymer solution 1 was spin-coated on a wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to prepare a resin film having a thickness of about 2 μm.
The resin film was immersed together with the wafer in a 2% aqueous sodium carbonate solution at 23° C. to measure the dissolution rate of the resin film. The results are shown in Table 1.
The dissolution rate was calculated by visually observing the immersed wafer and measuring the time until the resin film dissolved and the interference pattern disappeared, and dividing the film thickness by the time. The results are shown in Table 1. If the alkali dissolution rate is 140 nm/s or more, the material can be used as a photosensitive material without any problems. In particular, if it is 300 nm/s or more, it can be considered to be particularly good.

<Preparation of Photosensitive Resin Composition>
The following components were dissolved in PGMEA so that the total solids concentration was 30% by mass, thereby obtaining a photosensitive resin composition 1.
Polymer solution 1: 100 parts by mass (Here, polymer solution 1 was weighed out so that the solid content (the total amount of the photosensitive resin, the polyfunctional (meth)acrylic compound, and the component added later) was 100 parts by mass. The same applies to the other polymer solutions.)
Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass Photopolymerization initiator (manufactured by BASF, Ingacure OXE01): 5 parts by mass Adhesion assistant (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

[Yellow Index]
The photosensitive resin composition was prepared so that the total solid content concentration was 30% by mass. The same applies to the following examples and comparative examples.
The photosensitive resin composition thus obtained was spin-coated on Eagle XG glass (manufactured by Corning, thickness 0.5 mm) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film having a thickness of about 3.0 μm (±0.1 μm).
This thin film was exposed to g+h+i lines at an exposure dose of 100 mJ/cm ² using a g+h+i line mask aligner (PLA-600F) manufactured by Canon.
After exposure, the thin film was developed (with the wafer immersed) in a 2.0 mass % aqueous sodium carbonate solution at 23° C. for 60 seconds to obtain a thin film that had been exposed and developed with an exposure dose of 100 mJ/cm ² .
The thin film was heat-treated in air at 230° C. for 30 minutes. After cooling the thin film in air at room temperature, the thin film was again heat-treated in air at 230° C. for 30 minutes. The same operation was repeated, and heat treatment in air for 30 minutes was performed three times in total.
The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement points using a color difference meter CR-5 (manufactured by Konica Minolta), and the average value was taken as the YI value. The measurement type was transmission measurement, and uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm) was used for 100% calibration. The results are shown in Table 2. If the yellow index is 1.20 or less, the heat discoloration resistance can be considered to be good.

[Alkaline dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)]
The photosensitive resin composition was prepared so that the total solid content concentration was 30% by mass. The same applies to the following examples and comparative examples.
The obtained photosensitive resin composition was spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to prepare a resin film having a thickness of about 2 μm.
This resin film was immersed together with the wafer in a 2% aqueous sodium carbonate solution at 23° C., and the dissolution rate of the resin film was measured.
The dissolution rate was calculated by measuring the time it took for the resin film to dissolve and the interference pattern to disappear by visually observing the immersed wafer, and dividing the time by the film thickness. The results are shown in Table 2.

[Sensitivity Evaluation 1 of Photosensitive Resin Composition (Exposure Amount at Which Residual Film Rate is 90% or More)]
The photosensitive resin composition was prepared so that the total solid content concentration was 30% by mass. The same applies to the following examples and comparative examples.
The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer that had been treated with HMDS (hexamethyldisilazane), and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film A having a thickness of about 3.0 μm (±0.3 μm).
This thin film A was exposed to g+h+i rays at an exposure dose of 100 mJ/cm ² using a photomask having a gradation of light shielding rate of 1 to 100% using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc.
After exposure, the thin film was developed (with the wafer immersed) in a 2.0 mass % aqueous sodium carbonate solution at 23° C. for 60 seconds to obtain thin film B that had been exposed and developed at exposure doses of 1 to 100 mJ/cm ² .
From the film thicknesses of the thin films A and B obtained by the above method, the remaining film ratio was calculated according to the following formula.
Remaining film rate (%)=(film thickness of thin film B at each exposure dose/film thickness of thin film A)×100
The exposure dose at which the residual film ratio was 90% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 2. If the exposure dose at which the residual film ratio was 90% or more was 50 mJ/ ^cm2 or less, the photosensitive composition could be used without any problems.

[Sensitivity Evaluation 2 of Photosensitive Resin Composition (Film Remaining Rate after Exposure at Low Exposure Amount)]
(Residual film ratio at exposure dose of 5 mJ/ ^cm2 )
The photosensitive resin composition was prepared so that the total solid content concentration was 30% by mass. The same applies to the following examples and comparative examples.
The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer that had been treated with HMDS (hexamethyldisilazane), and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film A having a thickness of 3.0 μm (±0.3 μm).
This thin film A was exposed to g+h+i rays at an exposure dose of 5 mJ/ ^cm2 using a Canon g+h+i ray mask aligner (PLA-501F) through a photomask having a gradation of light shielding rate of 1 to 100%.
After the exposure, the thin film was developed in a 2.0 mass % aqueous sodium carbonate solution at 23° C. for 60 seconds (immersion with the wafer) to obtain a thin film B.
The remaining film ratio was calculated from the film thicknesses of the thin films A and B obtained by the above method according to the following formula. The results are shown in Table 2.
Remaining film rate (%)=(film thickness of thin film B at each exposure dose/film thickness of thin film A)×100

[Examples 2 to 3, Comparative Examples 1 to 3]
Polymer solutions 2 to 6 and photosensitive resin compositions 2 to 6 were prepared in the same manner as in Example 1 except that, for Examples 2 to 3, the type and amount of compound Q were changed as shown in Table 1, and for Comparative Examples 1 to 3, compound Q was either not added or was replaced with a compound other than compound Q (a silane coupling agent) and the amount added was changed as shown in Table 1. The results of measuring the physical properties are shown in Tables 1 and 2.

[Example 4]
<Preparation of polymer solution>
A polymer solution 7 containing a photosensitive resin 2 (polymer P) was prepared by ring-opening the MA unit of raw material polymer 2 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Details will be described below.
First, 100.30 g of MEK was added to 60.00 g of raw polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution.
Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the reaction was allowed to proceed for 2 hours at 70° C. The resulting 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. Liquid-liquid extraction and subsequent solvent replacement were then carried out as follows.
Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and the same operation was then carried out once more.
Solvent replacement: The obtained reaction mixture was subjected to removal of the solvent at 50° C. under reduced pressure using a rotary evaporator. The solid content concentration of the polymer solution was confirmed to be 27±2% by mass as measured by a heat-drying moisture meter, and the solvent removal operation was interrupted. Thereafter, PGMEA was added so that the solid content concentration was 18% by mass, and mixed until uniform. The solvent was removed at 50° C. under reduced pressure in the same manner, and the solid content concentration was adjusted to 27±2% by mass as measured by a heat-drying moisture meter. Then, PGMEA was added so that the solid content concentration was 18% by mass, and the operation of mixing until uniform was repeated two more times. Thereafter, the solvent was removed or PGMEA was added so that the solid content concentration was 30±3% by mass, and the operation of stirring until uniform was performed. The above operations remove the solvent used in the reaction, and the solvent is replaced with PGMEA.
Subsequently, 2% by weight of KBM-803 was mixed with respect to the solid content of the polymer solution (resin composition) as compound Q. As a result, a photosensitive resin 2 in which the structural units derived from maleic anhydride in the raw polymer were ring-opened with A-TMM-3LM-N, 4-HBA, and water, and a polymer solution (resin composition) 7 containing remaining (free) A-TMM-3LM-N, remaining (free) 4-HBA, and KBM-803 as compound Q were obtained.
The obtained polymer solution 7 was analyzed by gel permeation chromatography to measure the amounts of photosensitive resin 2, free polyfunctional (meth)acrylic compound, and free monofunctional (meth)acrylic compound contained in polymer solution 7, as well as the weight average molecular weight and polydispersity of the photosensitive resin. The results are shown in Table 1. The amount of free (meth)acrylic compound is shown as the ratio (%) of the peak area of the free (meth)acrylic compound to the peak area of the photosensitive resin in a gel permeation chromatography (GPC) chart of the resin mixture.
The measurement conditions for gel permeation chromatography are as follows.
The GPC measurement device used was an HLC-8320GPC EcoSEC manufactured by Tosoh Corporation. The column temperature was set to 40.0° C., and the pump flow rate was set to 0.350 mL/min.
・Peak position (retention time)
Photosensitive resin: Peak detected before 20 minutes (peak with shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA)
A-TMM-3LM-N: Sum of two peaks at 20.0-20.6 minutes and 20.6-21.5 minutes 4-HBA: 21.7-22.4 minutes Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).
The results of the physical property measurements are shown in Table 1.

<Preparation of Photosensitive Resin Composition>
Photosensitive resin composition 7 was obtained by dissolving the following components in PGMEA so that the total solids concentration was 30% by mass.
Polymer solution 7: 100 parts by mass (Here, polymer solution 7 was weighed so that the solid content (the total amount of the photosensitive resin, the polyfunctional (meth)acrylic compound, and the component added later) was 100 parts by mass.)
Polyfunctional acrylate (dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass Photopolymerization initiator (BASF Corporation, Ingacure OXE01): 5 parts by mass Adhesion aid (Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass Surfactant (DIC Corporation, F-556): 0.5 parts by mass The results of measuring the physical properties are shown in Tables 1 and 2.

[Example 5, Comparative Examples 4 to 10]
Polymer solutions 8 to 15 and photosensitive resin compositions 8 to 15 were prepared in the same manner as in Example 4 except that the type and amount of compound Q were changed as shown in Table 1 for Example 5, and that compound Q was either not added or was replaced with a compound other than compound Q (a silane coupling agent) and the amount added was changed as shown in Table 1 for Comparative Examples 4 to 10. The results of measuring the physical properties are shown in Tables 1 and 2.

[Comparative Examples 11 to 17]
Photosensitive resin 3 (polymer P) was prepared in the same manner as in Example 1, using 38.75 g of A-TMM-3LM-N and 99.71 g of MEK. Polymer solutions 16 to 22 and photosensitive resin compositions 16 to 22 were prepared in the same manner as in Example 1, except that compound Q was either not added or was replaced by a compound other than compound Q (a sulfide compound or a thiol compound) and the amount added was changed as shown in Table 1. The results of measuring the physical properties are shown in Tables 1 and 2.

[Example 6, Comparative Example 18]
The MA unit of the raw material polymer 1 was ring-opened with a monofunctional (meth)acrylic compound to prepare a photosensitive resin 4 (polymer P). The details are described below.
First, 18.44 g of MEK was added to 10.00 g of the raw material polymer 1 (0.052 mol in terms of MA) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added and reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution.
The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the following procedure.
The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product was dried at 40° C. for 12 hours. The polymer obtained was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass, and photosensitive resin 4 (polymer P) was prepared.
Polymer solutions 23 to 24 and photosensitive resin compositions 23 to 24 were prepared in the same manner as in Example 1, except that either compound Q was added or no compound was added as in Example 1. The results of measuring the physical properties are shown in Tables 1 and 2.

As shown in Table 2, Examples 1 to 3 in which "compound Q having a thiol group and an alkoxy group" was added to Comparative Example 1 (no chain transfer agent in the polymer chain, molar ratio of polyfunctional acrylate to maleic anhydride: 0.375) had a low yellow index and excellent transparency, and the residual film rate at an exposure dose of 5 mJ/ ^cm2 was significantly improved, resulting in improved sensitivity. However, in Comparative Examples 2 and 3 in which a silane coupling agent other than compound Q was added, no addition effect was observed.
Examples 4 and 5, in which Compound Q was added to Comparative Example 4 (containing a chain transfer agent in the polymer chain, molar ratio of polyfunctional acrylate to maleic anhydride: 0.375), had a low yellow index and excellent transparency, and the residual film rate at an exposure dose of 5 mJ/ ^cm2 was significantly improved, resulting in improved sensitivity. However, in Comparative Examples 5 to 10, in which a silane coupling agent other than Compound Q was added, no addition effect was observed.
In Comparative Examples 12 to 17, in which a compound not included in Compound Q (a sulfide compound or a thiol compound) was added to Comparative Example 11 (no chain transfer agent in the polymer chain, molar ratio of polyfunctional acrylate to maleic anhydride: 0.25), no addition effect was observed.
Furthermore, Example 6, in which Compound Q was added to Comparative Example 18 (no chain transfer agent in the polymer chain, molar ratio of monofunctional acrylate to maleic anhydride: 1.25), had a low yellow index and excellent transparency, and the residual film ratio at an exposure dose of 5 mJ/ ^cm2 was significantly improved. Furthermore, the exposure dose at which the residual film ratio became 90% or more was significantly reduced, and the sensitivity was improved.

As described above, the photosensitive resin composition containing the polymer solution of the Example had a higher residual film ratio at low exposure doses compared to the Comparative Example. Furthermore, since the exposure dose at which the residual film ratio was 90% or more was also low, it was possible to provide a resin cured product (film) that cured at low exposure doses, had high sensitivity, reduced yellowing, and excellent transparency. Furthermore, the alkali dissolution rate of the photosensitive resin composition of the Example was not affected by compound Q. In other words, the photosensitive resin composition of the Example had an excellent balance of these physical properties.

<Preparation of Color Filter>
A suitable amount of pigment dispersion NX-061 (green, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin compositions prepared in Examples 1 to 6 to prepare colored photosensitive resin compositions.
This was formed into a film on a substrate, and then exposed to light and developed with an alkali to form a green color filter.
Furthermore, by using NX-053 (blue) or NX-032 (red) manufactured by the same company instead of NX-061 as the pigment dispersion liquid, blue or red color filters could be formed.

<Preparation of Black Matrix>
A suitable amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin compositions prepared in Examples 1 to 6 to prepare black photosensitive resin compositions.
This was applied to a substrate as a film, and then exposed to light and developed with an alkaline solution to form a black matrix.

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

Claims (10)

A structural unit represented by general formula (NB),
A polymer comprising at least one structural unit selected from a structural unit represented by general formula (1) and a structural unit represented by general formula (2); and a compound having a thiol group and an alkoxy group or an oligomer thereof,
The compound having a thiol group and an alkoxy group includes a compound represented by the following general formula (a):
A polymer solution , in which the compound having a thiol group and an alkoxy group or an oligomer thereof is present in an amount of 0.25% by mass or more and 20% by mass or less relative to the polymer .

(In general formula (NB), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.)

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

(In general formula (2), ^Rs is a group having one (meth)acryloyl group.)

(In general formula (a), R each independently represents an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two R are alkoxy groups having 1 to 3 carbon atoms.
L represents an m+n valent organic chain which may contain one or more atoms selected from O, N, S, P and Si.
X represents a single bond or a divalent organic group which may contain a carbonyl group, a (thio)ester group or a (thio)amide group.
Q represents a single bond, or a divalent organic group which may contain a carbonyl group, a (thio)ester group, or a (thio)amide group.
The molar ratio m:n is 1:1 to 1:8, and the weight average molecular weight of the compound is 100 to 2000. The polymer solution of claim 1 further comprising a compound having two or more (meth)acryloyl groups. The polymer solution according to claim 1 or 2 , further comprising a compound having one (meth)acryloyl group. The polymer solution according to any one of claims 1 to 3 , wherein the polymer further comprises a structural unit represented by general formula (3).

The polymer solution according to any one of claims 1 to 4 , wherein the polymer further comprises a structural unit represented by general formula (MA).

The polymer solution according to any one of claims 1 to 5 , wherein the weight average molecular weight of the polymer is 1,000 or more and 20,000 or less. The polymer solution according to claim 1 , further comprising an organic solvent. 8. The polymer solution according to claim 7 , wherein the organic solvent is at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, and cyclohexanone. The polymer solution according to any one of claims 1 to 8 , which is used for forming a color filter or a black matrix. A photosensitive resin composition comprising the polymer solution according to any one of claims 1 to 9 and a photosensitizer.

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