TW202124486A - Resin composition, photosensitive resin composition and its cured product - Google Patents

Abstract

This resin composition contains: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); and a compound having at least two (meth)acryloyl groups. (In formula (NB), R1, R2, R3, and R4 are each independently a hydrogen atom or a C1-C30 organic group, and a1 is 0, 1, or 2.) (In formula (1), Rp is a group having at least two (meth)acryloyl groups.).

Description

Resin composition, photosensitive resin composition and cured product

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

A liquid crystal display device or a solid-state imaging element generally includes a color filter or a black matrix. The color filter or the black matrix has a structure in which a colored pattern or a protective film is formed on a substrate. As a method of forming a colored pattern or a protective film in these structures, a method of forming a photosensitive resin composition by photolithography has become the mainstream. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. The alkali-soluble resin At least the side chain contains a group having an acidic group and two or more different polymerizable unsaturated groups. In addition, in the examples of Patent Document 1, it is described that a methacrylic acid/allyl methacrylate/glycidyl adduct was synthesized as an alkali-soluble resin and used to prepare a photosensitive resin composition. Prior art literature Patent literature

Patent Document 1: International Publication No. 2012/147706

[The problem to be solved by the invention]

The photosensitive resin composition used to form a color filter or a black matrix uses a resin having the property of being cured by a polymerization reaction caused by light. The color filter or the black matrix is produced by patterning the photosensitive resin composition by exposure and development, and then curing it. In the photosensitive resin composition, "increasing sensitivity" is also considered to be a common issue, but with the complication or popularization of display devices or imaging devices, a higher level of high sensitivity is required. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, which can improve productivity. In addition, the photosensitive resin composition is required to have excellent processability in the development process using an alkaline developer.

The inventors of the present invention found that by improving the polymer used in the photosensitive resin composition or the blending of the composition, a photosensitive resin composition having good sensitivity, high alkali solubility and excellent developability can be obtained, thereby achieving The present invention. [Technical means to solve the problem]

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

（式（NB）中，R¹ 、R² 、R³ 及R⁴ 分別獨立地為氫原子或碳數1～30的有機基，a₁ 為0、1或2。）

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

（式（1）中，R^p 為具有兩個以上的（甲基）丙烯醯基之基。）

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

（式（NB）中，R¹ 、R² 、R³ 及R⁴ 分別獨立地為氫原子或碳數1～30的有機基，a₁ 為0、1或2。）

（式（1）中，R^p 為具有兩個以上的（甲基）丙烯醯基之基。）Furthermore, according to the present invention, there is provided a photosensitive resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); having two or more (methyl groups) Acrylic compounds; and photosensitizers.

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

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

Furthermore, according to the present invention, there is provided a cured product formed of the above-mentioned photosensitive resin composition. [Effects of Invention]

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

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description is appropriately omitted. Also, all the drawings are for illustration only. The shape or size ratio of each member in the drawing does not necessarily correspond to the actual article. In this specification, the symbol "a to b" in the description of the 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 the label of the group (atomic group) in the present specification, the label that is not labeled with substituted or unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl).

The symbol "(meth)acrylic acid" in this specification means the concept including both acrylic acid and methacrylic acid. The same applies to similar marks such as "(meth)acrylate". In particular, the "(meth)acryloyl group" in this specification means to include the acryloyl group represented by -C(=O)-CH=CH ₂ and -C(=O)-C(CH ₃ )=CH ₂ The concept of methacrylic acid base.

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

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

式（NB）中，R¹ 、R² 、R³ 及R⁴ 分別獨立地為氫原子或碳數1～30的有機基，a₁ 為0、1或2。

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

式（1）中，R^p 為具有兩個以上的（甲基）丙烯醯基之基。

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

The polymer P used in the resin composition of this embodiment contains the structural unit represented by formula (1). Thereby, the photosensitive resin composition containing the polymer P has excellent sensitivity when used for photolithography. It is considered that this is because the hardening reaction (polymerization reaction) is promoted by two or more (meth)acrylic groups contained in the structural unit represented by formula (1). In addition, the polymer P contains a structural unit represented by formula (NB). The structural unit (NB) is chemically strong. Therefore, the polymer P containing it as a structural unit has a small weight loss when it is subjected to a heat treatment, and is stable. Therefore, in order to manufacture a film or filter used in a liquid crystal display device or a solid-state imaging element that requires heat resistance, a photosensitive resin composition containing the polymer P can be suitably used.

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

式（2）中，R^s 為具有一個（甲基）丙烯醯基之基。 藉由除了含有式（1）所表示之結構單元以外，還含有式（2）所表示之結構單元，聚合物P具有更高的靈敏度及高鹼溶性，因此能夠適合使用於基於光微影法之加工。

In formula (2), R ^s is a group having one (meth)acryloyl group. By containing not only the structural unit represented by formula (1), but also the structural unit represented by formula (2), polymer P has higher sensitivity and high alkali solubility, so it can be suitably used for photolithography-based methods之processing.

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

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

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

In the structural unit represented by the formula (NB) constituting the polymer P ^{, examples of the organic group capable of constituting R 1} to R ^{4 having} 1 to 30 carbon atoms include substituted or unsubstituted linear or branched chains The alkyl group having 1 to 30 carbon atoms, more specifically, alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkaryl group, cycloalkyl, Alkoxy, heterocyclic, carboxyl, etc.

Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. Base, octyl, nonyl and decyl, etc. Examples of alkenyl groups include allyl groups, pentenyl groups, vinyl groups, and the like. As an alkynyl group, an ethynyl group etc. are mentioned, for example. As an alkylene group, a methylene (methylidene), an ethylene (ethylidene), etc. are mentioned, for example. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl, and anthracenyl. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example. As an alkaryl group, a tolyl group, a xylyl group, etc. are mentioned, for example. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, n-butoxy Pentyloxy, neopentyloxy, n-hexyloxy, etc. As a heterocyclic group, an epoxy group, an oxetanyl group, etc. are mentioned, for example.

^{As R 1} , R ² , R ³ and R ^{4 in} the structural unit represented by the formula (NB), hydrogen or an alkyl group is preferable, and hydrogen is more preferable. In addition, the hydrogen atom in the C 1-30 organic group of ^{R 1} , R ² , R ^3, and R ^{4 may be substituted with any atomic group.} For example, it may be substituted by a fluorine atom, a hydroxyl group, a carboxyl group, and the like. More specifically, as ^{the C 1-30 organic group of R 1} , R ² , R ^3, and R ⁴ , a fluorinated alkyl group or the like can be selected. In the structural unit represented by formula (NB), a _{1 is} preferably 0 or 1, more preferably 0.

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

In this embodiment, the polymer P has a structural unit represented by formula (1), in other words, has a structure containing two or more (meth)acrylic groups (-C(=O)-CH=CH ₂ ) unit. Thereby, the sensitivity of the polymer P in the exposure process can be improved.

In the structural unit represented by formula (1) constituting the polymer P, R ^p is a group containing two or more (meth)acrylic groups, preferably 2-6 (meth)acrylic groups The base is more preferably a base containing 3 to 5 (meth)acrylic groups. By optimally setting ^{the number of (meth)acrylic groups contained in R p} , the sensitivity of the polymer P containing it in the exposure process can be further improved. In addition, it is easy to balance the sensitivity and alkali solubility of the polymer P to a higher degree. In addition, the heat resistance of the polymer P can be improved.

R ^{p is} preferably a group represented by formula (1b) or a group represented by formula (1c). By being such a base, there is a tendency to easily obtain the above-mentioned various effects.

^{R p} in the formula (1) is preferably a group represented by the formula (1b), a group represented by the formula (1c), or a group represented by the formula (1d). By being such a base, there is a tendency to easily obtain the above-mentioned various effects.

式（1b）中， k為2或3， R為氫原子或甲基，複數個R可以相同亦可以不同， X¹ 為單鍵、碳數1～6的伸烷基或-Z-X-所表示之基（Z為-O-或-OCO-，X為碳數1～6的伸烷基），存在複數個之X¹ 可以相同亦可以不同， X¹ '為單鍵、碳數1～6的伸烷基或-X'-Z'-所表示之基（X'為碳數1～6的伸烷基，Z'為-O-或-COO-）， X² 為碳數1～12的k+1價的有機基。 從進一步提高靈敏度（聚合的容易性）等而言，R較佳為氫原子。 k可以為2，亦可以為3，但從進一步提高原料的獲得容易性或靈敏度之觀點而言，較佳為3。

In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. X ¹ is a single bond, an alkylene having 1 to 6 carbon atoms or represented by -ZX- the group (Z is -O- or -OCO-, X is an alkylene group having a carbon number of 1 to 6), presence of a plurality of X ¹ may be also the same or different, X ¹ 'is a single bond, 1 to 6 carbon atoms The alkylene group or the group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbons, and Z'is -O- or -COO-), X ² is a carbon number of 1 to 12 The k+1 valence organic base. From the viewpoint of further improving sensitivity (easiness of polymerization), etc., R is preferably a hydrogen atom. k may be 2 or 3, but from the viewpoint of further improving the availability or sensitivity of raw materials, 3 is preferred.

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 carbons, X ^{1 is} preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbons, and still more preferably -CH ₂ -(Methylene).

When X ¹ is a group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene having 1 to 6 carbons), the alkylene having 1 to 6 carbons of X may be straight The chain shape may also be branched. The alkylene having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH ₂ -CH ₂ -(extension Ethyl) or -CH ₂ -CH(CH ₃ )-.

When X ¹ ′ is an alkylene group having 1 to 6 carbon atoms, the specific aspect is the same as ^{X 1.} When X ¹ 'is the base represented by -X'-Z'-, the specific aspect of X'is the same as the above-mentioned X.

Examples of the k+1 valent organic group of X ² having 1 to 12 carbon atoms include any group obtained by removing k+1 hydrogen atoms from any organic compound. As the "arbitrary organic compound" herein, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X ^{2 is,} for example, a group obtained by removing k+1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbons (preferably 1 to 6 carbons). More preferably, it is a group obtained by removing k+1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. Furthermore, the hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group, etc.). In addition, the hydrocarbon is preferably a saturated hydrocarbon. As another aspect, X ² may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure, a group containing a heterocyclic structure (for example, an isocyanuric acid structure), and the like.

式（1c）中， k、R、X¹ 及X² 分別與式（1b）中之R、k、X¹ 及X² 同義，複數個R可以彼此相同亦可以不同，複數個X¹ 可以彼此相同亦可以不同， X³ 為碳數1～6的2價的有機基， X⁴ 及X⁵ 分別獨立地為單鍵或碳數1～6的2價的有機基， X⁶ 為碳數1～6的2價的有機基。

In formula (1c), k, R, X ¹ and X ² are synonymous with R, k, X ¹ and X ^{2 in} formula (1b) respectively. A plurality of R may be the same or different from each other, and a plurality of X ¹ may be mutually exclusive The same or different, X ³ is a divalent organic group with 1 to 6 carbons, X ⁴ and X ⁵ are each independently a single bond or a divalent organic group with 1 to 6 ^{carbons, and X 6} is a carbon 1 ~6 divalent organic group.

The specific aspects and preferred aspects of R, k, X ¹ and X ² are the same as those described in the general formula (1b). Examples of the divalent organic group having 1 to 6 carbons of X ³ and X ⁶ include groups obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbons. Furthermore, the hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group, etc.). In addition, the hydrocarbon is preferably a saturated hydrocarbon. Examples of the divalent organic group having 1 to 6 carbon atoms of X ⁴ and X ^{5 include linear or branched alkylene groups.} The carbon number of the linear or branched alkylene is preferably 1-3.

式（1d）中，n為2～5的整數，較佳為2或3， 關於R的具體態樣、較佳態樣等，與在通式（1b）中說明者相同。

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

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

In the structural unit represented by formula (2), R ^S is a group containing only one (meth)acryloyl group. In one embodiment, the polymer P may contain "the structural unit of formula (1) containing two or more (meth)acryloyl groups", and also "the formula (2) containing only one acryloyl group". The structural unit of ". Since the polymer P contains these two structural units, it is possible to achieve a higher degree of compatibility between sensitivity and developability. In particular, in the design of a general photosensitive resin composition, when the sensitivity is to be increased and the curability is improved, the curing proceeds too much and the developability tends to deteriorate. On the other hand, when the developability is desired to be improved, the curing tends to be Since it becomes insufficient, it is preferable that the polymer P contains the structural unit represented by formula (1) and the structural unit represented by formula (2) in combination, so that both sensitivity and developability can be balanced in a good balance. .

R ^S is a group represented by the following formula (2a), for example.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can also be adopted. In the formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group. The total carbon number of X ¹⁰ is preferably 1-30, more preferably 1-20, and still more preferably 1-10. In the formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group. The total carbon number of X ¹⁰ is preferably 1-30, more preferably 1-20, and still more preferably 1-10. As the ^{divalent organic group of X 10} , for example, an alkylene group is preferable. _{-CH 2} -which is a part of the 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 3 to 6 total carbons. By appropriately selecting a carbon number X (X is a chain length of ^{10) 10,} the formula (2) structural unit represented by the crosslinking reaction more easily, the sensitivity can be improved.

The divalent organic group (for example, alkylene) of X ^{10 may be substituted with any substituent.} As a substituent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc. are mentioned. In addition, the ^{divalent organic group of X 10} may be any group other than an alkylene group. For example, it may be a divalent group formed by connecting one or two or more groups selected from alkylene, cycloalkylene, arylene, ether group, carbonyl group, carboxyl group, etc. .

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

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

Furthermore, the content (ratio) of each structural unit contained in the polymer P can be based on the loading amount (molar amount) of the raw materials used when synthesizing the polymer, the amount of raw materials remaining after synthesis, and various spectra (such as , The existence and peak area of IR spectrum, ¹ H-NMR spectrum, ¹³ C-NMR spectrum) can be estimated/calculated.

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 still more preferably 3,000 to 12,000. By appropriately adjusting the weight average molecular weight, the sensitivity or the solubility to the alkali developer can be adjusted.

In addition, the degree of dispersion of the 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 still more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer P can be made homogeneous, which is preferable. Furthermore, these values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer P is preferably 150 to 250°C, more preferably 170 to 230°C. The polymer P has a relatively high glass transition temperature by mainly containing the structural unit represented by the formula (NB). This is preferable from the viewpoint that the pattern formed on the substrate can stably exist when manufacturing a liquid crystal display device or a solid-state imaging element. In addition, the glass transition temperature can be obtained by, for example, differential thermal analysis (DTA).

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

As the compound having two or more (meth)acrylic acid groups used in the resin composition of this embodiment (referred to as "polyfunctional (meth)acrylic compound" in this specification), for example, The compound represented by the following formula (1b-p), the compound represented by the formula (1c-p), and the compound represented by the formula (1d-p) are not limited to these. ^{The definitions and specific aspects of k, R, X 1} , X ¹ ′, and X ² in formula (1b-p) are the same as those in formula (1b) above. ^{In addition, the definitions and specific aspects of k, R, X 1} , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in the formula (1c-p) are the same as those in the above formula (1c). In formula (1b-p), formula (1c-p) and formula (1d-p), Y is a hydrogen atom or a (meth)acryloyl group or a combination of these. 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. R in the formula (1d-p) is the same as that in the above formula (1d).

As a specific example of the polyfunctional (meth)acrylic compound represented by Formula (1b-p), the compound of the following structure can be mentioned, but it is not limited to these. In addition, in the following compounds, Y represents a hydrogen atom or a (meth)acryloyl group or a combination of these.

As specific examples of the polyfunctional (meth)acrylic compound represented by formula (1c-p), the following compounds may be mentioned, but they are not limited to these.

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

Examples of the monofunctional (meth)acrylic compound used in the resin composition of the present embodiment include compounds represented by the following formula (2a-m). In the formula (2a-m), ^{the definitions of X 10} and R are the same as those in the formula (2a).

Specific examples of the compound represented by the formula (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, 2-(meth)acrylate Base) propylene oxyethyl-2-hydroxyethyl-phthalic acid, etc.

In the resin composition of this embodiment, the polyfunctional (meth)acrylic compound is based on the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) diagram of the resin composition It is blended in an amount of, for example, 5 to 150% with respect to the peak area of the polymer P. The lower limit of the peak area derived from the polyfunctional (meth)acrylic compound relative to the peak area of the polymer P is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, and more Preferably, it is more than 40%, and particularly preferably, it is more than 50%. The upper limit of the peak area derived from the polyfunctional (meth)acrylic compound with respect to the peak area of the polymer P is preferably 140% or less, more preferably 135% or less, still more preferably 130% or less, and more Preferably it is 125% or less, and particularly preferably it is 120% or less. By blending the polyfunctional (meth)acrylic compound in the above range, the obtained resin composition has excellent alkali solubility.

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

Since the resin composition of this embodiment has the above-mentioned structure, its alkali dissolution rate can be set to 250 nm/s or more, for example, Preferably it can be set to 280 nm/s or more.

The resin composition of this embodiment typically contains an organic solvent, and is provided in the form of a liquid or varnish. As the organic solvent, one or two or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

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

(Manufacturing of polymer P) Here, the method for producing the above-mentioned polymer P will be described. The polymer P can be produced (synthesized) by any method. The polymer P can be manufactured by, for example, the following steps: Step (I): A step of preparing a raw polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA); and Step (II): The raw polymer obtained in step (I) is combined with a compound having a hydroxyl group and two or more (meth)acrylic groups (hereinafter referred to as "multifunctional (meth)acrylic monomer") ) The reaction is carried out in the presence of a basic catalyst to prepare a polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (1) and optionally further containing the structural unit represented by the formula (MA) P of the step.

When the polymer P further contains the structural unit represented by formula (2), it can be manufactured by the following steps: in step (II), the raw polymer obtained in step (I), the polyfunctional (methyl) ) An acrylic monomer and a compound having a hydroxyl group and one (meth)acrylic acid group (hereinafter referred to as "monofunctional (meth)acrylic monomer") react in the presence of a basic catalyst to prepare a compound containing the formula ( NB) the step of the structural unit represented by the structural unit, the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the polymer P further containing the structural unit represented by the formula (MA) as the case may be.

When the polymer P further contains the structural unit represented by the formula (3), in step (II), the preparation contains the structural unit represented by the formula (NB), the structural unit represented by the formula (1) and/or the formula ( 2) The polymer of the structural unit represented by the formula (MA) and the structural unit represented by the formula (MA), followed by a step of treating the polymer with water in the presence of an alkali catalyst (step (III)).

When the polymer P contains a sulfide group, such a polymer P can be produced by using a base polymer into which the sulfide group is introduced in the step (II). Specifically, the base polymer containing a sulfide group can be produced by producing a base polymer containing the structural unit represented by the formula (NB), the structural unit represented by the formula (MA), and the sulfide group in the step (I) To get. The production of the base polymer into which the sulfide group is introduced will be described in detail below.

When using both a multifunctional (meth)acrylic monomer and a monofunctional (meth)acrylic monomer in step (II), it is preferable to first combine the multifunctional (meth)acrylic monomer with the base polymer. After the reaction, the monofunctional (meth)acrylic monomer is reacted with the obtained reaction mixture. (Step (I)) The step of preparing a raw polymer containing the structural unit represented by formula (NB) and the structural unit represented by formula (MA) in step (I) includes: by making formula (NBm) represented The monomer and maleic anhydride are polymerized (addition polymerization) to obtain the target raw material polymer. Furthermore, the definitions of R ¹ , R ² , R ³ , R ^4, and a ₁ in formula (NBm) are the same as those in formula (NB). The same applies to the preferred aspect. When preparing to introduce a sulfide group-containing raw material polymer in step (I), such raw material polymer can be prepared by making the monomer represented by the formula (NBm) and maleic anhydride in the thiol group-containing compound It is produced by polymerization (addition polymerization) in the presence. The thioether group introduced into the obtained raw polymer is derived from the thiol group contained in the thiol group-containing compound.

As the monomer represented by the formula (NBm), for example, norbornadiene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornadiene), 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 Alkene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenylethyl-2-norbornene, 2-ethynyl-5-norbornene, 5- Norbornene-2-carboxylic acid methyl ester, 5-norbornene-2,3-dicarboxylic acid anhydride, etc. In the polymerization, the monomer represented by the formula (NBm) may be used alone or in combination of two or more.

As the thiol group-containing compound used to produce the thioether group-introduced raw polymer, it is preferable to use a thiol group-containing compound having two or more thiol groups. 6-functional thiol-containing compound. By using such a thiol group-containing compound, the sensitivity of the obtained polymer P can be improved.

As specific examples of the thiol group-containing compound, compounds represented by the following formulas (s-1) to (s-20) can be given, but they are not limited to these. The thiol group-containing compound may be used singly or in combination of two or more.

The polymerization method of the monomer represented by the formula (NBm) and maleic anhydride is not limited, but a radical polymerization using a radical polymerization initiator is preferred. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used. As the azo compound, specifically, azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 1,1'-azobis (Cyclohexanecarbonitrile) (ABCN) and so on. Examples of organic peroxides include hydrogen peroxide, di(tertiary butyl) peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP). )Wait. Regarding the polymerization initiator, only one type may be used, or two or more types may be used in combination.

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

The synthesis of the raw polymer containing the structural unit represented by the formula (NB) and the structural unit represented by the formula (MA) can be carried out by the following treatment: the monomer represented by the formula (NBm), maleic anhydride And the polymerization initiator is dissolved in the solvent and put into the reaction vessel, and then heated to perform the addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. The molar ratio of the monomer represented by the formula (NBm) to maleic anhydride when it is charged into the reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1. Through such steps, "raw polymer" can be obtained. Furthermore, the base polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. It is typically a random copolymer or an alternating copolymer. Furthermore, it is generally known that maleic anhydride is a monomer with strong alternating copolymerizability.

The synthesis of the sulfide group-introduced raw polymer containing the structural unit represented by the formula (NB), the structural unit represented by the formula (MA), and the sulfide group is carried out by the following treatment: The monomer, maleic anhydride, and polymerization initiator are dissolved in a solvent and charged into the reaction vessel, and then heated, and the aforementioned thiol group-containing compound is added dropwise while performing addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. The molar ratio of the monomer represented by the formula (NBm) to maleic anhydride when it is charged into the reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1. In addition, from the viewpoint of controlling the content of sulfide groups in the base polymer into which sulfide groups are introduced and the molecular weight of the base polymer, it is relative to the monomer and the monomer represented by the formula (NBm) when charged into the reaction vessel The total molar amount of maleic anhydride is charged. The charged amount of the thiol group-containing compound is preferably 0.5-10 mol%, particularly preferably 1-8 mol%, and more preferably 2-6 mol%. Ear%.

Furthermore, after synthesizing the base polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and remaining polymerization initiators may be performed. Specifically, the organic phase 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. Then, this solution is mixed with a poor solvent such as methanol to precipitate the monomer. By filtering and drying the precipitate, the purity of the raw material polymer can be improved.

In the following steps (II) and (III), the base polymer obtained in step (I) is used to produce the polymer P of this embodiment. In the following description, it is described that a base polymer composed of a structural unit represented by formula (NB) and a structural unit represented by formula (MA) is used as the base polymer obtained in step (I), but even in The same method can also be used in the case of using a raw polymer into which a sulfide group is introduced. In this case, the obtained polymer P contains a sulfide group.

(Step (II)) By reacting the raw polymer obtained in step (I), the multifunctional (meth)acrylic monomer, and optionally the monofunctional (meth)acrylic monomer contained in the case, in the presence of a basic catalyst, Part of the structural unit represented by the formula (MA) contained in the base polymer is ring-opened, and when the structural unit represented by the formula (1) and a monofunctional (meth)acrylic monomer are used, the formula (2) is formed The structural unit represented to obtain the structural unit represented by the formula (NB) and the structural unit represented by the formula (1) and the structural unit represented by the formula (2) (when a monofunctional (meth)acrylic monomer is used) ) And polymer P containing the structural unit represented by formula (MA) according to the situation.

More specifically, first, a solution obtained by dissolving the base polymer in an appropriate organic solvent is prepared. As an organic solvent, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) can be used ) And other single solvents or mixed solvents, but are not limited to these, and various organic solvents used in the synthesis of organic compounds or polymers can be used.

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

As the polyfunctional (meth)acrylic monomer that can be used here, for example, the compound represented by the above formula (1b-p), the compound represented by the formula (1c-p), and the compound represented by the formula (1d-p) Among the compounds shown, Y is a hydrogen atom.

Next, the monofunctional (meth)acrylic monomer and the polymer obtained in step (II-i) are reacted in the presence of a basic catalyst, thereby obtaining a structural unit containing at least the formula (NB), The polymer of the structural unit of formula (1) and the structural unit of formula (2) (step (II-ii)).

Only one of steps (II-i) and (II-ii) may be implemented, but it is preferable to implement step (II-i). When both steps (II-i) and (II-ii) are implemented, it is preferable to implement step (II-ii) after step (II-i).

(Step (III)) When step (III) is implemented, a step of treating the polymer obtained in step (II) with water in the presence of a basic catalyst is used. The structural unit represented by formula (MA) contained in the polymer obtained in step (II) is ring-opened to form the structural unit represented by formula (3) by step (III) and step (II), thereby making it possible to produce a structure containing formula ( NB) The polymer P of the structural unit represented by the structural unit represented by the formula (1) and/or the structural unit represented by the formula (2) and the structural unit represented by the formula (3). When part of the structural unit represented by formula (MA) is ring-opened, and part of the structural unit of formula (MA) remains without ring-opening, polymer P contains formula (NB), formula (1) and formula (2) (In the case of using a monofunctional (meth)acrylic monomer in step (II)) and the structural unit of formula (3), it also contains a structural unit represented by formula (MA).

As the basic catalyst used in step (III), amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds can be mentioned.

In step (III), water is added to the reaction system containing the polymer obtained in step (II), and the obtained reaction solution is preferably heated at 60 to 80°C for about 0.25 to 6 hours, whereby the The structural unit of formula (MA) contained in the polymer is ring-opened to produce the structural unit represented by formula (3). The alkaline catalyst can directly use the catalyst remaining in the reaction system obtained in step (II). Therefore, step (III) is preferably implemented by adding water to the reaction mixture in situ without any post-treatment of the reaction mixture obtained in step (II).

(Manufacturing of resin composition) The resin composition of this embodiment can be produced by mixing the above-mentioned components by a well-known method. The resin composition of this embodiment is used as a resin material of the photosensitive resin composition demonstrated below.

(Photosensitive resin composition) The photosensitive resin composition of this embodiment contains the said polymer P, the compound (multifunctional (meth)acrylic compound) which has two or more (meth)acrylic acid groups, and a photosensitive agent. That is, the photosensitive resin composition of this embodiment contains the resin composition of this embodiment mentioned above and a photosensitive agent. Hereinafter, each component will be described.

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

啉基丙-1-酮、2-苄基-2-二甲基胺基-1-（4-

啉基苯基）-丁酮-1、2-（二甲基胺基）-2-〔（4-甲基苯基）甲基〕-1-〔4-（4-

啉基）苯基〕-1-丁酮等烷基苯酮（alkylphenone）系化合物；二苯甲酮、4,4'-雙（二甲基胺基）二苯甲酮、2-羧基二苯甲酮等二苯甲酮系化合物；安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等安息香系化合物；9-氧硫𠮿

（thioxanthone）、2-乙基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、2-氯-9-氧硫𠮿

、2,4-二甲基-9-氧硫𠮿

、2,4-二乙基-9-氧硫𠮿

等9-氧硫𠮿

系化合物；2-（4-甲氧基苯基）-4,6-雙（三氯甲基）對稱三

、2-（4-甲氧基萘基）-4,6-雙（三氯甲基）對稱三

、2-（4-乙氧基萘基）-4,6-雙（三氯甲基）對稱三

、2-（4-乙氧基羰基萘基）-4,6-雙（三氯甲基）對稱三

等鹵甲基化三

系化合物；2-三氯甲基-5-（2'-苯并呋喃基）-1,3,4-㗁二唑、2-三氯甲基-5-〔β-（2'-苯并呋喃基）乙烯基〕-1,3,4-㗁二唑、4-㗁二唑、2-三氯甲基-5-呋喃基-1,3,4-㗁二唑等鹵甲基化㗁二唑系化合物；2,2'-雙（2-氯苯基）-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙（2,4-二氯苯基）-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙（2,4,6-三氯苯基）-4,4',5,5'-四苯基-1,2'-聯咪唑等聯咪唑系化合物；1,2-辛二酮、1-〔4-（苯硫基）-2-（O-苯甲醯肟）〕、乙酮（ethanone）、1-〔9-乙基-6-（2-甲基苯甲醯基）-9H-咔唑-3-基〕-1-（O-乙醯肟）等肟酯系化合物；雙（η5-2,4-環戊二烯-1-基）-雙（2,6-二氟-3-（1H-吡咯-1-基）-苯基）鈦等二茂鈦系化合物；對二甲基胺基安息香酸、對二乙基胺基安息香酸等安息香酸酯系化合物；9-苯基吖啶等吖啶系化合物等。光自由基聚合起始劑可以單獨使用一種，亦可以組合使用兩種以上。As the photosensitive agent used in the photosensitive resin composition of this embodiment, a radical photopolymerization initiator can be mentioned. As the photoradical polymerization initiator, known compounds can be used, for example, 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-methylpropanyl)benzyl]phenyl}-2-methylprop-1- Ketone, 2-methyl-1-(4-methylthiophenyl)-2-

Linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Alkylphenone compounds such as phenylphenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone Benzophenone compounds such as methyl ketone; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; 9-oxysulfur 𠮿

(Thioxanthone), 2-ethyl-9-oxysulfur 𠮿

, 2-isopropyl-9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur 𠮿

, 2,4-Dimethyl-9-oxysulfur 𠮿

, 2,4-Diethyl-9-oxysulfur

Wait 9-oxysulfur 𠮿

Series compounds; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetric three

, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) symmetric three

, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl) symmetric three

, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) symmetric three

Isohalomethylation three

Series compounds; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-〔β-(2'-benzo Furyl) vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and other halomethylated 㗁Diazole compounds; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2, 4-Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds; 1,2-octanedione, 1-[4-(phenylthio)-2-(O- Benzyl oxime)], ethyl ketone (ethanone), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-ethyl Oxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl ) Titanocene compounds such as titanium; Benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenyl acridine, etc. The photoradical polymerization initiator may be used singly or in combination of two or more.

The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, and preferably 3 to 10 parts by mass with respect to 1000 parts by mass of the polymer P.

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

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

系顏料、硫靛（thioindigo）系顏料、蒽醌系顏料、喹啉黃系顏料、金屬錯合物系顏料、二酮吡咯并吡咯（diketo-pyrrolo-pyrrole）系顏料、𠮿

（xanthene）系顏料、吡咯亞甲基（pyrromethene）系顏料、染料色澱系顏料等。 作為無機顏料，能夠使用白色·體質顏料（氧化鈦、氧化鋅、硫化鋅、黏土、滑石、硫酸鋇、碳酸鈣等）、有色顏料（鉻黃、鎘系、鉻朱紅（chrome vermilion）、鎳鈦、鉻鈦、黃色氧化鐵、赤鐵氧化物（Bengala）、鉻酸鋅、鉛紅、群青、鐵藍、鈷藍、鉻綠、氧化鉻、釩酸鉍等）、增亮材料顏料（珠光顏料、鋁顏料、青銅顏料等）、螢光顏料（硫化鋅、硫化鍶、鋁酸鍶等）。As the pigment, organic pigments or inorganic pigments can be used. As organic pigments, azo-based pigments, phthalocyanine-based pigments, quinacridone-based pigments, perylene-based pigments, perinone-based pigments, isoindolinone-based pigments, isoindoline (isoindoline) can be used. ) Department of pigments, two 㗁

Pigments, thioindigo (thioindigo) pigments, anthraquinone pigments, quinoline yellow pigments, metal complex pigments, diketo-pyrrolo-pyrrole (diketo-pyrrolo-pyrrole) pigments, 𠮿

(Xanthene) pigments, pyrromethene pigments, dye lake pigments, etc. As inorganic pigments, white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (chrome yellow, cadmium series, chrome vermilion), nickel titanium can be used , Chromium titanium, yellow iron oxide, hematite oxide (Bengala), zinc chromate, lead red, ultramarine blue, iron blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening material pigments (pearlescent pigments) , Aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

As the dye, for example, known dyes described in Japanese Patent Application Publication No. 2003-270428, Japanese Patent Application Publication No. 9-171108, Japanese Patent Application Publication No. 2008-50599, and the like can be used.

When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only one type of coloring agent, and may contain two or more types. Colorants (especially pigments) can be used with appropriate average particle diameters according to the purpose or application. When transparency as a color filter is particularly required, it is preferably a small average particle diameter of 0.1 μm or less. In addition, when When hiding properties of paint or the like are required, a large average particle size of 0.5 μm or more is preferable. The colorant can be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silicon dioxide coating, wax coating, etc., depending on the purpose or application.

When the photosensitive resin composition contains a coloring agent, the amount may be appropriately set according to the purpose or application. However, from the viewpoint of compatibility of the coloring concentration and the dispersion stability of the coloring agent, it is relative to the non-volatile components of the photosensitive resin composition. (Components other than the solvent) As a whole, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.

As one aspect, the photosensitive resin composition may contain a light-shielding agent. By containing a light-shielding agent, it can be suitably used as a material for forming a black matrix of a liquid crystal display device or a solid-state imaging device. As a light-shielding agent, a well-known light-shielding agent can be used without a restriction|limiting in particular. For example, black pigments such as carbon black, bone black, graphite, iron black, and titanium black can be used as the sunscreen.

When the photosensitive resin composition contains a light-shielding agent, the photosensitive resin composition may contain only one type of light-shielding agent, and may contain two or more types. When the photosensitive resin composition contains a light-shielding agent, the amount may be appropriately set according to the purpose or application. However, from the viewpoint of compatibility of light-shielding performance and dispersion stability of the light-shielding agent, it is relative to the non-volatile components of the photosensitive resin composition. (Components other than the solvent) As a whole, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.

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

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

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

As one aspect, the photosensitive resin composition can contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking the polymer (which can chemically bond with the polymer) by the action of the active chemical species generated from the photopolymerization initiator. The cross-linking agent can not only chemically bond with the polymer, but also can react between the cross-linking agents to form a bond.

The crosslinking agent is preferably a multifunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a multifunctional (methyl) compound having two or more (meth)acrylic groups in one molecule. ) Acrylic compound (however, the crosslinking agent does not correspond to the aforementioned polymer). From the viewpoints of uniform curability and further improvement in sensitivity, it is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) possessed by the polymer. The upper limit of the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent is not particularly specified, and is, for example, 8 or less, preferably 6 or less.

As a crosslinking agent, the following can be mentioned specifically,.

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 Base) acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate (bisphenol A alkylene oxide di(meth) )acrylate), bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol tri( Addition of meth)acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, ethylene oxide Trimethylolpropane tri(meth)acrylate, ethylene oxide addition ditrimethylolpropane tetra(meth)acrylate, ethylene oxide addition neopentaerythritol tetra(meth)acrylate 、Ethylene oxide addition dineopentaerythritol hexa(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane tetra (Meth) acrylate, propylene oxide addition neopentyl erythritol tetra (meth) acrylate, propylene oxide addition dineopentaerythritol hexa (meth) acrylate, ε-caprolactone addition three Methylolpropane tri(meth)acrylate, ε-caprolactone addition ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone addition neopentaerythritol tetra(meth)acrylic acid Ester and ε-caprolactone add multifunctional (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate.

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, new Pentaerythritol tetravinyl ether, dineopentaerythritol pentavinyl ether, dineopentaerythritol hexavinyl ether, ethylene oxide addition, trimethylolpropane trivinyl ether, ethylene oxide addition Ditrimethylolpropane tetravinyl ether, ethylene oxide addition neopentyl erythritol tetravinyl ether, ethylene oxide addition dineopentaerythritol hexavinyl ether and other multifunctional vinyl ethers.

2-vinyloxyethyl (meth)acrylate (2-vinyloxyethyl (meth)acrylate), 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxy (meth)acrylate Ethyl, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-(meth)acrylate Vinyloxypentyl ester, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate Ester, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, etc. containing vinyl ether groups (Meth) acrylates.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diene Propyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether , Glycerol triallyl ether, neopentyl erythritol tetraallyl ether, dineopentol pentaerythritol pentaallyl ether, dineopentaerythritol hexaallyl ether, ethylene oxide addition trihydroxy Methyl propane triallyl ether, ethylene oxide addition ditrimethylolpropane tetraallyl ether, ethylene oxide addition neopentyl erythritol tetraallyl ether, ethylene oxide addition two Multifunctional allyl ethers such as neopentyl erythritol hexaallyl ether.

Allyl (meth)acrylate and other (meth)acrylates containing allyl groups. Tris (propylene oxyethyl) trimer isocyanate, tris (methacrylic oxyethyl) trimer isocyanate, alkylene oxide addition tris (propylene oxyethyl) trimer isocyanate, alkylene oxide addition tris ( Trimeric isocyanates containing polyfunctional (meth)acrylic groups such as methacryloxyethyl) trimer isocyanate. Triallyl isocyanate, etc. containing polyfunctional allyl-containing trimer isocyanates. By combining polyfunctional isocyanates such as phenylmethylene diisocyanate, isophorone diisocyanate, and stubbing diisocyanate with 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc., which contain hydroxyl groups Multifunctional amine ester (meth)acrylates obtained by the reaction of (meth)acrylates. Multifunctional aromatic vinyls such as divinylbenzene.

Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, and neopentaerythritol tetra(meth)acrylate are preferred. , Tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate.

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

The photosensitive resin composition may contain fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, development aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, and antioxidants according to various purposes or required characteristics. , Matting agent, defoaming agent, leveling agent, surfactant, antistatic agent, dispersant, slip agent, surface modifier, thixotropic agent, thixotropic additive, silane coupling agent, multivalent Phenolic compounds and other ingredients.

(Thin film, color filter, black matrix, liquid crystal display device and solid-state image sensor) By forming a film using the above-mentioned photosensitive resin composition, and exposing/developing the film to form a pattern, a patterned film can be obtained. This film is suitable for color filters or black matrices. That is, by forming a pattern using a photosensitive resin composition containing a colorant, a color filter can be obtained. Furthermore, by forming a pattern using a photosensitive resin composition containing a light-shielding agent, a black matrix can be obtained. Then, a liquid crystal display device or a solid-state imaging element equipped with a color filter or a black matrix can be manufactured.

The typical procedure of pattern formation will be described.

(Formation of photosensitive resin film) For example, the above-mentioned photosensitive resin composition is coated on an arbitrary substrate, and dried as necessary, thereby first obtaining a photosensitive resin film.

The substrate on which the composition is applied is not particularly limited. For example, glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, copper-clad laminates, and the like can be cited. The substrate may be an unprocessed substrate or a substrate with electrodes or elements formed on the surface. In order to improve adhesion, surface treatment can be performed. The coating method of the photosensitive resin composition is not specifically limited. It can be performed by spin coating using a spin coater, spray coating using a sprayer, dipping, printing, roll coating, inkjet method, etc.

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

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

(Exposure) Exposure is typically performed by irradiating active light to the photosensitive resin film through an appropriate photomask. Examples of active rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferred. From the viewpoint of pattern resolution or operability, the light source is preferably g-ray, h-ray, or i-ray of a mercury lamp, and particularly preferably i-ray. In addition, two or more lights may be mixed and used. As the exposure device, a contact aligner, a mirror projection aligner, or a stepper is preferable. The amount of light for exposure may be appropriately adjusted according to the amount of the photosensitive agent in the photosensitive resin film, etc., and is, for example, about 100 to 500 mJ/cm ² .

In addition, after exposure, the photosensitive resin film may be heated again as needed (heating after exposure: Post Exposure Bake). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. In addition, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By performing post-exposure heating, the reaction based on radicals generated from the photo radical polymerization initiator is promoted, and the hardening reaction is further promoted.

(development) By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained, and a pattern-equipped substrate can be manufactured. In the development step, an appropriate developer can be used to perform development using methods such as a dipping method, a puddle method, a spin spray method, and the like. By development, the exposed part (in the case of a positive type) or the unexposed part (in the case of a negative type) of the photosensitive resin film is eluted and removed to obtain a pattern.

The developer that can be used is not particularly limited. For example, an aqueous alkali solution or an organic solvent can be used. Specific examples of aqueous alkali solutions include (i) aqueous inorganic alkali solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, and (ii) organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine. Aqueous solution, (iii) Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) or butyl acetate, and ether solvents such as propylene glycol monomethyl ether. For example, water-soluble organic solvents such as methanol and ethanol, surfactants, etc. can be added to the developer.

In this embodiment, as the developer, an aqueous alkali solution is preferably used, and an aqueous solution of tetramethylammonium hydroxide, sodium carbonate, or potassium hydroxide is more preferably used. The concentration of the aqueous alkali solution is preferably from 0.1 to 10% by mass, and more preferably from 0.2 to 5% by mass.

Through the above steps, a pattern can be obtained/a substrate with a pattern can be manufactured, but various treatments can be performed after development. For example, after development, the pattern and the substrate can be cleaned with a rinse liquid. Examples of the rinse liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

In addition, the obtained pattern can be heated to fully harden it. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, more preferably 200 to 250°C. The heating time is not particularly limited, and is, for example, in the range of 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a temperature-rising oven capable of setting a temperature program, and the like. As the ambient gas when the heat treatment is performed, air or inert gas such as nitrogen and argon may be used. In addition, heating may be performed under reduced pressure.

An example of the structure of a liquid crystal display device and/or a solid-state imaging element provided with a color filter and/or a black matrix is schematically shown in FIG. 1. A black matrix 11 and color filters 12 are formed on the substrate 10. In addition, a protective film 13 and a transparent electrode layer 14 are provided on the upper part of the black matrix 11 and the color filter 12. The substrate 10 is usually made of a material through which light passes. For example, in addition to being made of glass, it is also made of polyester, polycarbonate, polyolefin, polysulfide, cyclic olefin polymer, or the like. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical solution treatment, and the like as needed. The substrate 10 is preferably composed of glass.

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

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

The implementation aspects of the present invention will be described in detail based on examples and comparative examples. In addition, the present invention is not limited to the Examples.

The compounds used in the examples are sometimes represented by the following abbreviations or trade names. ·MA: Maleic anhydride ·NB: 2-Norbornene ·MEK: Methyl ethyl ketone ·4-HBA: 4-hydroxybutyl acrylate

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

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

·VISCOAT#802：以下式所表示之三新戊四醇丙烯酸酯、單及二新戊四醇丙烯酸酯、聚新戊四醇丙烯酸酯的混合物（Osaka Organic Chemical Industry Co.,Ltd.製造）

·VISCOAT#802: a mixture of trineopentaerythritol acrylate, mono- and dineopentaerythritol acrylate, and polyneopentaerythritol acrylate represented by the following formula (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

n=1：10-20% n=2：55-65% n=3：5-15%

n=1: 10-20% n=2: 55-65% n=3: 5-15%

＜Synthesis of raw polymer＞ (Synthesis of raw polymer 1) Into a reaction vessel of appropriate size equipped with a stirrer and a cooling tube, 588.36g (6.0 mol) of maleic anhydride, 564.90g (6.0 mol) of 2-norcamphene, and 2,2'-co 55.26g (0.24 mol) of dimethyl azodis(2-methylpropionic acid). These were dissolved in a mixed solvent composed of 1716.8 g of methyl ethyl ketone and 188.3 g of toluene to prepare a solution. Nitrogen was passed through the solution for 30 minutes to remove oxygen, and then it was heated at 65°C for 1.5 hours while stirring, and then further heated at 80°C for 6 hours, thereby making the maleic anhydride and 2-norcampan The olefin is polymerized to produce a polymerization solution. The polymerization solution obtained in the above was added dropwise to 14230.2 g of methanol, thereby precipitating a white solid. The obtained white solid was further washed with 3557.5 g of methanol, and then vacuum dried at a temperature of 120°C, thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride The polymer (raw polymer 1) 1027.2g. The obtained polymer was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 7236, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.83.

(Synthesis of raw polymer 2) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norcamphene (451.92 g, 4.8 mol in 2-norbornene conversion) and maleic anhydride (MAN, 470.69) g, 4.8mol) and 2281.74g of methyl ethyl ketone (MEK), and stirred/dissolved. Next, the dissolved oxygen in the system was removed by bubbling with nitrogen and the temperature was raised. When the internal temperature reached 80°C, it took 1 hour to add dimethyl 2,2'-azobisisobutyrate ( Manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21g, 0.19mol) and neopentylerythritol tetrakis (3-mercaptopropionate) (PEMP (the thiol containing the above formula (s-2)) Base compound), 93.82g, 0.19mol) dissolved in MEK193.4g. After that, it was further reacted at 80°C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained in the above was added dropwise to 3686.4 g of methanol, thereby precipitating a white solid. The obtained white solid was further washed with 3686.4 g of methanol, and then vacuum-dried at a temperature of 120°C, thereby obtaining a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. And thioether-based polymer (raw polymer 2) 910.1g. The obtained polymer was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.62.

＜Preparation of resin composition＞ The following method was used to produce a resin composition containing polymer P and a polyfunctional (meth)acrylic compound.

(Preparation Example 1) A polymer P1 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 99.71 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 16 to prepare a dissolving liquid. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 6.00 g (0.333 mol) of water was added to the reaction solution, and the reaction was carried out at 70° C. for 0.5 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Thereafter, the polymer was purified by the following procedure. • Use excess toluene to re-precipitate the polymer. · The operation of washing the polymer powder obtained by reprecipitation with excess toluene was repeated twice. · The operation of washing the polymer powder after the above washing twice with excess water was performed 3 times. · The obtained reaction product was dried at 40°C for 12 hours. Through the above, 60.20 g of polymer P1 in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3LM-N, 4-HBA and water was obtained.

(Preparation Example 2) A resin mixture containing a polymer P2 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. The details will be described below. First, 99.71 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 16 to prepare a dissolving liquid. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 6.00 g (0.333 mol) of water was added to the reaction solution, and the reaction was carried out at 70° C. for 0.5 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the following procedure, followed by solvent replacement. Liquid-liquid extraction: the reaction solution was diluted with MEK, and then water was added for treatment to remove the water phase from the reaction solution, and then the same operation was further performed once. • Solvent replacement: the obtained reaction mixture was removed by using a rotary evaporator at 50°C under reduced pressure. It was confirmed that the solid content concentration of the polymer solution was 27±2% by mass in the measurement based on the heating and drying moisture meter, and the operation of removing the solvent was interrupted. Then, PGMEA was added so that the solid content concentration might become 18 mass %, and it mixed until it became uniform. By the same operation, the solvent was removed under reduced pressure and at 50°C, and the solid content concentration was adjusted to 27±2% by mass in the measurement based on the heat-drying moisture meter, and then the further addition was repeated twice. PGMEA is an operation in which the solid content concentration becomes 18% by mass and is mixed until it becomes uniform. After that, the solvent was removed or PGMEA was added so that the solid content concentration became 30±3% by mass, and the operation was stirred until it became uniform. Through the above operation, the solvent used in the reaction is removed and the solvent is replaced with PGMEA. Through the above, a polymer P2 containing the structural unit derived from maleic anhydride in the raw polymer ring-opened with A-TMM-3LM-N, 4-HBA and water and the residual (free) A-TMM-3LM-N and residual (free) 4-HBA resin mixture (resin composition) 2. The obtained resin composition 2 was analyzed by gel permeation chromatography to measure the polymer P2, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition. Amount, as well as the weight average molecular weight and polydispersity of polymer P2. The results are shown in Table 1. Furthermore, the amount of free (meth)acrylic compound is based on the ratio of the peak area of the free (meth)acrylic compound to the peak area of the polymer P in the gel permeation chromatography (GPC) diagram of the resin mixture (% )Express. Furthermore, the measurement conditions of the gel permeation chromatography method are as follows. · As a GPC measuring device, TOSOH CORPORATION's HLC-8320GPC EcoSEC was used. The column temperature is set to 40.0°C, and the pump flow rate is set to 0.350 mL/min. ·Peak position (hold time) Polymer P: The peak detected before 20 minutes (Compared with A-TMM-3LM-N and 4-HBA, the peak with shorter retention time and higher molecular weight) A-TMM-3LM-N: The sum of the two peaks of 20.0～20.6 points and 20.6～21.5 points 4-HBA: 21.7～22.4 points ·Measurement conditions: Analyzed with a differential refractive index detector (RI detector).

(Preparation Example 3) A resin mixture containing a polymer P3 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. The details will be described below. First, 99.71 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 16 to prepare a dissolving liquid. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, to obtain a resin composition 3. GPC measurement was performed on the obtained resin composition 3, and the polymer P3, the amount of free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and the amount of polymer P3 contained in the composition were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 4) A resin mixture containing polymer P4 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. The details will be described below. First, 100.30 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of the base polymer 16 to prepare a dissolving liquid. 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 the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, and resin composition 4 was obtained. GPC measurement was performed on the obtained resin composition 4, and the polymer P4, the amount of free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and the polymer P4 contained in the composition were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 5) A resin mixture containing polymer P5 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 99.71 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 2 to prepare a dissolving liquid. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, and resin composition 5 was obtained. GPC measurement was performed on the obtained resin composition 5, and the amount of polymer P5, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and polymer P5 were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 6) A resin mixture containing polymer P6 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 100.30 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 2 to prepare a dissolving liquid. 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 the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, and resin composition 6 was obtained. GPC measurement was performed on the obtained resin composition 6, and the amount of polymer P6, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and polymer P6 were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 7) A resin mixture containing polymer P7 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 102.43 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 2 to prepare a dissolving liquid. Next, 116.24 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, and resin composition 7 was obtained. GPC measurement was performed on the obtained resin composition 7, and the amount of polymer P7, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and polymer P7 contained in the composition were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 8) A resin mixture containing polymer P8 in which the MA unit of the base polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 97.74 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of the base polymer 16 to prepare a dissolving liquid. 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 the reaction was carried out at a temperature of 70°C for 2 hours. Then, 27.00 g (0.187 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, and resin composition 8 was obtained. GPC measurement was performed on the obtained resin composition 8, and the amount of polymer P8, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound contained in the composition, and polymer P8 were measured The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 9) A resin mixture containing polymer P9 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 99.86 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 2 to prepare a dissolving liquid. 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 the reaction was carried out at a temperature of 70°C for 2 hours. Then, 40.51g (0.281 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, and resin composition 9 was obtained. GPC measurement was performed on the obtained resin composition 9 to measure the amount of polymer P9, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and polymer P9 contained in the composition. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 10) A resin mixture containing polymer P10 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 100.03 g of MEK was added to 60.00 g of the base polymer 2 (0.312 mol in terms of MA) to prepare a dissolving liquid. 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 the reaction was carried out at a temperature of 70°C for 2 hours. Then, 27.00 g (0.187 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, to obtain a resin composition 10. GPC measurement was performed on the obtained resin composition 10, and the amount of polymer P10, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and polymer P10 contained in the composition were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 11) A polymer P11 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 99.93 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 2 to prepare a dissolving liquid. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, to obtain a resin composition 11. Thereafter, the resin composition 11 was purified by the following procedure. • Use excess toluene to re-precipitate the polymer. · The operation of washing the polymer powder obtained by reprecipitation with excess toluene was repeated twice. · The operation of washing the polymer powder after the above washing twice with excess water was performed 3 times. · The obtained reaction product was dried at 40°C for 12 hours. Through the above, 34.35 g of polymer P11 in which the structural unit derived from maleic anhydride in the base polymer 2 was ring-opened with A-TMM-3LM-N, 4-HBA and water was obtained.

(Preparation Example 12) A resin mixture containing polymer P12 in which the MA unit of the base polymer 2 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was produced. The details will be described below. First, 99.93 g of MEK was added to 60.00 g (0.312 mol in terms of MA) of base polymer 2 to prepare a dissolving liquid. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 56.27g (0.390 mol) of 4-HBA was further added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced. Then, without post-processing the obtained reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the reaction was carried out at 70°C for 2 hours. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, to obtain a resin composition 12. GPC measurement was performed on the obtained resin composition 12, and the amount of polymer P12, free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and polymer P12 contained in the composition were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1.

(Preparation Example 13) To the resin composition 3 obtained by the same method as the preparation example 3, the "additive" described in Table 1 was added in an amount indicated by the "additive amount" described in Table 1 to prepare a resin composition 13. Here, the additive amount is set to a weight ratio with respect to the solid content of the resin composition 3 (the total amount of the polymer P3 and the polyfunctional (meth)acrylic compound). GPC measurement was performed on the obtained resin composition 13, and the polymer P3, the amount of free polyfunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and the amount of polymer P3 contained in the composition were measured. The weight average molecular weight and polydispersity. The results are shown in Table 1. Furthermore, the measurement conditions of the gel permeation chromatography method are as follows. · As a GPC measuring device, TOSOH CORPORATION's HLC-8320GPC EcoSEC was used. The column temperature is set to 40.0°C, and the pump flow rate is set to 0.350 mL/min. ·Peak position (hold time) Polymer P: The peak detected before 19.3 minutes (Compared with A-TMM-3LM-N, A-9550 and 4-HBA, the retention time is shorter and the molecular weight is higher) Multifunctional (meth)acrylic compound (A-TMM-3LM-N and A-9550): the sum of the two peaks of 19.3 to 19.8 points and 19.8 to 21.0 points 4-HBA: 21.7～22.4 points ·Measurement conditions: Analyzed with a differential refractive index detector (RI detector).

(Preparation Example 14) To the resin composition 12 obtained by the same method as the preparation example 12, the "additive" described in Table 1 was added in an amount indicated by the "additive amount" described in Table 1 to prepare a resin composition 14. Here, the additive amount is set to a weight ratio with respect to the solid content of the resin composition 12 (the total amount of the polymer P12 and the polyfunctional (meth)acrylic compound). GPC measurement was performed on the obtained resin composition 14 to measure the amount of polymer P12, free multifunctional (meth)acrylic compound and free monofunctional (meth)acrylic compound, and polymer P12 contained in the composition. The weight average molecular weight and polydispersity. The results are shown in Table 1. Furthermore, the measurement conditions of the gel permeation chromatography method are as follows. · As a GPC measuring device, TOSOH CORPORATION's HLC-8320GPC EcoSEC was used. The column temperature is set to 40.0°C, and the pump flow rate is set to 0.350 mL/min. ·Peak position (hold time) Polymer P: The peak detected before 19.5 minutes (Compared with VISCOAT#802, A-TMM-3LM-N and 4-HBA, the retention time is shorter and the molecular weight is higher) Multifunctional (meth)acrylic compound (A-TMM-3LM-N and VISCOAT#802): the sum of the two peaks of 19.5-20.6 points and 20.6-21.5 points 4-HBA: 21.7～22.4 points ·Measurement conditions: Analyzed with a differential refractive index detector (RI detector).

(Preparation Example 15) A polymer P13 in which the MA unit of the base polymer 1 was ring-opened with a monofunctional (meth)acrylic compound was produced. The details will be described below. First, 18.44 g of MEK was added to 10.00 g (0.052 mol in terms of MA) of the base polymer 1 to prepare a dissolving liquid. Next, 9.38 g (0.065 mol) of 4-HBA was added to this dissolving liquid, and then 3.00 g (0.030 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution, thereby removing the water phase from the reaction solution. Thereafter, the polymer was purified by the following procedure. • Use excess water to re-precipitate the polymer. · The operation of washing the polymer powder obtained by reprecipitation with excess water was repeated twice. The obtained reaction product was dried at 40°C for 12 hours. Through the above, 9.5 g of polymer P13 in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with 4-HBA was obtained. GPC measurement was performed on the obtained polymer P13, and the weight average molecular weight and polydispersity of the polymer P13 were measured. The results are shown in Table 1. In addition, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P13. Thereby, it was confirmed that the unreacted monofunctional (meth)acrylic compound was not contained in the obtained polymer P13.

(Preparation Example 16) A polymer P14 in which the MA unit of the base polymer 2 was ring-opened with a monofunctional (meth)acrylic compound was produced. The details will be described below. First, 18.44 g of MEK was added to 10.00 g (0.052 mol in terms of MA) of the base polymer 2 to prepare a dissolving liquid. Next, 9.38 g (0.065 mol) of 4-HBA was added to this dissolving liquid, and then 3.00 g (0.030 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution, thereby removing the water phase from the reaction solution. Thereafter, the polymer was purified by the following procedure. • Use excess water to re-precipitate the polymer. · The operation of washing the polymer powder obtained by reprecipitation with excess water was repeated twice. The obtained reaction product was dried at 40°C for 12 hours. Through the above, 8.7g of polymer P14 in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with 4-HBA was obtained. GPC measurement was performed on the obtained polymer P14, and the weight average molecular weight and polydispersity of the polymer P14 were measured. The results are shown in Table 1. In addition, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P14. Thereby, it was confirmed that the unreacted monofunctional (meth)acrylic compound was not contained in the obtained polymer P14.

(Preparation Example 17) A resin composition 17 containing a polymer P15 in which the MA unit of the base polymer 2 was ring-opened with a monofunctional (meth)acrylic compound was produced. The details will be described below. First, 18.44 g of MEK was added to 10.00 g (0.052 mol in terms of MA) of the base polymer 2 to prepare a dissolving liquid. Next, 9.38 g (0.065 mol) of 4-HBA was added to this dissolving liquid, and then 3.00 g (0.030 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with formic acid aqueous solution and citric acid aqueous solution, thereby removing the water phase from the reaction solution. Furthermore, liquid-liquid extraction was performed by the same procedure as in Preparation Example 2, followed by solvent replacement, to obtain a resin composition 17. GPC measurement was performed on the obtained resin composition 17, and the polymer P15 contained in the composition, the amount of free monofunctional (meth)acrylic compound, and the weight average molecular weight and polydispersity of the polymer P15 were measured. The results are shown in Table 1.

The following Table 1 also shows the components used in each synthesis example and their loading amount (maleic anhydride (MA) conversion).

[Table 1] Preparation Example No. Polymer P (Resin composition No.) Raw polymer (Meth) acrylic compound that reacts with raw polymer Loading ratio (mole ratio) (vs MA) Multifunctional (meth)acrylic acid/monofunctional (meth)acrylic acid/water additive Adding dose Weight average molecular weight of polymer P (Mw) Polydispersity of polymer P (Mw/Mn) Amount of remaining polyfunctional (meth)acrylic compound (vs polymer P) (based on GPC area) (%) Amount of remaining monofunctional (meth)acrylic compound (vs polymer P) (based on GPC area) (%) Preparation Example 1 Polymer P1 Raw polymer 1 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.25/1.25/1.07 - 11300 1.83 0.0 0.0 Preparation Example 2 Polymer P2 (Resin composition 2) Raw polymer 1 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.25/1.25/1.07 - 10400 1.85 20.4 16.3 Preparation Example 3 Polymer P3 (Resin composition 3) Raw polymer 1 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.25/1.25/0.54 - 9900 1.81 21.1 25.6 Preparation Example 4 Polymer P4 (resin composition 4) Raw polymer 1 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.375/1.25/0.54 - 8500 1.64 33.4 23.8 Preparation Example 5 Polymer P5 (resin composition 5) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.25/1.25/0.54 - 5500 1.51 17.9 23.8 Preparation Example 6 Polymer P6 (resin composition 6) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.375/1.25/0.54 - 5800 1.52 26.9 23.4 Preparation Example 7 Polymer P7 (Resin composition 7) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.75/1.25/0.54 - 5000 1.40 80.7 28.3 Preparation Example 8 Polymer P8 (resin composition 8) Raw polymer 1 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.375/0.60/0.54 - 5000 1.51 63.5 17.3 Preparation Example 9 Polymer P9 (resin composition 9) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.375/0.90/0.54 - 5200 1.45 33.9 19.3 Preparation Example 10 Polymer P10 (resin composition 10) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.375/0.60/0.54 - 4800 1.42 35.3 11.8 Preparation Example 11 Polymer P11 (resin composition 11) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.50/1.25/0.54 - 6900 1.56 0.0 0.0 Preparation Example 12 Polymer P12 (resin composition 12) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.50/1.25/0.54 - 5500 1.49 46.7 25 Preparation Example 13 Polymer P3 (resin composition 13) Raw polymer 1 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.25/1.25/0.54 A-9550 15 parts by weight 9900 1.81 37.7 25.1 Preparation Example 14 Polymer P12 (resin composition 14) Raw polymer 2 A-TMM-3LM-N (3-functional) 4-HBA (monofunctional) 0.50/1.25/0.54 VISCOAT#802 30 parts by weight 5500 1.49 115.3 42.8 Preparation Example 15 Polymer P13 (resin composition 15) Raw polymer 1 4-HBA (monofunctional) 1.25 - 7800 1.62 0.0 0.0 Preparation Example 16 Polymer P14 (resin composition 16) Raw polymer 2 4-HBA (monofunctional) 1.25 - 4400 1.51 0.0 0.0 Preparation Example 17 Polymer P15 (Resin composition 17) Raw polymer 2 4-HBA (monofunctional) 1.25 - 4400 1.50 0.0 13.7

(Examples 1 to 12, Comparative Examples 1 to 5) In each example and each comparative example, the alkali solubility of the polymer P or the resin composition obtained in the above preparation example was evaluated. In addition, a photosensitive resin composition was prepared using the polymer P or resin composition, and its performance was evaluated. ＜Evaluation＞ [Developability evaluation] (Dissolution rate of polymer P in alkaline developer) The polymer P1 obtained in Preparation Example 1, the polymer P11 obtained in Preparation Example 11, the polymer P13 obtained in Preparation Example 15, and the polymer P14 obtained in Preparation Example 16 were dissolved in propylene glycol monomethyl ether. Acetate (PGMEA) was used to prepare a solution with a solid content concentration of 30% by mass. Next, spin-coat the above solution or the resin composition 2-10, 12-14, 17 obtained in Preparation Examples 2-10, 12-14, 17 on the wafer, and dry the PGMEA, and then pre-baked at a temperature of 100°C Bake (pre-bake) for 2 minutes to produce a resin film with a thickness of 2μm±0.2. The resin film and the wafer were immersed in a 2% sodium carbonate aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured. The dissolution rate is calculated by visually observing the immersed wafer, measuring the time until the resin film dissolves and no interference pattern is visible, and dividing the film thickness by the time. The structure is shown in Table 2. If the alkali dissolution rate is 180nm/s or more, it can be used as a photosensitive material without any problems, if it is 300nm/s or more, it can be regarded as good developability, and if it is 500nm/s or more, it can be regarded as particularly developability. good.

[Sensitivity Evaluation of Photosensitive Resin Composition 1 (The amount of exposure at which the residual film rate becomes 95% or more)] First, the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration became 30% by mass to obtain a photosensitive resin composition. ·Polymer P1 (polymer P1 of Preparation Example 1), polymer P11 (polymer P11 of Preparation Example 11), polymer P13 (polymer P13 of Preparation Example 15), or polymer P14 (polymer of Preparation Example 16 P14) or resin composition 2-10, 12-14, 17: 100 parts by mass (Here, with respect to resin compositions 2-10, 12-14, and 17, weighed so that the solid content (the total amount of polymers P2 to P10, P12, P15 and the polyfunctional (meth)acrylic compound) becomes 100 parts by mass .) ·Multifunctional acrylate (dineopentaerythritol hexaacrylate): 50 parts by mass ·Photopolymerization initiator (manufactured by BASF, Irgacure OXE01): 5 parts by mass ·Adhesion aid (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass ·Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated by HMDS (Hexamethyldisilazane) and baked on a hot plate at 100°C for 120 seconds to obtain a thickness of 3.0μm (±0.3μm ) Film A. The film A was passed through a gray-scale mask with a light-shielding rate of 1-100%, and a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. was used at an exposure of ^{100mJ/cm 2} The exposure of g+h+i rays is eliminated. After exposure, the film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (including wafer immersion), thereby obtaining film B that was exposed and developed at each exposure amount of ^{1-100 mJ/cm 2} . Based on the film thicknesses of film A and film B obtained by the above method, the residual film rate is calculated by the following formula. Residual film rate (%)=(film thickness of film B for each exposure amount/film thickness of film A)×100 Then, the exposure amount at which the residual film rate becomes 95% or more is used as the sensitivity of each photosensitive resin composition. The results are shown in Table 2. If the exposure amount at which the residual film ratio becomes 95% or more is 60 mJ/cm ² or less, it can be used as a photosensitive material without any problems.

[Sensitivity evaluation of resin composition 2 (residual film rate after low exposure exposure)] (Residual film rate at 5mJ/cm ² exposure) Spin-coating the photosensitive resin composition prepared in the above sensitivity evaluation 1 On a 3-inch silicon wafer treated by HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds, a film A with a thickness of 3.0μm (±0.3μm) was obtained. The film A was passed through a gray-scale mask with a light-shielding rate of 1-100%, and a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. was used at an exposure of ^{5mJ/cm 2} The exposure of g+h+i rays is eliminated. After the exposure, the film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (together with wafer immersion), whereby film B was obtained. Based on the film thicknesses of film A and film B obtained by the above method, the residual film rate is calculated by the following formula. Residual film rate (%) = (film thickness of film B for each exposure/film thickness of film A)×100

(Residual film rate at 10mJ/cm ² exposure) The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and then heated at 100°C. Bake on a hot plate for 120 seconds to obtain a film A with a thickness of 3.0 μm (±0.3 μm). The film A was passed through a gray-scale mask with a light-shielding rate of 1-100%, and a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. was used at an exposure amount of ^{10mJ/cm 2} The exposure of g+h+i rays is eliminated. After the exposure, the film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (together with wafer immersion), whereby film B was obtained. Based on the film thicknesses of film A and film B obtained by the above method, the residual film rate is calculated by the following formula. Residual film rate (%)=(film thickness of film B/film thickness of film A for each exposure amount)×100 The results are shown in Table 2. If the residual film rate is 50% or more, the sensitivity can be regarded as good, and if the residual film rate is 80% or more, the sensitivity can be regarded as particularly good.

[Yellow Index] The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., thickness 0.5mm), and baked on a hot plate at 100°C In 120 seconds, a film with a thickness of approximately 3.0 μm (±0.1 μm) was obtained. Next, the film was exposed to g+h+i rays using a g+h+i ray mask aligner (PLA-600F) manufactured by Canon Inc. at ^{an exposure amount of 100 mJ/cm 2.} After exposure, the film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (together with wafer immersion), thereby obtaining a film exposed and developed with an exposure amount of ^{100 mJ/cm 2.} The film was heat-treated at 230°C under air for 30 minutes. After the film was cooled in air at room temperature, the film was heated again at 230°C under air for 30 minutes. The same operation was repeated, and the heat treatment under air was performed 3 times for 30 minutes in total. Using a color-difference meter CR-5 (manufactured by Konica Minolta, Inc.), the yellow index (YI) of the film obtained by the above method was measured three times by changing the measurement position, and the average value was taken as the value of YI. The measurement type is transmission measurement, and 100% correction uses uncoated EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., thickness 0.5mm). The results are shown in Table 2. The smaller the value of the yellow index, the better the heat discoloration resistance, and if it is 1.35 or less, it can be used as a photosensitive material without any problems.

The results of the developability evaluation and the sensitivity evaluation are summarized below. [Table 2] Example No. The used polymer P/resin composition No. Performance evaluation of polymer P/resin composition Performance evaluation of photosensitive resin composition Alkali dissolution rate DR (nm/s) 95% residual film exposure (mJ/cm ² ) 0mJ/cm ² (unexposed part) Residual film rate during exposure Residual film rate at 2.5mJ/cm ^{2 exposure} Residual film rate at 5mJ/cm ^{2 exposure} Residual film rate at 10mJ/cm ^{2 exposure} Yellow index after heat treatment (YI) Comparative example 1 Polymer P1 242 15 0.0% - 0.0% 0.0% 1.37 Example 1 Resin composition 2 391 17 0.0% - 0.0% 83.5% 1.30 Example 2 Resin composition 3 343 26 0.0% - 0.0% 84.8% 1.35 Example 3 Resin composition 4 545 30 0.0% - 0.0% 81.5% 1.19 Example 4 Resin composition 5 352 60 0.0% - 51.2% 69.8% 1.03 Example 5 Resin composition 6 723 45 0.0% - 48.1% 81.9% 0.90 Example 6 Resin composition 7 ＞1000 59 0.0% - 80.0% 81.8% 0.98 Example 7 Resin composition 8 766 18 0.0% - 0.0% 85.0% 1.19 Example 8 Resin composition 9 923 30 0.0% - 57.0% 82.0% 0.8 Example 9 Resin composition 10 971 25 0.0% - 63.0% 91.0% 0.77 Comparative example 2 Resin composition 11 149 ＞60 0.0% - 0.0% 40.0% 1.12 Example 10 Resin composition 12 ＞1000 35 0.0% 1.8% 55.0% 80.0% 0.88 Example 11 Resin composition 13 500 16 0.0% - 2.5% 85.5% 1.33 Example 12 Resin composition 14 ＞1000 twenty two 0.0% 39.8% 62.5% 94.8% 0.82 Comparative example 3 Polymer P13 175 60 0.0% - 0.0% 0.0% 1.35 Comparative example 4 Polymer P14 172 ＞60 0.0% - 22.8% 37.9% 0.99 Comparative example 5 Resin composition 17 148 ＞60 0.0% - 2.2% 31.0% 1.04

The photosensitive resin composition of the example has a good alkali dissolution rate, and therefore is excellent in developability. The photosensitive resin composition of the example has a ^{high residual film rate when exposed to an exposure amount of 10 mJ/cm 2} , in other words, it is cured at a low exposure amount, and it can be said that the sensitivity is high. Therefore, the photosensitive resin composition of the Example has a high sensitivity and a low yellow index in a well-balanced manner.

＜Production of color filter＞ The photosensitive resin composition prepared in Examples 1-12 was prepared by adding an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., green) to the photosensitive resin composition. Things. By forming a film on a substrate, and performing exposure, alkali development treatment, etc., a green color filter can be formed. In addition, instead of NX-061, NX-053 (blue), NX-032 (red), etc. manufactured by the company can be used as a pigment dispersion to form a blue or red color filter.

＜Creation of black matrix＞ A black photosensitive resin composition in which an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin composition prepared in Examples 1-12 was prepared . By forming a film on a substrate, and performing exposure, alkali development treatment, etc., a black matrix can be formed.

This application claims priority based on Japanese Application Special Application No. 2019-189162 filed on October 16, 2019 and Japanese Application Special Application No. 2020-005974 filed on January 17, 2020, and reveals all of its contents Incorporated here.

10: substrate 11: black matrix 12: Color filter 13: Protective film 14: Transparent electrode layer

[FIG. 1] A diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging element.

10: substrate

11: black matrix

12: Color filter

13: Protective film

14: Transparent electrode layer

Claims (21)

A resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); and a compound having two or more (meth)acrylic groups,

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

In formula (1), R ^p is a group having two or more (meth)acryloyl groups. The resin composition of claim 1, wherein the aforementioned polymer further contains a structural unit represented by formula (2),

In formula (2), R ^s is a group having one (meth)acryloyl group. Such as the resin composition of claim 1, in which, The weight average molecular weight of the aforementioned polymer is 1,000 or more and 20,000 or less. Such as the resin composition of claim 1, in which, In the gel permeation chromatography (GPC) chart of the resin composition, the peak area derived from the aforementioned compound having two or more (meth)acrylic groups is 5% or more and 150% relative to the peak area of the aforementioned polymer. %the following. The resin composition of claim 1, wherein the aforementioned polymer further contains a structural unit represented by formula (3),

. The resin composition of claim 1, wherein the aforementioned polymer further contains a structural unit represented by formula (MA),

. The resin composition of claim 1, which further contains a compound having one (meth)acryloyl group. Such as the resin composition of claim 7, in which, In the gel permeation chromatography (GPC) chart of the resin composition, the peak area derived from the aforementioned compound having one (meth)acryloyl group is 5% to 60% relative to the peak area of the aforementioned polymer. For example, the resin composition of claim 1 has an alkali dissolution rate of 250 nm/s or more. Such as the resin composition of claim 1, which further contains an organic solvent. Such as the resin composition of claim 10, in which, The aforementioned solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, and cyclohexanone. The resin composition of any one of claims 1 to 11, which is used to form a color filter or a black matrix. A photosensitive resin composition comprising: a polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (1); a compound having two or more (meth)acryloyl groups; and Sensitizer,

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

In formula (1), R ^p is a group having two or more (meth)acryloyl groups. The photosensitive resin composition of claim 13, wherein the aforementioned polymer further contains a structural unit represented by formula (2),

In formula (2), R ^s is a group having one (meth)acryloyl group. Such as the photosensitive resin composition of claim 13, wherein: The weight average molecular weight of the aforementioned polymer is 1,000 or more and 20,000 or less. Such as the photosensitive resin composition of claim 13, wherein: In the gel permeation chromatography (GPC) diagram of the photosensitive resin composition, the peak area derived from the compound having two or more (meth)acrylic groups is 5% or more relative to the peak area of the polymer. And less than 150%. The photosensitive resin composition of claim 13, wherein the aforementioned polymer further contains a structural unit represented by formula (3),

. The photosensitive resin composition of claim 13, wherein the aforementioned polymer further contains a structural unit represented by formula (MA),

. The photosensitive resin composition of claim 13, which further contains a compound having one (meth)acryloyl group. Such as the photosensitive resin composition of claim 19, wherein: In the gel permeation chromatography (GPC) diagram of the photosensitive resin composition, the peak area derived from the compound having one (meth)acryloyl group is 5% or more and 60% relative to the peak area of the polymer. the following. A cured product formed from the photosensitive resin composition of any one of claims 13 to 20.

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