TW202237676A - Copolymer and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide: a resin composition which exhibits good developing performance when used as a photosensitive material, which has excellent storage stability, and which yields a cured product having excellent solvent resistance even if cured at a low temperature; a copolymer that is useful for preparing this resin composition; and a method for producing the copolymer. This copolymer contains a constituent unit (a) having a group represented by formula (1) or formula (2), a constituent unit (b) having a hydroxyl group and a constituent unit (c) having an acid group, and has a glass transition temperature of 30 DEG C or lower.

Description

Copolymer and method for producing the same

The present invention relates to a copolymer, a resin composition, a color filter, an image display element and a method for producing the copolymer.

In general, organic electroluminescent (EL) display devices (especially, WRGB method combining white light-emitting organic EL and color filters), image display elements such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements In the image imaging element such as, set color filter, black matrix, color filter protective film, photo spacer, protrusion for liquid crystal alignment, or film and fine graphics.

In recent years, along with the flexibility and wearability of displays, the conversion of substrate materials from glass to organic materials such as resins is progressing. An organic material with poor heat resistance compared to glass. Therefore, in a member formed by thermally curing a resin composition on a substrate, it is desirable to lower the temperature at which the resin composition is thermally cured, depending on the heat resistance of the substrate made of an organic material. For example, color filters are conventionally formed by thermosetting a resin composition on a substrate at a temperature of 210-230°C. However, when a color filter is formed on a flexible substrate made of resin, since the substrate has poor heat resistance, it is required to heat-cure the resin composition at a temperature of 80-150°C.

In particular, in color filters used in organic EL display devices, in order to improve color reproducibility, there is a tendency to increase the content of the colorant contained in the resin composition. In general, it is difficult to light-cure a resin composition containing a large amount of colorant. Therefore, in the resin composition used for the color filter of the organic EL display device, it is more important to harden it by thermal crosslinking. Therefore, in the resin composition used for the color filter of an organic electroluminescent display apparatus, especially, the necessity of improving the thermosetting property at low temperature is increasing.

Conventionally, there are, for example, those described in Patent Document 1 and Patent Document 2 regarding resin compositions used as color filter materials. Patent Document 1 discloses a photosensitive coloring composition containing the following (a) to (e). (a) A polymerization initiator whose 365nm absorption coefficient in methanol is 1.0×10 ³ mL/gcm or more, (b) 365nm absorption coefficient in methanol is 1.0×10 ² mL/gcm or less and 254nm absorption coefficient is 1.0×10 ³ mL/gcm or more polymerization initiator, (c) compound with unsaturated double bond, (d) alkali-soluble resin, (e) coloring material. Patent Document 2 discloses a photosensitive composition for color filters containing a furyl group-containing compound, a photopolymerizable functional group-containing compound, a photopolymerization initiator, and a colorant. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-041058 [Patent Document 2] Japanese Patent Laid-Open No. 2017-194662

[Problem to be Solved by the Invention]

However, the conventional resin composition has not obtained a cured product that has good developability and storage stability when used as a photosensitive material, and is excellent in solvent resistance when cured at a low temperature. The present invention is made in view of the above circumstances, and its object is to provide a resin composition, a copolymer useful for preparing the resin composition, and a method for producing the copolymer, and the development of the resin composition when used as a photosensitive material It has good properties and excellent storage stability, and even when it is cured at low temperature, a cured product with excellent solvent resistance can be obtained. In addition, the object of the present invention is to provide a color filter and an image display device having the color filter. The color filter has excellent developability and can obtain solvent resistance even if it is hardened at a low temperature. A coloring pattern made of a cured product of an excellent cured resin composition. [Means to solve the problem]

The present invention includes the following aspects. [1] A copolymer characterized by containing A structural unit (a) having a group represented by the following formula (1) or the following formula (2), a structural unit (b) having a hydroxyl group, and a structural unit (c) having an acid group, Its glass transition temperature is below 30°C.

(式(1)中，R ¹及R ²各自獨立，表示碳數1~10之烷基。＊表示連結部位)。

(In formula (1), R ¹ and R ² are each independently representing an alkyl group having 1 to 10 carbon atoms. * represents a linking site).

(式(2)中，R ³表示碳數1~10之烷基。＊表示連結部位)。

(In formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site).

[2] The copolymer described in [1], wherein the structural unit (b) is a structural unit derived from a hydroxyalkyl (meth)acrylate. [3] The copolymer as described in [1] or [2], wherein the structural unit (c) is a structural unit derived from an unsaturated carboxylic acid. [4] The copolymer as described in any one of [1] to [3], wherein the aforementioned structural unit (a) is derived from the group represented by the aforementioned formula (1) or the aforementioned formula (2) and (methyl ) is a structural unit of an acryloxy compound.

[5] The copolymer as described in any one of [1] to [4], which contains 1 to 40 mol% of the aforementioned structural unit (a), 1 to 60 mol% of the aforementioned structural unit (b), and the aforementioned structure Unit (c) 1~60 mole%. [6] The copolymer as described in any one of [1] to [5], wherein the total amount of ester groups contained in the group represented by the aforementioned formula (1) or the aforementioned formula (2) is equal to the amount of the aforementioned structural unit (b The molar ratio of the total amount of hydroxyl groups contained in ) is 10:90~90:10. [7] The copolymer described in any one of [1] to [6], wherein the weight average molecular weight is 1,000 to 50,000.

[8] A resin composition characterized by comprising the copolymer (A) described in any one of [1] to [7] and a solvent (B), wherein the solvent (B) contains a hydroxyl group-containing solvent. [9] Further containing a reactive diluent (C), a photopolymerization initiator (D), and the resin composition described in [8]. [10] It further contains a colorant (E) and the resin composition described in [9].

[11] The resin composition as described in [10], which contains: 10-90 parts by mass of the aforementioned copolymer (A), Aforesaid solvent (B) 30～1000 mass parts, 10-90 parts by mass of the aforementioned reactive diluent (C), 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (D), 3-80 parts by mass of the aforementioned colorant (E).

[12] A color filter characterized by having a colored pattern made of a hardened resin composition as described in [10] or [11]. [13] An image display device characterized by comprising the color filter described in [12].

[14] A method for producing a copolymer, characterized by having the following steps (I) to (III): The solvent heating step (I) of heating the solvent (B-1) to 60~90° C. to prepare the heated solvent (B-1h); Dissolving the monomer (m-a), the hydroxyl-containing monomer (m-b) and the acid group-containing monomer (m-c) having the group represented by the following formula (1) or the following formula (2) in the solvent (B -2) The resulting monomer solution is dropped into the aforementioned solvent (B-1h) which has been heated, At the same time, the polymerization initiator solution formed by dissolving the polymerization initiator in the aforementioned solvent (B-2) is dropped to the aforementioned solvent (B-1h) to make a mixed solution in the dripping polymerization step (II); and The post-polymerization step (III) of reacting at 60-90° C. for 1-5 hours while stirring the aforementioned mixed solution; Either or both of the aforementioned solvent (B-1) and the aforementioned solvent (B-2) contain a hydroxyl group-containing solvent.

(式(1)中，R ¹及R ²各自獨立，表示碳數1~10之烷基。＊表示連結部位)。

(In formula (1), R ¹ and R ² are each independently representing an alkyl group having 1 to 10 carbon atoms. * represents a linking site).

(式(2)中，R ³表示碳數1~10之烷基。＊表示連結部位)。

(In formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site).

[15] The method for producing a copolymer as described in [14], wherein in the solvent heating step (I), the temperature is raised after adding a chain transfer agent to the solvent (B-1). [Invention effect]

According to the present invention, it is possible to provide a resin composition, a copolymer useful for preparing the resin composition, and a method for producing the copolymer. The resin composition has good alkali developability when used as a photosensitive material, and can be stored It has excellent stability and can obtain a cured product with excellent solvent resistance even when it is cured at low temperature. Also, according to the present invention, a color filter and a color filter having the same can be provided, This color filter has a colored pattern formed of a cured product of a resin composition that has good developability and can be cured at a low temperature to obtain a cured product excellent in solvent resistance.

Hereinafter, the copolymer of the present invention, the method for producing the copolymer, the resin composition, the color filter, and the image display device will be described in detail. However, the present invention is not limited to the embodiments shown below.

In addition, in this specification, what shows (meth)acrylate means that either acrylate or methacrylate may be used. In addition, the sign of (meth)acrylic acid means that either acrylic acid or methacrylic acid may be used.

＜Copolymer (A)＞ The copolymer (A) of the present embodiment contains a structural unit (a) having a group represented by the following formula (1) or the following formula (2) (hereinafter also referred to simply as "structural unit (a)") , a structural unit (b) having a hydroxyl group (hereinafter also referred to only as "structural unit (b)"), and a structural unit (c) having an acidic group (hereinafter also referred to only as "structural unit (c)") .

(式(1)中，R ¹及R ²各自獨立，表示碳數1~10之烷基。＊表示連結部位)。

(In formula (1), R ¹ and R ² are each independently representing an alkyl group having 1 to 10 carbon atoms. * represents a linking site).

(式(2)中，R ³表示碳數1~10之烷基。＊表示連結部位)。

(In formula (2), R ³ represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site).

＜Structural unit (a)＞ The structural unit (a) is a structural unit derived from a monomer (m-a) having a group represented by the above formula (1) or the above formula (2) (hereinafter also simply referred to as "monomer (m-a)") . The group represented by the above formula (1) or the above formula (2) of the structural unit (a) contained in the copolymer (A) is combined with the structural unit by thermosetting the resin composition containing the copolymer (A). (b) The hydroxyl group which it has carries out transesterification, and produces|generates a crosslinked structure. Therefore, even if the resin composition containing a copolymer (A) is cured at a low temperature of 50° C. to 150° C., a cured film excellent in solvent resistance can be obtained.

R ¹ and R ² in the above formula (1) are each independently an alkyl group having 1 to 10 carbon atoms. R ¹ and R ² are each independently, preferably an alkyl group with 2 to 6 carbons, more preferably an alkyl group with 2 to 3 carbons, and most preferably both R ¹ and R ² are ethyl with 2 carbons. When R ¹ and R ² are ethyl groups, when the resin composition containing the copolymer (A) is thermally cured, R ¹ and R ² undergo transesterification with the hydroxyl group of the structural unit (b) to generate ethanol. Ethanol produced during thermosetting of the resin composition is preferable because it can be easily evaporated and removed by heating for thermosetting the resin composition.

Also, R in the above formula (2) is an alkyl group having ¹ to 10 carbon atoms. R ³ is preferably an alkyl group with 2 to 6 carbons, more preferably an alkyl group with 2 to 3 carbons, and even more preferably an ethyl group with 2 carbons. When R ³ is an ethyl group, when the resin composition containing the copolymer (A) is thermally cured, R ³ and the hydroxyl group of the structural unit (b) undergo transesterification to generate ethanol. Ethanol produced during thermosetting of the resin composition is preferable because it can be easily evaporated and removed by heating for thermosetting the resin composition.

The monomer (m-a) providing the structural unit (a) is not particularly limited as long as it is a compound copolymerizable with the hydroxyl group-containing monomer (m-b) and the acid group-containing monomer (m-c) described later. As the monomer (m-a), for example, one having a group represented by the above formula (1) or the above formula (2) and an ethylenically unsaturated bond can be used from the viewpoint of reactivity when synthesizing the copolymer (A). monomer. As a group which has an ethylenically unsaturated bond, a vinyl group and a (meth)acryloxy group are mentioned specifically,.

Examples of the monomer (m-a) having a group represented by the above formula (1) or the above formula (2) and an ethylenically unsaturated bond include an ethylenically unsaturated group-containing isocyanate compound and a malonate diester or Reactant of acetyl acetate. These monomers (m-a) may be used alone or in combination of two or more.

The ethylenically unsaturated group-containing isocyanate compound that forms the monomer (m-a) is preferably a compound represented by the following formula (3).

(式(3)中，R ⁴表示氫原子或甲基。R ⁵表示-CO-、-COOR ⁶- (此處，R ⁶為碳原子數1~6之伸烷基)或-COO-R ⁷O-CONH-R ⁸- (此處，R ⁷為碳原子數2~6之伸烷基；R ⁸為可具有取代基之碳原子數2~12之伸烷基或碳原子數6~12之伸芳基))。

(In formula (3), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents -CO-, -COOR ⁶ - (here, R ⁶ is an alkylene group with 1 to 6 carbon atoms) or -COO-R ⁷ O-CONH-R ⁸ - (Here, R ⁷ is an alkylene group with 2 to 6 carbon atoms; R ⁸ is an alkylene group with 2 to 12 carbon atoms that may have a substituent or an alkylene group with 6 to 6 carbon atoms 12 of the aryl)).

R ⁴ in formula (3) represents a hydrogen atom or a methyl group. R ⁵ in formula (3) represents -CO-, -COOR ⁶ - or -COO-R ⁷ O-CONH-R ⁸ -. Here, R6 is an alkylene group having 1 to ⁶ carbon atoms. ^R7 is an alkylene group having 2 to 6 carbon atoms. In addition, R ⁸ is an alkylene group having 2 to 12 carbon atoms or an arylylene group having 6 to 12 carbon atoms which may have a substituent. Among them, R ⁵ in formula (3) is preferably -COOR ⁶ -. When R ⁵ is -COOR ⁶ -, R ⁶ is preferably an alkylene group having 1 to 4 carbon atoms.

As the ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3), specifically, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl ( Meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1, 1-Dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, (meth)acryl isocyanate, and the like.

Also, as the ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3), an equimolar ratio of 2-hydroxyalkyl (meth)acrylate and diisocyanate compound (1 mole: 1 mole ear) reaction product. As the alkyl group contained in the above-mentioned 2-hydroxyalkyl (meth)acrylate, ethyl or n-propyl is preferred, and ethyl is more preferred. As the diisocyanate compound mentioned above, for example, hexamethylene diisocyanate, 2,4-(or 2,6-) toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis( Isocyanatomethyl)cyclohexane, lysine diisocyanate, and the like.

Among these isocyanate compounds containing ethylenically unsaturated groups, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanate Acidyl propyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (methyl) ) acrylate, 4-isocyanatocyclohexyl (meth)acrylate and (meth)acryl isocyanate are preferred, 2-isocyanatoethyl (meth)acrylate and 2-isocyanate More preferred is propyl (meth)acrylate. These ethylenically unsaturated group-containing isocyanate compounds may be used alone or in combination of two or more.

As the malonate diester reacted with the ethylenically unsaturated group-containing isocyanate compound, for example, dimethyl malonate, diethyl malonate, di(n-propyl malonate), malonate Diethyl malonate or dimethyl malonate is preferred in view of the ease of acquisition, cost, and quality of di(i-propyl ester). As the acetyl acetate reacted with the ethylenically unsaturated group-containing isocyanate compound, acetyl acetate methyl, acetyl acetate ethyl, etc. are mentioned, for example.

The reaction of the ethylenically unsaturated group-containing isocyanate compound with malonic acid diester or acetoacetate can be carried out regardless of the presence or absence of a solvent. When performing the above reaction using a solvent, a solvent inert to isocyanato groups is used. In the above reaction, organometallic salts of tin, zinc, lead, etc., tertiary amines, etc. can also be used as catalysts. Generally speaking, the above reaction can be carried out at a temperature of -20~150°C, preferably at a temperature of 25~130°C. If the temperature of the above reaction is -20°C or higher, a sufficient reaction rate can be obtained. In addition, if the temperature of the above reaction is below 150°C, the polymerization of the raw material having C=C (double bond) can prevent the monomer (m-a) that provides the structural unit (a) generated after the reaction from gelling. change.

<Structural unit (b) having a hydroxyl group> The structural unit (b) having a hydroxyl group contained in the copolymer (A) does not have the group represented by the above formula (1) or the above formula (2), but has a hydroxyl group. The structural unit (b) is a structural unit derived from a monomer (m-b) having a hydroxyl group (hereinafter also simply referred to as "monomer (m-b)") (except for those conforming to the aforementioned structural unit (a)). The hydroxyl group of the structural unit (b) contained in the copolymer (A) is expressed by the formula (1) or formula (2) possessed by the structural unit (a) by thermosetting the resin composition containing the copolymer (A). The indicated group is transesterified to generate a cross-linked structure.

The monomer (m-b) providing the structural unit (b) does not have the group represented by the above formula (1) or the above formula (2), and is not particularly limited as long as it is a monomer having a polymerizable unsaturated bond and a hydroxyl group. As a monomer (m-b), the (meth)acrylate derivative which has a hydroxyl group is mentioned, for example. Such a monomer (m-b) specifically includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate , 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. These monomers (m-b) may be used alone or in combination of two or more.

As the monomer (m-b), among the above-mentioned monomers, from the viewpoint of the reactivity when synthesizing the copolymer (A), the low-temperature curability of the resin composition containing the copolymer (A), and the ease of acquisition, Hydroxyalkyl (meth)acrylate is preferred. As the hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate are preferred, From the viewpoint of lowering the glass transition temperature of the copolymer (A), 4-hydroxybutyl (meth)acrylate is more preferable.

<Structural unit (c) having an acid group> The structural unit (c) having an acid group contained in the copolymer (A) does not have a group represented by the above formula (1) or the above formula (2) and a hydroxyl group, but has an acid group. Structural unit (c) is a structural unit derived from a monomer (m-c) having an acid group (hereinafter, also simply referred to as "monomer (m-c)") (but, conforming to structural unit (a) and structural unit (b ) are excluded). When the copolymer (A) contains the structural unit (c), the alkali developability at the time of using the resin composition containing a copolymer (A) as a photosensitive material becomes favorable.

As the acid group which the structural unit (c) has, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned. Among these acid groups, a carboxyl group is preferable as the acid group contained in the structural unit (c) from the viewpoint of ease of acquisition. As the monomer (m-c) providing the structural unit (c), it does not have the group and hydroxyl group represented by the above formula (1) or the above formula (2), as long as it is a monomer with a polymerizable unsaturated bond and an acid group, it can be No particular limitation. As a monomer (m-c), unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid, unsaturated phosphonic acid, etc. are mentioned, for example.

As the monomer (m-c), specifically, (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α- Cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid , citraconic anhydride and other unsaturated carboxylic acids or their anhydrides; 2-acrylamide-2-methylpropanesulfonic acid, tertiary butylacrylamidesulfonic acid, p-styrenesulfonic acid and other unsaturated sulfonic acids ; Unsaturated phosphonic acid such as vinylphosphonic acid; etc. These monomers (m-c) may be used alone or in combination of two or more.

As the monomer (m-c), among these monomers, unsaturated carboxylic acid is preferably used because it can be easily obtained and the resin composition containing the copolymer (A) has excellent alkali developability. More preferably (meth)acrylic acid is used.

Here, the ratio of the structural unit (a), structural unit (b), and structural unit (c) contained in a copolymer (A) is demonstrated. Although the ratio of the structural unit (a) contained in the copolymer (A) is not particularly limited, it is preferably 1-40 mole%, more preferably 5-30 mole%, most preferably 10-20 mole% %. Although the proportion of the structural unit (b) contained in the copolymer (A) is not particularly limited, it is preferably 1-60 mole%, more preferably 10-50 mole%, most preferably 20-40 mole% %. Although the proportion of the structural unit (c) contained in the copolymer (A) is not particularly limited, it is preferably 1-60 mol%, more preferably 10-50 mol%, most preferably 15-40 mol% %.

Therefore, the copolymer (A) preferably contains 1-40 mol% of the structural unit (a), 1-60 mol% of the structural unit (b), and 1-60 mol% of the structural unit (c). In the copolymer (A) of this embodiment, if the ratio of the structural unit (a) to the structural unit (b) is 1 mol % or more, the structure will be improved by thermosetting the resin composition containing the copolymer (A). The hydroxyl group of the unit (b) is transesterified with the group represented by the formula (1) or formula (2) of the structural unit (a). Therefore, a crosslinked structure is sufficiently generated. Therefore, the resin composition containing the copolymer (A) containing 1 mol% or more of the structural unit (a) and the structural unit (b) can obtain a cured composition with good solvent resistance even if it is thermally cured at a low temperature. things.

When the ratio of the structural unit (a) in a copolymer (A) is 40 mol% or less, the storage stability of the resin composition containing a copolymer (A) becomes more favorable. Moreover, if the ratio of a structural unit (a) is 40 mol% or less, it becomes easy to ensure content of a structural unit (b) and a structural unit (c). Therefore, it becomes easy to acquire the effect by containing a structural unit (b) and a structural unit (c).

Moreover, when the ratio of the structural unit (b) in a copolymer (A) is 60 mol% or less, gelation at the time of the polymerization reaction for manufacturing a copolymer (A) can be prevented. Moreover, the crosslinked structure by the transesterification reaction of a structural unit (a) and a structural unit (b) will not generate|occur|produce excessively, and the storage stability of the resin composition containing a copolymer (A) becomes more favorable. Moreover, if the ratio of a structural unit (b) is 60 mol% or less, it becomes easy to ensure content of a structural unit (a) and a structural unit (c). Therefore, it becomes easy to acquire the effect by containing a structural unit (a) and a structural unit (c).

When the ratio of the structural unit (c) in a copolymer (A) is 1 mol% or more, the resin composition containing a copolymer (A) will have sufficiently high alkali developing speed. If the proportion of the structural unit (c) in the copolymer (A) is 60 mol% or less, since the alkali developing speed of the resin composition containing the copolymer (A) is moderately suppressed, it becomes easy to form a delicate graphics. Moreover, if the ratio of the structural unit (c) in a copolymer (A) is 60 mol% or less, it becomes easy to ensure content of a structural unit (a) and a structural unit (b). Therefore, even when the resin composition containing the copolymer (A) is cured at a low temperature, it becomes easier to obtain a cured product excellent in solvent resistance.

In copolymer (A), the molar ratio of ester group to hydroxyl group ((a):(b)) is preferably 10:90~90:10, more preferably 30:70~70:30, 40:60~ 60:40 is better. The molar ratio ((a):(b)) of the ester group to the hydroxyl group is the total amount of the ester group shown in the above formula (1) or the above formula (2) that the structural unit (a) has and the structural unit (b) ) is the molar ratio of the total amount of hydroxyl groups contained. When the molar ratio ((a):(b)) of the ester group to the hydroxyl group is within the above range, the resin composition containing the copolymer (A) is thermally cured to easily form a hydroxyl group of the structural unit (b) A crosslinked structure resulting from transesterification with the group represented by the formula (1) or formula (2) that the structural unit (a) has. Therefore, a cured product having better solvent resistance can be obtained.

The total amount of the content of the structural unit (a) and the content of the structural unit (b) contained in the copolymer (A) is preferably 20-80 mol%, more preferably 20-60 mol%, and 25-40 Mole% is better. If the total amount of the content of the structural unit (a) and the content of the structural unit (b) is 20 to 80 mol%, the resin composition containing the copolymer (A) will have better storage stability, even at low temperature. A hardened product with excellent solvent resistance can also be obtained when it is cured. Moreover, since it becomes easy to ensure content of a structural unit (c), it becomes easy to obtain the resin composition with more favorable alkali developability when used as a photosensitive material.

When the resin composition containing the copolymer (A) contains, in addition to the copolymer (A), a compound having a hydroxyl group as a reactive diluent (C), the structural unit (b) contained in the copolymer (A) has The total amount of hydroxyl groups in the reactive diluent (C) is preferably reduced by the amount corresponding to the amount of hydroxyl groups contained in the reactive diluent (C). Specifically, the molar ratio of the total amount of ester groups in the above formula (1) or the above formula (2) contained in the structural unit (a) to the total amount of hydroxyl groups contained in the resin composition is 10:90 ~90:10 is better, 30:70~70:30 is better, 40:60~60:40 is even better. The total amount of hydroxyl groups contained in the resin composition is the sum of the hydroxyl groups contained in the structural unit (b) and the hydroxyl groups contained in the reactive diluent (C). If the above-mentioned molar ratio is within the above-mentioned range, by thermosetting the resin composition containing the copolymer (A), it becomes easy to produce the formula (1) that the hydroxyl group and the structural unit (a) contained in the resin composition have Or the cross-linked structure caused by the transesterification of the group represented by the formula (2). Therefore, a cured product having better solvent resistance can be obtained.

＜Other structural units (d)＞ The copolymer (A) of this embodiment can also contain other structural units (d) that can be copolymerized with these structural units (a)~(c) if necessary (but, in accordance with the structural units (a)~(c) (c) except).

The monomer (m-d) (hereinafter, simply referred to as "monomer (m-d)") providing another structural unit (d) preferably does not contain a blocking agent such as a compound having a blocked isocyanate group. If the copolymer (A) contains a structural unit derived from a blocking agent, in the cured product obtained by applying, exposing, and developing a resin composition containing this, heating and curing it, there may be The case of remaining blocking agent. The blocking agent remaining in the cured product may have a bad influence on the insulation of the cured product, or may deteriorate the solvent resistance of the cured product. Also, the blocking agent remaining in the cured product may cause dark spots due to outgassing in an image display device having a color filter having a colored pattern made of the cured product.

Specific examples of monomers (md) providing other structural units (d) include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylates, (meth) Acrylate, (meth)acrylamide, vinyl compound, unsaturated dicarboxylic acid diester, monomaleimide, glycidyl (meth)acrylate, (meth)acrylamide benzene, (Meth)acrylonitrile, acrolein, etc. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p - nitrostyrene, p-cyanostyrene, p-acetylaminostyrene and the like. Examples of cyclic olefins having a norbornene structure include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4 .0.1 ^2,5 .1 ^7,10 ]dode-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dode-3-ene, dicyclopentadiene, Tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, Tricyclo[4.4.0.1 ^2,5 ]Undec-3-ene, Tricyclo[6.2.1.0 ^1,8 ]Undec-9-ene, Tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodeca-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 7,12 ] ^dodeca- 3-ene, Pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] Penta-4-ene, etc. As diene, butadiene, isoprene, chloroprene, etc. are mentioned. Examples of (meth)acrylate include meth (meth)acrylate, ethyl (meth)acrylate, iso-propyl (meth)acrylate, tertiary butyl (meth)acrylate, Amyl (meth)acrylate, benzyl (meth)acrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, Dialkyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5- Ethyl norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxy ethyl acrylate, isobornyl ( Meth)acrylate, adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate base) acrylate, perfluoro-n-propyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate ester, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy Polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, biphenoxyethyl (meth)acrylate, naphthalene (meth)acrylate, Anthracene (meth)acrylate, ethoxylated phenyl (meth)acrylate, etc. Examples of (meth)acrylamide include (meth)acrylamide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-di-isopropylamide , (meth)acrylic acid anthracenamide, etc. Examples of the vinyl compound include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, and the like. As unsaturated dicarboxylic acid diester, diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc. are mentioned. Examples of monomaleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, and N-(4-hydroxyphenyl)maleimide. imide, etc.

Among them, it is preferable to use (meth)acrylate as the monomer (m-d). From the viewpoint of adjusting the glass transition temperature of the copolymer (A) to 30°C or less, the glass transition temperature of the homopolymer The temperature is preferably below -20°C, especially preferably 2-ethylhexyl (meth)acrylate or 4-hydroxybutyl acrylate. These monomers (m-d) may be used alone or in combination of two or more.

When the copolymer (A) contains other structural units (d), the ratio is not particularly limited, but it is preferably more than 0 mole % to less than 80 mole %, more preferably 10 to 60 mole %, most preferably 15~50 mole%. By containing the other structural unit (d), the copolymer (A) can suitably improve properties such as solvent resistance in a cured product of a resin composition containing the copolymer (A). If the content of other structural units (d) is 80 mol% or less, it becomes easy to ensure the content of structural units (a) to structural units (c), including the effects of structural units (a) to structural units (c) become significant.

(weight average molecular weight (Mw)) The polystyrene-equivalent weight average molecular weight of the copolymer (A) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 3,000 to 40,000. When the weight average molecular weight of the copolymer (A) is 1,000 or more, the alkali developability of the resin composition containing the copolymer (A) when used as a photosensitive material becomes good, and pattern defects are less likely to occur after alkali development. On the other hand, when the weight average molecular weight of a copolymer (A) is 50,000 or less, the developing time when using the resin composition containing a copolymer (A) as a photosensitive material becomes appropriate, and practicality is ensured.

(Glass transition temperature (Tg)) The glass transition temperature (Tg) of the copolymer (A) is 30°C or lower, preferably 20°C or lower, more preferably 0°C or lower. If the glass transition temperature of the copolymer (A) exceeds 30°C, it will adversely affect the curability at low temperatures. Therefore, the glass transition temperature of the copolymer (A) is set to be 30° C. or lower. The glass transition temperature of the copolymer (A) is preferably -50°C or higher, more preferably -40°C or higher, and even more preferably -30°C or higher. When the glass transition temperature of a copolymer (A) is -50 degreeC or more, the resin composition containing a copolymer (A) becomes what can obtain the cured film excellent in heat resistance.

(acid value) The acid value (JIS K6901 5.3) of a copolymer (A) can be selected suitably. The acid value of the copolymer (A) is preferably 20-300 KOHmg/g, more preferably 30-200 KOHmg/g when the resin composition containing the copolymer (A) is used as a photosensitive material. When the acid value of a copolymer (A) is 20KOHmg/g or more, the alkali developability at the time of using the resin composition containing a copolymer (A) as a photosensitive material becomes favorable. On the other hand, if the acid value of the copolymer (A) is 300 KOHmg/g or less, when the resin composition containing the copolymer (A) is used as a photosensitive material, since it becomes an exposed part (photohardened part) The developer is difficult to dissolve, so the pattern shape becomes good.

(the equivalent number of the base represented by the above formula (1) or the above formula (2)) The copolymer (A) contains a group represented by the above formula (1) or the above formula (2) in the molecule. The number of equivalents of the base represented by the above formula (1) or the above formula (2) may be appropriately selected, but is preferably 300~6000, more preferably 1000~3000. If the number of equivalents of the group represented by the above formula (1) or the above formula (2) is 300 or more, when the hydroxyl group is sufficiently present in the resin composition containing the copolymer (A), by making it thermally hardened, the A cross-linked structure resulting from transesterification between the hydroxyl group in the resin composition and the group represented by the formula (1) or formula (2) of the structural unit (a) is sufficiently formed. Therefore, a cured product having better solvent resistance can be obtained.

The equivalent number of the group represented by the above formula (1) or the above formula (2) in the copolymer (A) is the group represented by the above formula (1) or the above formula (2) contained in the copolymer (A). The mass of the copolymer (A) per 1 mole. The equivalent number of the base represented by the above formula (1) or the above formula (2) is obtained by dividing the mass of the copolymer (A) by the above formula (1) or the above formula (2) contained in the copolymer (A) The molar number of the indicated base is obtained (g/mol). The equivalent number of the groups represented by the above formula (1) or the above formula (2) is a theoretical value calculated from the feed amount of the monomer (m-a). In fact, as described in the production method of the copolymer (A) described later, the group represented by the above formula (1) or the above formula (2) in the copolymer (A) is partly derived from the monomer ( The hydroxyl group in m-b) or the hydroxyl group-containing solvent that can be used as the solvent (B-1) and/or the solvent (B-2) is present in the copolymer (A) in a transesterified state.

＜Method for producing copolymer (A)＞ The copolymer (A) of the present embodiment can be produced, for example, by a method of sequentially performing the solvent heating step (I), the dropping polymerization step (II) and the post-polymerization step (III) shown below. (solvent heating step (I)) The temperature of the solvent (B-1) was raised to 60~90°C, and the heated solvent (B-1h) was prepared. In the solvent heating step (I), a chain transfer agent described later may be added to the solvent (B-1), and then the temperature may be raised. By adding the chain transfer agent to the solvent (B-1) and then raising the temperature, the degree of polymerization of the copolymer (A) synthesized in the dropwise polymerization step (II) and the post-polymerization step (III) can be controlled. The concentration of the chain transfer agent in the solvent (B-1) may be, for example, 0.1 to 10% by mass, and is not particularly limited.

(drop polymerization step (II)) While stirring the heated solvent (B-1h), drop the polymerization initiator solution together with the monomer solution into the heated solvent (B-1h) to form a mixed solution for dropwise polymerization. Monomer solution, in order to make the monomer (m-a), hydroxyl-containing monomer (m-b) and acid group-containing monomer (m-c) having the group represented by above-mentioned formula (1) or above-mentioned formula (2), and The monomer (m-d) to be used is dissolved in the solvent (B-2). The polymerization initiator solution is obtained by dissolving the polymerization initiator in the solvent (B-2). In the manufacturing method of the copolymer (A) of this embodiment, either or both of solvent (B-1) and solvent (B-2) contain a hydroxyl group containing solvent.

In the liquid polymerization step (II), the chain transfer agent solution described later can also be added dropwise instead of the chain transfer agent that can be added in the solvent heating step (I). The chain transfer agent solution is obtained by dissolving the chain transfer agent in the solvent (B-2). In addition, in the solvent heating step (I), a part of the chain transfer agent used in the production of the copolymer (A) can be added to the solvent (B-1) and the temperature can be raised, and in the submerged polymerization step (II), the The chain transfer agent solution obtained by dissolving the remainder obtained by removing a part of the chain transfer agent used in the solvent (B-2) is dropped into the heated solvent (B-1h).

(post-polymerization step (III)) After completion of the dropping of the monomer solution and the polymerization initiator solution, the mixed solution was further stirred at 60 to 90° C. for 1 to 5 hours.

"Solvent (B-1)" The solvent (B-1) used in the solvent heating step (I) may be only a hydroxyl-containing solvent, or only a hydroxyl-free solvent, or both a hydroxyl-containing solvent and a hydroxyl-free solvent. By. The solvent (B-1) is preferably a solvent containing a hydroxyl group containing a hydroxyl group, more preferably a solvent containing only a hydroxyl group.

Examples of hydroxyl-containing solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) alkylene glycol monoalkyl ethers; 2-hydroxypropionate methyl ester, 2-hydroxypropyl Ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, etc. The carboxylate; 3-methoxy-1-butanol; diethylene glycol, etc.

Among these hydroxyl group-containing solvents, in the drop polymerization step (II) and/or the post-polymerization step (III), the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) are hindered The effect of the transesterification reaction is high, so it is better to use a grade 1 and/or grade 2 alcohol solvent and an ether solvent. Among them, it is more preferable to use propylene glycol monomethyl ether, ethylene glycol monomethyl ether and 3-methoxyl-1-butanol. These hydroxyl group-containing solvents may be used alone or in combination of two or more.

Examples of solvents that do not contain a hydroxyl group include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. (poly) alkylene glycol monoalkyl ether acetates; ethers of diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ether Ketones such as base ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3- Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate ester, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, n-propyl pyruvate, ethyl Esters of methyl acetylacetate, ethyl acetylacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethyl Carboxylic acid amides such as formamide and N,N-dimethylacetamide, etc.

Among solvents that do not contain hydroxyl groups, from the viewpoints of ease of acquisition, cost, and quality, it is better to use ether-based solvents, such as propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl Ether is better. These hydroxyl group-free solvents may be used alone or in combination of two or more.

When the solvent (B-1) used in the solvent heating step (I) contains a hydroxyl group-containing solvent, the content ratio of the hydroxyl group-containing solvent in the solvent (B-1) is preferably 10 to 100% by mass, and 20 to 90% by mass. The mass % is more preferable, and 40-80 mass % is more preferable. If the content ratio of the hydroxyl group-containing solvent is 10% by mass or more, in the dropping polymerization step (II) and/or the post-polymerization step (III), the ester group derived from the monomer (m-a) and the ester group derived from the monomer (m-a) can be sufficiently obtained. The effect of the transesterification reaction of the hydroxyl group of the monomer (m-b). When the solvent (B-1) contains a solvent that does not contain a hydroxyl group, the remaining amount of the ester group derived from the monomer (m-a) in the copolymer (A) can be increased, and the ester group derived from the monomer (m-a) can be increased as the resin composition when hardened The effect of the amount of crosslinking reaction caused by the transesterification reaction between the ester group of (m-a) and the hydroxyl group derived from monomer (m-b).

"The temperature of the solvent and the mixed solution" In the production method of this embodiment, in the solvent heating step (I), the solvent (B-1) is added to the reaction vessel, and the temperature is raised to 60-90°C. Moreover, in the dripping polymerization process (II) and post-polymerization process (III), it was made to react at 60-90 degreeC for 1-5 hours, stirring a mixed solution. The temperature of the solvent (B-1h) in the solvent heating step (I) and the temperature of the mixed solution in the dropping polymerization step (II) and the post-polymerization step (III) may be the same or different.

In this embodiment, since the temperature of the solvent (B-1h) in the solvent heating step (I) is above 60°C, and the temperature of the mixed solution in the dropwise polymerization step (II) and the post-polymerization step (III) is 60°C As above, in the dropping polymerization step (II) and the post-polymerization step (III), the polymerization reaction of the monomers (m-a) to (m-c) and the optionally used monomer (m-d) proceeds sufficiently.

Since the temperature of the solvent (B-1h) in the solvent heating step (I) is below 90°C, and the temperature of the mixed solution in the dropwise polymerization step (II) and the post-polymerization step (III) is below 90°C, the dropwise polymerization In the step (II) and the post-polymerization step (III), the ester exchange reaction between the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) can be suppressed. In addition, when the above temperature is 90°C or lower, when a reaction product of an isocyanate compound having an ethylenically unsaturated group and a malonate diester or acetoacetate is used as the monomer (m-a), the following can be obtained: Effect. That is, in the dropping polymerization step (II) and the post-polymerization step (III), dissociation of the malonate diester or acetoacetate from the group represented by the above formula (1) or the above formula (2) can be prevented, Generates isocyanate groups. Therefore, the isocyanate group generated by the dissociation of the group represented by the above formula (1) or the above formula (2) can be prevented from being separated from the hydroxyl group derived from the monomer (m-b) or the acid derived from the monomer (m-c). radical reaction, and the copolymer (A) in the process of production is gelled.

In the dropwise polymerization step (II), drop the polymerization initiator solution and the monomer solution into the solvent (B-1h) heated to 60~90°C in the solvent heating step (I) to make a mixed solution and carry out polymerization at the same time . In the dropwise polymerization step (II), the chain transfer agent solution may be further dropped into the heated solvent (B-1h) to prepare a mixed solution containing the chain transfer agent.

In the dropwise polymerization step (II), it is preferable to simultaneously drop the polymerization initiator solution and the monomer solution into the heated solvent (B-1h). In this case, the molecular weight of the copolymer (A) can be accurately controlled, and gelation of the copolymer (A) during production can be prevented. In the dropwise polymerization step (II), when dropping the chain transfer agent solution into the heated solvent (B-1h), the chain transfer agent solution may also be dropped simultaneously with the polymerization initiator solution and the monomer solution. Moreover, before or after dropping a polymerization initiator solution and a monomer solution, you may drop a chain transfer agent solution.

The dropping speed of the polymerization initiator solution, monomer solution, and chain transfer agent solution depends on the capacity of the reaction vessel, the volume of the heated solvent (B-1h) and the polymerization initiator solution, monomer solution, and chain transfer agent solution etc. The scale of the reaction is appropriately determined. The dropping speed of polymerization initiator solution, monomer solution, and chain transfer agent solution, for example, when using a 1L reaction vessel, is preferably set at a speed of 0.1~5mL/min. The dropping time of the polymerization initiator solution, the monomer solution, and the chain transfer agent solution can be set at, for example, 30 minutes to 1 hour. The dropping speed and dropping time of the polymerization initiator solution, the monomer solution, and the chain transfer agent solution may be different from each other, or partly or all of them may be the same.

In this embodiment, the polymerization initiator solution, the monomer solution, and the chain transfer agent solution used as needed are individually prepared. (polymerization initiator solution) A polymerization initiator solution is what melt|dissolved a polymerization initiator in a solvent (B-2). The polymerization initiator is not particularly limited, but examples include 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobisisobutyronitrile, peroxide Benzoyl, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more.

The concentration of the polymerization initiator in the polymerization initiator solution is preferably such that a mixed solution having a uniform concentration can be easily obtained, for example, 16 to 50% by mass, and is not particularly limited. The usage amount of the polymerization initiator solution, the polymerization initiator contained in the polymerization initiator solution is preferably 0.5 to 20 mass parts with respect to 100 mass parts of the total feed amount of the monomers, More preferably, it is the quantity of 1.0-10 mass parts. The total feed amount of the above monomers is the mass of the monomer (m-a)~monomer (m-d) in the monomer solution.

(monomer solution) Monomer solution, for making the monomer (m-a) having the group represented by above-mentioned formula (1) or above-mentioned formula (2), the monomer (m-b) containing hydroxyl group, the monomer (m-c) containing acid group and optionally The monomer (m-d) used was dissolved in the solvent (B-2). As the monomer (m-a) to the monomer (m-d), those exemplified in the item of the copolymer (A) can be used.

The monomer solution can be produced by dissolving the monomers (m-a)~(m-d) individually in the solvent (B-2) and then mixing them, or by mixing the monomers (m-a)~(m-d) It is produced by dissolving in solvent (B-2). The total concentration of the monomers (m-a)~(m-d) in the monomer solution is preferably a concentration that can easily obtain a mixed solution of uniform concentration, for example, it can be set at 50~95% by mass, and it is not particularly limited.

Although the ratio of each monomer (m-a)~(m-c) used in the manufacture of the copolymer (A) is not particularly limited, the monomer (m-a) is 1~40 mol%, and the monomer (m-b) is 1~60 mol%. %, monomer (m-c) 1~60 mol% is better, monomer (m-a) 5~30 mol%, monomer (m-b) 10~50 mol%, monomer (m-c) 10~50 mol% Mole% is more preferable, monomer (m-a) is 10~20 mole%, monomer (m-b) is 20~40 mole%, monomer (m-c) is 15~40 mole%.

When the copolymer (A) contains a structural unit (d), the ratio of each monomer (m-a) to (m-d) used in the manufacture of the copolymer (A) is not particularly limited, but the monomer (m-a) is 1 to 40 Mole %, monomer (m-b) 1~60 mole%, monomer (m-c) 1~60 mole%, monomer (m-d) more than 0~80 mole% is better, monomer (m-a) 5~ 30 mol%, monomer (m-b) 10~50 mol%, monomer (m-c) 10~50 mol%, monomer (m-d) 10~60 mol%, monomer (m-a) 10~ 20 mol%, monomer (m-b) 20~40 mol%, monomer (m-c) 15~40 mol%, monomer (m-d) 15~50 mol%, and more preferably.

(chain transfer agent solution) The chain transfer agent solution is obtained by dissolving the chain transfer agent in the solvent (B-2). In the dropwise polymerization step (II), the degree of polymerization of the copolymer (A) synthesized in the post-polymerization step (III) can be controlled by dropping the chain transfer agent solution. Therefore, the copolymer (A) of a desired molecular weight range can be produced easily. Although it does not specifically limit as a chain transfer agent, For example, polyfunctional mercaptan can be used preferably. Multifunctional thiols are compounds with two or more mercapto groups in the molecule.

-2,4,6(1H,3H,5H)-三酮、參-[(3-巰基丙醯氧基)-乙基]-異三聚氰酸酯、二季戊四醇陸(3-巰基丙酸酯)等。The multifunctional thiol is not particularly limited, but examples thereof include mercaptoacetic acid, 1,2-ethanedithiol, 1,4-bis(3-mercaptobutyryloxy)butane, tetraethylene glycol bis( 3-mercaptopropionate), trimethylolethane ginseng (3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptopropane ester), pentaerythritol four (3-mercaptobutyrate), pentaerythritol four (3-mercaptopropionate), 1,3,5-ginseng (3-mercaptobutyloxyethyl)-1,3,5 -three

-2,4,6(1H,3H,5H)-trione, ginseng-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, dipentaerythritol tertiary (3-mercaptopropionic acid esters), etc.

As the chain transfer agent, among the above, from the viewpoints of ease of acquisition, cost and quality, pentaerythritol tetra(3-mercaptobutyrate) and/or mercaptoacetic acid, pentaerythritol tetra(3-mercaptopropane) acid esters) are preferred. The concentration of the chain transfer agent in the polymerization initiator solution is preferably such that a mixed solution having a uniform concentration can be easily obtained. For example, it can be set at 0.1 to 10% by mass, and is not particularly limited.

The amount of the chain transfer agent solution used, the chain transfer agent contained in the mixed solution is preferably 0.5 to 20 parts by mass, for example, with respect to 100 parts by mass of the total feed amount of monomers, more preferably It becomes the quantity of 1.0-10 mass parts. The total feed amount of the above-mentioned monomers is the mass of the monomer (m-a)~monomer (m-d) in the monomer solution. By setting the amount of the chain transfer agent solution used within the above range, the copolymer (A) in the desired molecular weight range can be easily produced in the post-polymerization step (III).

"Solvent (B-2)" As the solvent (B-2) used in the dropping polymerization step (II), the same one as the solvent (B-1) used in the solvent heating step (I) can be used. Solvent (B-2), like solvent (B-1), may be only a hydroxyl-containing solvent, may only be a hydroxyl-free solvent, or may contain both a hydroxyl-containing solvent and a hydroxyl-free solvent. Party. The solvent (B-2) is preferably a solvent containing a hydroxyl group containing a hydroxyl group, more preferably a solvent containing only a hydroxyl group.

In the manufacturing method of the copolymer (A) of this embodiment, either or both of solvent (B-1) and solvent (B-2) contain a hydroxyl group containing solvent. Therefore, when the solvent (B-1) used in the solvent heating step (I) does not contain a hydroxyl group-containing solvent, the solvent (B-2) used in the polymerization step (II) contains a hydroxyl group-containing solvent dropwise.

The content ratio of the hydroxyl group-containing solvent contained in the total amount of the solvent (B-1) used in the solvent heating step (I) and the solvent (B-2) used in the dropping polymerization step (II) is 10 to 100% by mass % is better, 20-90 mass % is more preferable, and 40-80 mass % is more preferable. If the content ratio of the hydroxyl group-containing solvent is 10% by mass or more, in the dropping polymerization step (II) and/or the post-polymerization step (III), the ester group derived from the monomer (m-a) and the ester group derived from the monomer (m-a) can be sufficiently obtained. Effect of the transesterification reaction of the hydroxyl group of the monomer (m-b). When one or both of the solvent (B-1) and the solvent (B-2) contains a solvent not containing a hydroxyl group, if the content ratio of the solvent containing a hydroxyl group is 90% by mass or less, the improved copolymer (A ) in the remaining amount of the ester group derived from the monomer (m-a) increases as a result of the transesterification reaction between the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) when the resin composition is hardened The effect of the amount of cross-linking reaction.

In the production method of this embodiment, since the solvent (B-1) used in the solvent heating step (I) and/or the solvent (B-2) used in the drop polymerization step (II) contains a hydroxyl group-containing solvent, it can The effect shown below is obtained. In a mixed solution containing a hydroxyl group-containing solvent, if the monomer (m-a) (m-b) (m-c) and optionally the monomer (m-d) are polymerized at 60~90°C, the ester derived from the monomer (m-a) group, it is easy to carry out transesterification reaction with the hydroxyl group of the solvent containing hydroxyl group. Therefore, in the dropping polymerization step (II) and/or the post-polymerization step (III), part of the ester group of the group represented by the above-mentioned formula (1) or the above-mentioned formula (2) that the monomer (m-a) has and the hydroxyl group-containing The hydroxyl group possessed by the solvent undergoes transesterification reaction.

If the ester group derived from the monomer (ma) is transesterified with the hydroxyl group contained in the solvent containing the hydroxyl group, then in the mixed solution, a base having the ester group derived from the monomer (ma) is generated (in formula (1) R ¹ and R ² , or R ³ in formula (2)) alcohol. Since this reaction is a reversible reaction, a part of the generated alcohol undergoes a transesterification reaction (reverse reaction) with the generated compound through a transesterification reaction to generate a monomer (ma) and a hydroxyl group-containing solvent. Therefore, even if the ester group derived from the monomer (ma) undergoes a transesterification reaction with the hydroxyl group contained in the hydroxyl group-containing solvent, the ester group derived from the monomer (ma) remains moderately in the mixed solution.

When the monomer (ma) has a group shown in formula (1), for example, if R in the formula ( ¹ ) carries out transesterification with the hydroxyl group contained in the solvent containing the hydroxyl group, then the compound with the formula ( 1) The base formed by the reaction of R1 in ^formula ( ¹ ) becomes a steric hindrance, and the transesterification reaction between R2 and the hydroxyl group in formula (1) is difficult to occur. Therefore, it is speculated that when the monomer (ma) has a group shown in formula (1), it is only derived from a part of the ester group of the monomer (ma), and carries out a transesterification reaction with the hydroxyl group of the solvent containing the hydroxyl group. The ester group of the monomer (ma) remained moderately.

Thus, in this embodiment, in the dropping polymerization step (II) and/or the post-polymerization step (III), since the ester group derived from the monomer (m-a) undergoes transesterification with the hydroxyl group contained in the hydroxyl group-containing solvent, Therefore, the transesterification reaction of the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) is moderately hindered. Therefore, in the post-polymerization step (III), gelation of the copolymer (A) during production can be prevented. Moreover, the storage stability of the resin composition containing a copolymer (A) becomes favorable.

Also, in this embodiment, by moderately inhibiting the above-mentioned transesterification reaction in the dropping polymerization step (II) and/or post-polymerization step (III), before thermosetting the resin composition containing the copolymer (A), it can be The ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) are prevented from decreasing. Accordingly, a copolymer (A) in which the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) remain moderately can be obtained. Moreover, the compound produced by the transesterification reaction of the ester group derived from the monomer (m-a) and the hydroxyl group which the hydroxyl-containing solvent has has a crosslinked structure by transesterification with the monomer (m-b). Therefore, by thermosetting the resin composition containing the copolymer (A), a crosslinked structure due to transesterification of the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) is sufficiently formed , A hardened product with good solvent resistance can be obtained.

Though the amount of the solvent (B-1) used in the solvent heating step (I) and the solvent (B-2) used in the dropping polymerization step (II) is not particularly limited, relative to the total feed amount of the monomer (i.e. , the mass of monomer (m-a)~monomer (m-d) in monomer solution) 100 parts by mass, for example, the total amount of solvent (B-1) and solvent (B-2) is 30~1,000 parts by mass Preferably, it is more preferably 50 to 800 parts by mass. If the total amount of solvent (B-1) and solvent (B-2) is 1,000 parts by mass or less with respect to 100 parts by mass of the total feed amount of monomers, the content of The viscosity of the reaction liquid of a copolymer (A) becomes appropriate. In addition, by setting the total amount of the solvent (B-1) and the solvent (B-2) at 1,000 parts by mass or less, when the chain transfer agent solution is dropped in the drop polymerization step (II), the chain transfer effect can be suppressed. Reduction of the molecular weight of the copolymer (A). Also, by setting the total amount of the solvent (B-1) and the solvent (B-2) to be 30 parts by mass or more with respect to 100 parts by mass of the total feed amount of monomers, the post-polymerization step (III) is prevented In the abnormal polymerization reaction, the polymerization reaction can be carried out stably. As a result, gelation of the copolymer (A) during production can be prevented, and a colorless copolymer (A) can be obtained.

In the production method of this embodiment, in the post-polymerization step (III), the mixed solution obtained in the polymerization step (II) is dripped with stirring, and reacted at 60 to 90° C. for 1 to 5 hours. The reaction time in the post-polymerization step (III) may be 1 to 5 hours, preferably 1 to 4 hours, more preferably 2 to 3 hours. When the reaction time is 1 to 5 hours, the copolymer (A) having an appropriate molecular weight can be produced in good yield.

The copolymer (A) of the present embodiment contains a structural unit (a) having a group represented by the above-mentioned formula (1) or the above-mentioned formula (2), a structural unit (b) having a hydroxyl group, and a structural unit ( c), the glass transition temperature is below 30°C. Therefore, the resin composition containing the copolymer (A) according to this embodiment has good alkali developability when used as a photosensitive material, has excellent storage stability, and can obtain excellent solvent resistance even when it is cured at a low temperature. of hardening.

In the production method of the copolymer (A) of the present embodiment, the solvent (B-1) used in the solvent heating step (I) and/or the solvent (B-2) used in the dropwise polymerization step (II) is composed of Solvent for hydroxyl-containing solvents. In the solvent heating step (I), the temperature of the solvent (B-1) is raised to 60-90°C, and in the post-polymerization step (III), the mixed solution is reacted at 60-90°C. Therefore, in the dropping polymerization step (II) and/or the post-polymerization step (III), the transesterification reaction of the ester group derived from the monomer (m-a) and the hydroxyl group derived from the monomer (m-b) is moderately inhibited. As a result, the copolymer (A) of this embodiment which fully contains the structural unit (a) which has the group represented by said formula (1) or the said formula (2) and the structural unit (b) which has a hydroxyl group can be obtained.

On the other hand, conventionally, when a solvent is used for polymerization of a copolymer, a solvent which does not react with a monomer is selected and used. Therefore, in the prior art, when the copolymer is polymerized using a solvent, the monomer and the solvent do not react. Therefore, in the prior art, it is not assumed that the reaction of the monomer and the solvent is used, and there is no method of controlling the properties of the copolymer by the reaction of the monomer and the solvent.

＜Resin composition＞ Next, the resin composition of this embodiment is demonstrated. The resin composition of this embodiment contains the copolymer (A) and solvent (B) of this embodiment. The resin composition of this embodiment may contain not only a copolymer (A) and a solvent (B), but also a reactive diluent (C) and a photopolymerization initiator (D). Such a resin composition is preferably used as a photosensitive resin composition. The resin composition of the present embodiment may further contain a coloring agent (E) in addition to the above-mentioned copolymer (A) to the photopolymerization initiator (D). Such a resin composition is preferably used as a material for coloring patterns for forming color filters, black matrices, black column spacers, and the like.

(Solvent (B)) In the resin composition of the present embodiment, the solvent (B) contains a hydroxyl group-containing solvent. The solvent (B) may only be a hydroxyl group-containing solvent. In the resin composition of this embodiment, since the solvent (B) contains a solvent containing a hydroxyl group, the ester group contained in the structural unit (a) of the copolymer (A) and the solvent containing a hydroxyl group contained in the solvent (B) The hydroxy group carried out the transesterification reaction moderately hinders the transesterification reaction between the ester group of the structural unit (a) and the hydroxyl group of the structural unit (b), and improves the storage stability.

As for the hydroxyl group-containing solvent used as solvent (B), there is no particular limitation as long as it is a solvent containing hydroxyl group, and it can be used as solvent (B-1) and solvent (B-2) in the step of producing copolymer (A). ) use the same solvent. Examples of the hydroxyl group-free solvent usable as the solvent (B) are the same solvents that can be used as the solvent (B-1) and solvent (B-2) in the step of producing the copolymer (A).

The content ratio of the hydroxyl group-containing solvent in the solvent (B) can be set in the same manner as the content ratio of the hydroxyl group-containing solvent in the solvent (B-1) used in the step of producing the copolymer (A). The solvent (B) may be the same as or different from the solvent (B-1) and/or solvent (B-2) used in the step of producing the copolymer (A).

The resin composition of the present embodiment can be obtained by appropriately mixing the copolymer (A) isolated from the reaction solution containing the copolymer (A) obtained in the polymerization step (III) after producing the copolymer (A) with solvent (B) method to manufacture. As the resin composition of this embodiment, the reaction liquid containing the copolymer (A) obtained at the time of manufacture of a copolymer (A) can also be used as it is. At this time, it is not necessary to isolate the copolymer (A) from the reaction solution. Also, when the solvent (B-1) and/or solvent (B-2) used in the manufacture of the copolymer (A) are contained in the reaction liquid, the solvent (B-1) and/or solvent (B-1) in the reaction liquid can be directly used The solvent (B-2) was used as the solvent (B). A solvent (B) may also be added to the reaction solution if necessary.

In the resin composition of this embodiment, the compounding quantity of a copolymer (A) and a solvent (B) may be suitably adjusted depending on the purpose of use of a resin composition. In the resin composition of this embodiment, for example, with respect to 100 mass parts of copolymers (A), it is preferable to contain 30-1,000 mass parts of solvent (B), and it is more preferable to contain 50-800 mass parts. When the content of the solvent (B) is 30 parts by mass or more, the viscosity of the resin composition will be appropriate. Also, by setting the blending amount of the solvent (B) to 30 parts by mass or more, abnormal polymerization reaction can be prevented, hardening as a resin composition can be performed stably, and coloring and gelation of the resin composition can be prevented. When the content of the solvent (B) is 1,000 parts by mass or less, the viscosity of the resin composition can be controlled within an appropriate range.

(Reactive diluent (C)) The reactive diluent (C) is optionally contained together with the photopolymerization initiator (D). The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule. The reactive diluent (C) may be a monofunctional monomer or a polyfunctional monomer, preferably a polyfunctional monomer having a plurality of polymerizable functional groups. Viscosity adjustment becomes easy by setting it as a resin composition containing a reactive diluent (C). Also, by making the resin composition containing the reactive diluent (C), the adhesion of the cured product of the resin composition to the substrate can be improved, or the strength of the cured product of the resin composition can be adjusted.

Regarding the monofunctional monomer used as the reactive diluent (C), examples include (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide, Ethoxymethyl(meth)acrylamide, Propoxymethyl(meth)acrylamide, Butoxymethoxymethyl(meth)acrylamide, Methyl(meth)acrylate , ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate base) acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate Acrylates, (meth)acrylates such as 2,2,3,3-tetrafluoropropyl (meth)acrylates, half (meth)acrylates of phthalic acid derivatives; styrene, α-methacrylate Aromatic vinyl compounds such as methyl styrene, α-chloromethyl styrene, vinyl toluene, etc.; carboxylic acid esters such as vinyl acetate, vinyl propionate, etc. These monofunctional monomers may be used alone or in combination of two or more.

Regarding the polyfunctional monomer used as the reactive diluent (C), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Acrylates, Propylene Glycol Di(meth)acrylate, Polypropylene Glycol Di(meth)acrylate, Butylene Glycol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, 1,6-Hexyl Glycol Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Glycerin Di(meth)acrylate, Pentaerythritol Di(meth)acrylate, Pentaerythritol Tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis (4-(Meth)acryloxypolyethoxyphenyl)propane, 2-Hydroxy-3-(meth)acryloxypropyl (meth)acrylate, Ethylene Glycol Diglycidyl Ethyl ether di(meth)acrylate, Diethylene glycol dielycidyl ether di(meth)acrylate, Diglycidyl phthalate di(meth)acrylate, Glycerin triacrylate, Glycerin Polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. Reactant with 2-hydroxyethyl (meth)acrylate, (meth)acrylates such as tri(meth)acrylate of ginseng (hydroxyethyl)isocyanurate; divinylbenzene , diallyl phthalate, diallyl phenyl phosphonate and other aromatic vinyl compounds; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, sub- Methylbis(meth)acrylamide, (meth)acrylamide methylene ether, condensation products of polyols and N-methylol(meth)acrylamide, etc. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers, it is preferable to use a multifunctional (meth)acrylate as the reactive diluent (C) from the viewpoint of improving the development form of the resin composition or improving the curability. One or more of hydroxymethylpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are more preferable.

When the resin composition contains a reactive diluent (C), the blending amount of each component is based on the copolymer (A) 10-90 parts by mass, solvent (B) 30-1,000 parts by mass, reactive diluent (C) 10-90 parts by mass, copolymer (A) 20-80 parts by mass, solvent (B) 50-800 parts by mass, more preferably 20-80 parts by mass of reactive diluent (C), 30-75 parts by mass of copolymer (A), 100-700 parts by mass of solvent (B), reactive diluent (C) is more preferably 25 to 70 parts by mass. If the compounding quantity of each component falls within the said range, it will become a resin composition with suitable viscosity, and can be suitably used for various coatings, adhesives, adhesives for printing inks, etc.

(Photopolymerization initiator (D)) The photopolymerization initiator (D) is not particularly limited, but examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, etc.; acetophenone, 2,2-dimethoxy Base-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1 -[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone -Acetophenones such as 1; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.; xanthone, thioxanthone Ketones, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl di Ketals such as methyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl) benzophenone, 3,3',4,4'- Four (t-butyldioxycarbonyl) benzophenone and other benzophenones; acyl phosphine oxides; ethyl ketone 1-[9-ethyl-6-(2-methylbenzoyl) Base)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. These photopolymerization initiators (D) may be used alone or in combination of two or more.

When the resin composition contains the photopolymerization initiator (D), its content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C), 0.5-20 parts by mass is more preferable, and 1-15 parts by mass is still more preferable.

(colorant (E)) The coloring agent (E) is optionally contained. The coloring agent (E) is not particularly limited as long as it is dissolved or dispersed in the solvent (B), and examples thereof include dyes, pigments, and the like. The coloring agent (E) may be used alone or in combination of two or more depending on the color of the cured product of the target resin composition. As the colorant (E), only a dye may be used, only a pigment may be used, or a dye and a pigment may be used in combination.

As the dye, from the viewpoints of solubility in the solvent (B) and alkaline developer, interaction with other components in the resin composition, heat resistance, etc., acidic dyes having acidic groups such as carboxylic acid and sulfonic acid are used. Preferred are dyes, salts of acid dyes and nitrogen compounds, and sulfonamides of acid dyes.

Examples of such dyes include Acid Alizarin Violet N; Acid Black 1, 2, 24, 48; Acid Blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83 , 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid magenta; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and its derivatives, etc. Among these dyes, it is preferable to use azo-based, dibenzopyran-based, anthraquinone-based or phthalocyanine-based acid dyes. These dyes may be used alone or in combination of two or more depending on the color of the cured product of the target resin composition.

Examples of pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc. yellow pigments; C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73, etc. orange pigments; C.I. Red pigments of 216, 224, 242, 254, 255, 264, 265, etc.; blue pigments of C.I. pigment blue 15, 15:3, 15:4, 15:6, 60, etc.; C.I. pigment violet 1, 19, 23 , 29, 32, 36, 38, etc. purple pigments; C.I. pigment green 7, 36, 58, 59, etc. green pigments; C.I. pigment brown 23, 25, etc. brown pigments; C.I. Pigment black 1, 7, carbon black, titanium Black, black pigments such as iron oxide, etc. These pigments may be used alone or in combination of two or more depending on the color of the cured product of the target resin composition.

When a pigment is used as the colorant (E), a known dispersant may be contained in the resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant excellent in dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, dehydrated Sorbitol fatty ester dispersant, aliphatic denatured ester dispersant, etc.

Products such as EFKA (manufactured by EFKA Chemicals BV (EFKA)), Disperbyk-161 (manufactured by BYK), DISPARLON (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) can also be used as polymer dispersants. name marketer. The type and blending amount of the dispersant may be appropriately set depending on the type of pigment to be used.

When the resin composition contains the colorant (E), its content is preferably 3 to 80 parts by mass, 5 to 80 parts by mass relative to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). More preferably 70 parts by mass, more preferably 10 to 60 parts by mass. The resin composition containing the copolymer (A) of the present embodiment is excellent in storage stability, and can obtain a cured product excellent in solvent resistance even when it is cured at a low temperature. Therefore, for example, content of a coloring agent (E) can be made into 20 mass parts or more with respect to 100 mass parts of total amounts of a copolymer (A) and a reactive diluent (C). When the resin composition containing 20 parts by mass or more of the colorant (E) is used as a material of a color filter, the color reproducibility in an image display device including a color filter can be improved.

In the resin composition of this embodiment, in addition to the above-mentioned components, well-known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor may be blended in order to impart predetermined characteristics. The compounding quantity of these additives is not specifically limited in the range which does not inhibit the effect of this invention.

Since the resin composition of this embodiment contains the copolymer (A) of this embodiment, crosslinking reaction fully progresses even at low temperature. Therefore, the resin composition of this embodiment can be cured at a low temperature. Specifically, the resin composition of this embodiment is preferably cured at a temperature of 150°C or lower, more preferably 100°C or lower, most preferably 80°C or lower. If the temperature for curing the resin composition is 150° C. or lower, the amount of energy required for curing the resin composition may be small. Also, when the resin composition contains the colorant (E) having poor heat resistance, deterioration of the colorant (E) accompanying thermal hardening can be suppressed, and a cured product exhibiting the original properties of the colorant (E) can be easily obtained. Therefore, as a coloring agent (E), what consists of various materials can be used. Also, when a cured product is formed by applying a resin composition on a substrate and thermally curing it, the cured product can be formed even if the substrate is made of a material with poor heat resistance. Therefore, as the substrate, for example, those made of various materials such as resin for flexible displays can be used.

The resin composition of this embodiment is preferably cured at a temperature of 50°C or higher, more preferably 60°C or higher, and still more preferably 70°C or higher. If the temperature for curing the resin composition is 50°C or higher, a cross-linked structure due to transesterification can be fully formed in a short time, and a cured product with good solvent resistance can be efficiently formed. The heating time (curing time) for curing the resin composition in this embodiment can be appropriately determined depending on the size and thickness of the cured product, the temperature for making it harden, etc. For example, it can be set at 10 minutes to 4 hours to determine 20 minutes to 2 hours is better.

The resin composition of this embodiment can be manufactured by the method of mixing the above-mentioned components using a well-known mixing apparatus. The solvent contained in each component used as a raw material when manufacturing the resin composition of this embodiment can be used as a solvent (B). When the resin composition of the present embodiment contains components other than the copolymer (A) and the solvent (B), for example, it can also be used in a resin composition containing the previously produced copolymer (A) and solvent (B), Manufactured by adding and mixing reactive diluent (C), photopolymerization initiator (D) and colorant (E).

Since the resin composition of the present embodiment contains the copolymer (A) of the present embodiment, it has excellent storage stability, and can obtain a cured product excellent in solvent resistance even when it is cured at low temperature. Therefore, the resin composition of this embodiment can be preferably used as, for example, color filters, black matrices, color filter protective films, photo spacers, protrusions for liquid crystal alignment, microlenses, insulating films for touch panels, Materials such as adhesives and adhesive sheets for electronic materials around flexible printed wiring boards.

When the resin composition of this embodiment contains the copolymer (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D) of this embodiment, it can be preferably used as alkali developability photosensitive material. In particular, it is suitable for use in combination with organic electroluminescent (EL) displays (for black pixel definition layers (PDL)), liquid crystal display devices, and devices using charge-coupled devices (CCD)/complementary metal-oxide semiconductor (CMOS) Resist for color filters of solid-state imaging devices, etc.

Also, when the resin composition of the present embodiment contains the copolymer (A) of the present embodiment, the solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the coloring agent (E), it can Forms a colored pattern made of a hardened product with excellent solvent resistance at low temperature. Therefore, deterioration of the colorant (E) accompanying thermal hardening can be suppressed, and a colored pattern exhibiting the original characteristics of the colorant (E) can be formed. Therefore, the above-mentioned resin composition can be preferably used as a photosensitive material for color filters.

＜Color Filter＞ Next, the color filter of the present embodiment will be described. The color filter of this embodiment has a substrate and a plurality of pixels formed by three colored patterns of a red (R) pattern, a green (G) pattern, and a blue (B) pattern formed on the substrate. , a black matrix formed on the border of each coloring pattern, and a protective film formed on the pixels and the black matrix.

As the substrate, well-known ones can be used, such as glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide imide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, etc. substrates, array substrates, etc. In the color filter of this embodiment, organic substrates such as polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, and polyimide substrates with relatively low heat resistance temperatures can be used. Use as a substrate suitable for flexible substrates.

In the color filter of this embodiment, the black matrix and the three colored patterns of each pixel are formed by containing the copolymer (A) of this embodiment, solvent (B), reactive diluent (C), light A colored pattern formed by hardening the resin composition of the present embodiment of the polymerization initiator (D) and the coloring agent (E). It does not specifically limit as a protective film, A well-known thing can be used.

Next, an example of the manufacturing method of the color filter of this embodiment will be described. In manufacturing the color filter of this embodiment, first, on the substrate, a coloring pattern to be a black matrix and three kinds of coloring patterns to form each pixel are respectively formed. Firstly, a colored pattern to become a black matrix is formed on the substrate, and then, within the range divided by the black matrix, a red pattern, a green pattern, and a blue pattern are respectively formed to form each pixel. The sequence of forming the red pattern, the green pattern and the blue pattern is not particularly limited.

Each colored pattern can be formed by photolithography using the resin composition of this embodiment. Specifically, the resin composition of the present embodiment is coated on a substrate to form a coating film. Then, the coated film is exposed through a photomask having a specified pattern shape, and the exposed part is photohardened. Then, the unexposed part of the coating film was subjected to alkali development and removed using an aqueous alkali solution. Thereafter, by performing baking, the exposed portion of the coating film is heated to be hardened. Through the above steps, a colored pattern having a specified shape and formed from the cured product of the resin composition of this embodiment can be obtained.

The method of applying the resin composition to form a colored pattern is not particularly limited, and for example, screen printing, roll coating, curtain coating, spray coating, spin coating and the like can be used. After coating the resin composition, the coating film may be heated by heating means such as a circulating oven, an infrared heater, a heating plate, etc., to volatilize and remove the solvent (B) contained in the coating film. The heating for removing the solvent (B) in the coating film can be performed at a temperature of 50°C to 120°C, for example. Moreover, heating for removing the solvent (B) in a coating film can be performed for 30 seconds - 30 minutes, for example. The heating temperature and heating time for removing the solvent (B) in the coating film can be appropriately set depending on the composition of the resin composition, the thickness of the coating film, and the like.

When exposing the coating film, a known negative-type mask can be used as a photomask, for example. When exposing the coating film, it is preferable to use active energy rays such as ultraviolet rays and excimer laser light. The light source used for exposure is not particularly limited, and for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. The amount of energy ray irradiated to the coating film can be appropriately selected depending on the thickness of the coating film and the composition of the resin composition, for example, it can be set at 30~2000mJ/cm ² .

The alkali aqueous solution used for alkali development is not particularly limited. For example, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; amines such as ethylamine, diethylamine, and dimethylethanolamine can be used It is an aqueous solution of compounds; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethyl Aniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methyl Aqueous solutions of p-phenylenediamine compounds such as oxyethylaniline and their sulfates, hydrochlorides, or p-toluenesulfonates can be appropriately selected depending on the composition of the resin composition. Additives such as defoamers and surfactants may also be added to these alkaline aqueous solutions as needed. Also, in this embodiment, it is preferable to wash the substrate with water to remove the aqueous alkali solution and to dry it after the alkali development by the aqueous alkali solution and before baking.

In this embodiment, the temperature at which the exposed portion of the coating film is heated to be cured by baking is appropriately selected depending on the thickness of the coating film, the composition of the resin composition, and the like. In this embodiment, since the coating film is formed using the resin composition containing the copolymer (A) of this embodiment, the exposed part of a coating film can be cured even at low temperature.

The temperature for heating the exposed portion of the coating film may be, for example, 210°C or lower, or 150°C or lower, 100°C or lower, or 80°C or lower if necessary. If the temperature of the exposed portion of the heated coating film is 210° C. or lower, a material with low heat resistance such as a substrate with low heat resistance can be used as a material of the color filter. When the temperature of the exposed portion of the coating film is heated to 150° C. or lower, the amount of energy required to harden the coating film is small, which is preferable. In addition, if the temperature of the exposed part of the heated coating film is 150°C or lower, the degradation of the colorant (E) can be suppressed, and a colorant (E) containing poor heat resistance, which is difficult to use as a material for conventional colored patterns, can be formed. Coloring graphics. In addition, when the temperature of the exposed portion of the coated film is heated to 150°C or lower, colored patterns can be formed on substrates with poor heat resistance that have been difficult to use as substrates of color filters in the past.

The temperature at which the exposed portion of the coating film is heated is preferably 50°C or higher, more preferably 60°C or higher, and still more preferably 70°C or higher. If the temperature of the exposed part of the heating coating film is 50°C or higher, the copolymer (A) and the reactive diluent (C) are fully cross-linked, so the solvent resistance of the colored pattern becomes good, and a good color can be obtained. graphic shape. Also, if the temperature of the exposed portion of the coating film is heated to 50° C. or higher, the exposed portion of the coating film can be heated for a short time to efficiently produce colored patterns. The time for heating the exposed portion of the coating film can be appropriately selected depending on the temperature of the exposed portion of the heating coating film, the thickness of the coating film, and the composition of the resin composition. For example, it can be set at 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

Next, a protective film is formed by a known method on the colored pattern to become the black matrix and the three colored patterns that form each pixel. Through the above steps, the color filter of this embodiment can be obtained.

In the color filter of this embodiment, the three kinds of colored patterns and black matrix forming each pixel are formed by containing the copolymer (A), solvent (B), reactive diluent (C) and photopolymerization of the present embodiment. A colored pattern formed by hardening the resin composition of the present embodiment of the initiator (D) and the colorant (E). The resin composition of the present embodiment has good alkali developability, and can obtain a cured product excellent in solvent resistance even if it is cured at a low temperature. Therefore, in the color filter of this embodiment, pixels and black matrices can be formed by curing the resin composition at a low temperature, and there are many options for materials that can be used for the color filter.

Therefore, in the color filter of this embodiment, for example, it can contain the coloring agent (E) which is poor in heat resistance, and can have the pixel and/or black matrix which have a favorable pattern shape. In addition, by forming pixels and a black matrix using a method of curing a resin composition at a low temperature, it is possible to obtain a color filter including a substrate made of a material having poor heat resistance.

On the other hand, when a conventional resin composition is used to form a colored pattern instead of the resin composition of this embodiment, if the temperature at which the exposed portion of the coating film is heated to make it harden does not reach 210°C, the coloring pattern of the cured product will be reduced. Insufficient solvent resistance. Therefore, when forming a colored pattern using a conventional resin composition, the temperature of the exposed portion of the heated coating film cannot be set to 210° C. or lower. Therefore, in the prior art, it was difficult to use a colorant (E) having poor heat resistance as a material for colored patterns. In addition, it is also difficult to use a substrate having poor heat resistance as a substrate of a color filter.

In the color filter of this embodiment, it is illustrated that the coloring pattern is composed of the copolymer (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D) of this embodiment. And the case of the pixel and the black matrix made of the hardened resin composition of the colorant (E). However, instead of the photopolymerization initiator (D), a resin composition blended with a curing accelerator and a known epoxy resin can also be used.

In this case, for example, a colored pattern can be formed by the method shown below. First, on the substrate, the resin composition is coated by the inkjet method to form a coating film with a specified pattern shape. Next, the coating film is heated to be hardened. By the above method, it is possible to form a colored pattern made of a hardened resin composition having a desired shape. A resin composition in which a curing accelerator and a known epoxy resin is blended instead of the photopolymerization initiator (D) can obtain a cured product excellent in solvent resistance even if it is cured at a low temperature. Therefore, in this case, the pixel and the black matrix can also be formed by curing the resin composition at a low temperature, and there are many options for the material that can be used for the color filter.

＜Image display components＞ Next, the image display element of this embodiment will be described. Regarding the liquid crystal display element as the image display element of this embodiment, for example, a first substrate with a color filter and a first electrode formed on its surface and a second substrate with a second electrode formed on its surface are separated by a spacer. The plate is arranged so that the first electrode and the second electrode face each other, and the liquid crystal composition is sandwiched between the first substrate and the second substrate. In the liquid crystal display element of this embodiment, the color filter of this embodiment is provided as a color filter. In the liquid crystal display element of the present embodiment, known members can be used for members other than the color filter.

The liquid crystal display element of this embodiment can be manufactured using the manufacturing method shown below, for example. First, a color filter and a first electrode are sequentially formed on the first substrate. A color filter can be formed using the above-mentioned manufacturing method. The first electrode can be formed using a known method. Next, a second electrode and a spacer are formed on the second substrate by a known method. Thereafter, the first substrate and the second substrate are arranged and bonded so that the first electrode and the second electrode face each other, and a liquid crystal composition is injected between the first substrate and the second substrate to perform packaging. Through the above steps, the liquid crystal display element of this embodiment can be obtained.

Since the liquid crystal display element of this embodiment includes the color filter of this embodiment, it is possible to use a method of curing the resin composition at a low temperature to form pixels and black matrices of the color filter. Therefore, as a material usable for a liquid crystal display element, a material having poor heat resistance can be used, and there are many options for usable materials.

In the above-mentioned embodiment, although the liquid crystal display element was used as an example of the image display element of the present embodiment, the image display element of the present embodiment is not limited as long as it is equipped with the color filter of the present embodiment. in liquid crystal display elements. The image display device of this embodiment may be, for example, an organic EL display device or a solid-state imaging device using a CCD device/CMOS device. [Example]

Hereinafter, the present invention will be further specifically described by way of examples and comparative examples. In addition, this invention is not limited only to the following Examples.

[Synthesis Example 1] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 212.5 g of propylene glycol monomethyl ether (manufactured by Sankyo Chemical Co., Ltd.) was added as a solvent (B-1), and the While stirring under nitrogen substitution, the temperature was raised to 78°C (solvent heating step (I)).

Next, 26.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was dissolved in 77.3 g of propylene glycol monomethyl ether as a solvent (B-2). into a polymerization initiator solution. Also, make the MOI-DEM of 41.0g (13 mol%), the 4-hydroxybutyl acrylate of 37.4g (26 mol%), the methacrylic acid of 19.8g (23 mol%) and 69.9g (38 mol %) of 2-ethylhexyl acrylate (2EHA), dissolved in 60.5 g of propylene glycol monomethyl ether as a solvent (B-2) and mixed to make a monomer solution. Afterwards, in the aforementioned flask containing the solvent (B-1h) heated to 78°C, while stirring the solvent (B-1h) in the flask, drop the polymerization initiator solution and the single The bulk solution is made into a dropwise polymerization of a mixed solution (dropwise polymerization step (II)). The dropping rate was set at 1.7 ml/min for both the polymerization initiator solution and the monomer solution.

After completion of the dropping, the mixed solution was reacted at 78° C. for 3 hours to produce a copolymer (A) while stirring the mixed solution (post-polymerization step (III)). To the reaction liquid containing the copolymer (A) thus obtained, propylene glycol monomethyl ether as a solvent (B) was added so that components other than the solvent became 35% by mass, and the polymer composition of Synthesis Example 1 was obtained.

[Synthesis Examples 2~11, Comparative Synthesis Examples 1~3] Except for using the materials described in Tables 1 to 3 at the ratios described in Tables 1 to 3, the same procedure as in Synthesis Example 1 was carried out to obtain polymer compositions in Synthesis Examples 2 to 11 and Comparative Synthesis Examples 1 to 3.

[Synthesis Example 12] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 212.5 g of propylene glycol monomethyl ether (manufactured by Sankyo Chemical Co., Ltd.) as a solvent (B-1) and as a chain 1.75 g of thioglycolic acid as a transfer agent was stirred while nitrogen substitution was carried out, and the temperature was raised to 78° C. (solvent heating step (I)).

Next, 26.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was dissolved in 77.3 g of propylene glycol monomethyl ether as a solvent (B-2). into a polymerization initiator solution. Also, make MOI-DEM of 63.0g (20 mol%), 4-hydroxybutyl acrylate of 57.6g (40 mol%), methacrylic acid of 17.2g (20 mol%) and 36.8g (20 mol%) mol%) of 2-ethylhexyl acrylate (2EHA) was dissolved in 60.5 g of propylene glycol monomethyl ether as a solvent (B-2) to prepare a monomer solution. Afterwards, in the aforementioned flask containing the solvent (B-1h) heated to 78°C, while stirring the solvent (B-1h) in the flask, drop the polymerization initiator solution and the single The bulk solution is made into a dropwise polymerization of a mixed solution (dropwise polymerization step (II)). The dropping rate was set at 1.7 ml/min for both the polymerization initiator solution and the monomer solution.

After completion of the dropping, the mixed solution was reacted at 78° C. for 3 hours to produce a copolymer (A) while stirring the mixed solution (post-polymerization step (III)). To the reaction liquid containing the copolymer (A) thus obtained, propylene glycol monomethyl ether as a solvent (B) was added so that components other than the solvent became 35% by mass, and the polymer composition of Synthesis Example 12 was obtained.

In Tables 1 to 3, (m-a) represents a monomer having a group represented by the above formula (1) or the above formula (2). (m-b) represents a hydroxyl group-containing monomer. (m-c) represents an acid group-containing monomer. (d) represents other monomers that do not meet (m-a) (m-b) (m-c). Also, in Tables 1 to 3, (the number of equivalents of formula (1) (2)) represents the group represented by the above formula (1) or the above formula (2) contained in the molecule of the copolymer (A) equivalent number.

Materials used in Table 1 to Table 3 are as follows. ・MOI-DEM: Karenz (registered trademark) MOI-DEM (reaction product of 2-isocyanatoethyl methacrylate and diethyl malonate, manufactured by Showa Denko Co., Ltd.) ・AOI-DEM: Karenz (registered trademark) AOI-DEM (reaction product of ethyl 2-isocyanatoacrylate and diethyl malonate, manufactured by Showa Denko Co., Ltd.) ・4-Hydroxybutyl acrylate (manufactured by Mitsubishi Chemical Corporation) ・2-Hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) ・2-Hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) ・2-Hydroxypropyl acrylate (HOP-A(N)) (manufactured by Kyoeisha Chemical Co., Ltd.) ・Methacrylic acid (manufactured by Kuraray society Co., Ltd.) ・Acrylic acid (manufactured by Toagosei Co., Ltd.)

・2EHA: 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.) ・TCDMA: Tricyclo[5.2.1.0 ^2,6 ]decyl-8-methacrylate (manufactured by Hitachi Chemical Co., Ltd.) ・GMA : Epoxypropyl methacrylate (manufactured by NOF Corporation) ・MOI-BP: Karenz (registered trademark) MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino] Ethyl methacrylate, manufactured by Showa Denko Co., Ltd.) ・MOI-BM: Karenz (registered trademark) MOI-BM (2-[0-(1'-methylpropyleneamino)carboxyamino]ethylmethyl base acrylate, Showa Denko Co., Ltd.)

Regarding the polymer compositions of Synthesis Examples 1 to 12 and Comparative Synthesis Examples 1 to 3 shown in Tables 1 to 3, the weight average molecular weight (Mw), glass transition temperature (Tg), and The physical properties of storage stability and acid value were evaluated. The results are shown in Tables 1 to 3, respectively.

＜Weight average molecular weight (Mw)＞ About the copolymer (A) contained in the polymer composition of Synthesis Examples 1-12 and Comparative Synthesis Examples 1-3, the weight average molecular weight (Mw) was measured, respectively. The weight average molecular weight is the weight average molecular weight in terms of standard polystyrene measured under the following conditions using gel permeation chromatography (GPC). String: Shodex (registered trademark) LF-804＋LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40°C Sample: 0.2% by mass tetrahydrofuran solution of copolymer Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL/min

＜Glass transition temperature (Tg)＞ The polymer compositions of Synthesis Examples 1-12 and Comparative Synthesis Examples 1-3 were coated on a glass substrate, and dried at 50° C. under reduced pressure for 24 hours. Thereafter, it was redissolved in acetone, and dried again at 50° C. under reduced pressure for 24 hours. The solid content of the copolymer solution from which volatile components have been removed in this way is measured according to JIS-K7121 at a heating rate of 10°C/min under a nitrogen stream using DSC (differential scanning calorimeter method, measuring machine: SEIKO DSC6200 (intermediate point) glass transfer point). The obtained result was defined as the glass transition temperature (Tg) of the copolymer (A).

＜Storage stability＞ After adjustment, equal amounts of the polymer compositions of Synthesis Examples 1 to 12 and Comparative Synthesis Examples 1 to 3 whose components other than solvents were 35% by mass were put into glass containers, and capped to prevent the entry of dust, etc., to make samples. After measuring the viscosity of each sample, they were left to stand in a thermostat kept at 12°C for 3 months. Then, the viscosity of each sample left standing for 3 months was measured. In addition, the measurement of the viscosity was carried out at 25° C. and a rotation speed of 10 rpm using an E-type viscometer (RE-80L, produced by Toki Sangyo Co., Ltd., cone No. 3).

For each sample, calculate the viscosity increase ratio {(1-(viscosity after standing for 3 months/viscosity before standing))× 100(%)}, evaluated by the criteria shown below. ◎: Viscosity increase rate below 10% ○: Viscosity increase rate 10.1%~20% △: The viscosity increase rate is above 20.1%

As shown in Tables 1 to 3, it can be confirmed that the polymer compositions of Synthesis Examples 1 to 12 and Comparative Synthesis Examples 1 to 3 all have excellent storage stability as ◎ or ○ in the evaluation of storage stability.

＜Acid value＞ The acid values of the polymer compositions of Synthesis Examples 1-12 and Comparative Synthesis Examples 1-3 were measured respectively, and determined as the acid value of the copolymer (A). It is the acid value of curable polymer measured in accordance with JIS K6901 5.3. That is, the acid value means the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer.

[Examples 1-12, Comparative Examples 1-3] Mix the polymer compositions of Synthesis Examples 1 to 12 and Comparative Synthesis Examples 1 to 3 shown in Table 1 to Table 3, propylene glycol monomethyl ether acetate as (B) solvent, and (C) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a reactive diluent, (D) ethyl ketone as a photopolymerization initiator, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (manufactured by BASF Japan Co., Ltd.), as (E) The dye of the colorant (VALIFAST blue 2620) was used to prepare the resin compositions of Examples 1-12 and Comparative Examples 1-3.

In the copolymer (A) shown in Table 4, the amount of the solvent contained in the reaction liquid used at the time of manufacture of copolymer (A) was not contained. The amount of solvent (B) shown in Table 4 is obtained by combining the solvent (propylene glycol monomethyl ether) contained in the polymer composition with the solvent (propylene glycol monomethyl ether acetate) added during the production of the resin composition. Calculated amount. The content ratio of the hydroxyl group-containing solvent in the solvent (B) shown in Table 4 was 79.1% by mass.

About the resin composition of Examples 1-12 and Comparative Examples 1-3, alkali developability and solvent resistance were evaluated by the method shown below. (1) Alkali developability The resin compositions of Examples and Comparative Examples were spin-coated on a square glass substrate (alkali-free glass substrate) with a length of 5 cm and a width of 5 cm in plan view so that the thickness after exposure was 2.5 μm to form coating films. Next, the solvent in the coating film was volatilized and removed by heating at 100° C. for 3 minutes.

Next, place a photomask with a specified pattern at a distance of 100 μm from the coating film, and expose the coating film to ultraviolet rays with a wavelength of 365 nm at an energy ray amount of 40 mJ/cm ² through the photomask to photocure the exposed part. Next, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23° C. and a pressure of 0.3 MPa to dissolve unexposed portions and develop. After that, a prescribed pattern is formed by baking at 100° C. for 20 minutes.

Then, the pattern after the alkali development was observed by using an electron microscope S-3400 manufactured by Hitachi Advanced Technology Co., Ltd., and the residue after the alkali development was confirmed, and the evaluation was performed according to the criteria shown below. The results are shown in Table 5. ○: No residue of unexposed parts ×: There are residues of unexposed parts

(2) Solvent resistance The resin compositions of Examples and Comparative Examples were spin-coated on a square glass substrate (alkali-free glass substrate) with a length of 5 cm and a width of 5 cm in plan view so that the thickness after exposure was 2.5 μm to form coating films. Next, the solvent in the coating film was volatilized and removed by heating at 100° C. for 3 minutes.

Next, exposure was performed by irradiating ultraviolet light with a wavelength of 365 nm at an energy ray amount of 40 mJ/cm ² to photocure the exposed portion. Thereafter, by baking at 80° C. for 30 minutes, or at 100° C. for 20 minutes, the coating film is hardened to form a cured film. The prepared cured film was immersed in 20g of propylene glycol monomethyl ether at 23°C for 15 minutes, and the color change (ΔEab) before and after immersion was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Based on the results Carry out the evaluation of solvent resistance. The results are shown in Table 5.

As shown in Table 5, the evaluation of alkali developability of the cured films obtained by curing the resin compositions of Examples 1 to 12 was good. Also, for the cured films obtained by curing the resin compositions of Examples 1 to 12, the coating film was cured at a temperature of 80°C for 30 minutes, and when the temperature was set at 100°C for a fixed time. In either case of 20 minutes, ΔEab was less than 3, and the solvent resistance was good.

On the other hand, the cured films obtained by curing the resin compositions of Comparative Examples 1 to 3 were evaluated as good in alkali developability, but the temperature for curing the coating film was set at 80°C and the time was set at 30 minutes In ΔEab, it is 3 or more, and the solvent resistance is insufficient. [Industrial availability]

According to the present invention, there is provided a resin composition that has good alkali developability when used as a photosensitive material, has excellent storage stability, and can obtain a cured product having excellent solvent resistance even when it is cured at a low temperature. The resin composition is a useful copolymer, and a method for producing the copolymer. Also, according to the present invention, there are provided a colored pattern made of a cured product of a resin composition having good developability and a cured product having excellent solvent resistance even when cured at a low temperature, and a color filter having the same. A light sheet, and an image display element provided with the color filter. The resin composition of the present invention can be preferably used as materials for transparent films, protective films, insulating films, outer coatings, photo spacers, black matrixes, black column spacers, color filter resists, etc. in a wide range of uses.

Claims (15)

A kind of copolymer, it is characterized in that containing the structural unit (a) that has the base shown in following formula (1) or following formula (2), has the structural unit (b) of hydroxyl group, and has the structural unit ( c), the glass transition temperature of which is below 30°C,

(In formula (1), R ¹ and R ² are independently independent and represent an alkyl group with 1 to 10 carbons; * represents a linking site),

(In formula (2), R ³ represents an alkyl group with 1 to 10 carbon atoms; * represents a linking site). The copolymer according to claim 1, wherein the aforementioned structural unit (b) is a structural unit derived from hydroxyalkyl (meth)acrylate. The copolymer according to claim 1 or claim 2, wherein the aforementioned structural unit (c) is a structural unit derived from an unsaturated carboxylic acid. The copolymer of claim 1 or claim 2, wherein the aforementioned structural unit (a) is derived from a compound having a group represented by the aforementioned formula (1) or the aforementioned formula (2) and a (meth)acryloxy group Structural units. Such as the copolymer of claim 1 or claim 2, which contains the aforementioned structural unit (a) 1~40 mol%, the aforementioned structural unit (b) 1~60 mol%, the aforementioned structural unit (c) 1~60 mol% Ear%. The copolymer of claim 1 or claim 2, wherein the total amount of the ester groups contained in the groups shown in the aforementioned formula (1) or the aforementioned formula (2) and the total amount of the hydroxyl groups contained in the aforementioned structural unit (b) The molar ratio is 10:90~90:10. Such as the copolymer of claim 1 or claim 2, wherein the weight average molecular weight is 1,000~50,000. A resin composition, characterized in that it contains the copolymer (A) and solvent (B) as any one of claim 1 to claim 7, The aforementioned solvent (B) includes a hydroxyl group-containing solvent. The resin composition according to claim 8, which further contains a reactive diluent (C) and a photopolymerization initiator (D). The resin composition according to claim 9, which further contains a colorant (E). The resin composition according to claim 10, which contains: 10-90 parts by mass of the aforementioned copolymer (A), Aforesaid solvent (B) 30～1000 mass parts, 10-90 parts by mass of the aforementioned reactive diluent (C), 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (D), 3-80 parts by mass of the aforementioned colorant (E). A color filter characterized by having a colored pattern made of a hardened resin composition as claimed in Claim 10 or Claim 11. An image display element, characterized by having a color filter as claimed in claim 12. A method for producing a copolymer, characterized by comprising the following steps (I) to (III): a solvent heating step of raising the temperature of the solvent (B-1) to 60~90°C and preparing the heated solvent (B-1h) (I); Dissolving the monomer (ma), hydroxyl-containing monomer (mb) and acid group-containing monomer (mc) having the group shown in the following formula (1) or following formula (2) The monomer solution formed in the solvent (B-2) is dropped into the above-mentioned solvent (B-1h) which has been heated up, and at the same time, the polymerization initiator obtained by dissolving the polymerization initiator in the above-mentioned solvent (B-2) The solution is dripped into the aforementioned solvent (B-1h) to make the dropwise polymerization step (II) of the mixed solution; and the post-polymerization step (III) is made to react at 60~90°C for 1~5 hours while stirring the aforementioned mixed solution ; Either or both of the aforementioned solvent (B-1) and the aforementioned solvent (B-2) contain a hydroxyl group-containing solvent,

(In formula (1), R ¹ and R ² are independently independent and represent an alkyl group with 1 to 10 carbons; * represents a linking site),

(In formula (2), R ³ represents an alkyl group with 1 to 10 carbon atoms; * represents a linking site). The method for producing a copolymer according to claim 14, wherein in the solvent heating step (I), the temperature is raised after adding a chain transfer agent to the solvent (B-1).