Resin composition, modified resin composition and method for producing modified resin composition

Abstract

The resin composition contains a copolymer precursor (PA), an ethylenically unsaturated compound (e) having a functional group reactive with an acid group, a basic catalyst (B), and a solvent (C), and is characterized in that: the copolymer precursor (PA) contains a structural unit (a-1) having a blocked isocyanate group, a structural unit (a-2) having a hydroxyl group, and a structural unit (a-3) having an acid group; the content of the basic catalyst (B) is 0.5-12 parts by mass per 100 parts by mass of the total of the copolymer precursor (PA) and the ethylenically unsaturated compound (e).

Description

Technical Field

[0001] This disclosure relates to resin compositions, modified resin compositions, photosensitive resin compositions, photosensitive coloring compositions, resin-cured films, image display elements, methods for manufacturing resin compositions, and methods for manufacturing modified resin compositions. Background Technology

[0002] In recent years, from the perspective of resource and energy conservation, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet light and electron beams have been widely used in various coating, printing, paint, and adhesive fields. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are also used in solder resists and photoresists for color filters. The requirements for the properties of curable photosensitive resin compositions are becoming increasingly diverse and demanding, including the need for short-time curing for productivity and low-temperature curing to inhibit thermal damage to the components being applied.

[0003] Color filters generally consist of a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and a protective film formed on the pixels and the black matrix. Color filters with this configuration are typically manufactured by sequentially forming the black matrix, pixels, and protective film on the transparent substrate. Various methods have been proposed for forming the pixels and black matrix (hereinafter referred to as "colored patterns"). Among these, the pigment / dye dispersion method, which uses a photolithography process involving repeated coating, exposure, development, and baking with a photosensitive resin composition as a resist to create colored patterns, has become the mainstream method due to its excellent durability and low pinhole defects.

[0004] Generally, the photosensitive resin composition used in photolithography contains alkali-soluble resin, reactive diluent, photopolymerization initiator, colorant, and solvent. While pigment / dye dispersion methods offer the aforementioned advantages, the repeated baking required to form black matrices, R, G, and B patterns often presents limitations, such as the need for high heat resistance in the photosensitive resin composition and the restriction to using only colorants capable of withstanding high baking temperatures.

[0005] In recent years, photosensitive resin compositions with low-temperature curability have been proposed that also correspond to components with low heat resistance, such as organic EL. For example, Patent Documents 1 to 3 disclose coloring compositions having specific partial structures and hydroxyl groups as photosensitive resin compositions that can obtain cured products with excellent solvent resistance even under low-temperature curing conditions and are suitable for use in color filters and the like.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2021-102759

[0009] Patent Document 2: Japanese Patent Application Publication No. 2023-021219

[0010] Patent Document 3: Japanese Patent Application Publication No. 2023-059924 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, in recent years, there has been a growing demand for low-temperature curing. This, in turn, may result in incomplete curing of the film, leading to reduced solvent resistance due to substitution. Therefore, it is required that the cured product exhibit high solvent resistance even under low-temperature curing conditions. In addition, excellent developability of the photosensitive resin composition is also required.

[0013] This disclosure provides a resin composition that can efficiently introduce olefinic unsaturated groups into a resin having terminal isocyanate groups and hydroxyl groups, and can be transformed into a modified resin composition that contributes to improved developability. Furthermore, it provides a modified resin composition that contributes to improved developability, a photosensitive resin composition that yields a resin-cured film with excellent solvent resistance, and a photosensitive coloring composition. This disclosure further provides a resin-cured film with excellent solvent resistance and an image display element having the resin-cured film.

[0014] Methods for solving problems

[0015] The contents of this disclosure include the following schemes.

[0016] [1]

[0017] A resin composition comprising: Copolymer precursor (PA); Alkene unsaturated compounds having functional groups that are reactive with acid groups (e); Alkaline catalyst (B); and Solvent (C), The above copolymer precursor (PA) contains: Structural units with terminal isocyanate groups (a-1); Structural units containing hydroxyl groups (a-2); and Structural units containing acid groups (a-3), The content of the alkaline catalyst (B) is 0.5 to 12 parts by mass relative to the total of 100 parts by mass of the copolymer precursor (PA) and the olefinic unsaturated compound (e).

[0018] [2]

[0019] A modified resin composition comprising: copolymer (A); Alkaline catalyst (B); and Solvent (C), The copolymer (A) described above is a copolymer obtained by addition reaction of an olefinic unsaturated compound (e) having a functional group that is reactive with an acid group with a portion of the acid group in the structural unit (a-3) of the copolymer precursor (PA). The above copolymer precursor (PA) contains: Structural units with terminal isocyanate groups (a-1); Structural units containing hydroxyl groups (a-2); and Structural units containing acid groups (a-3), The content of the alkaline catalyst (B) is 0.5 to 12 parts by mass relative to 100 parts by mass of the copolymer (A).

[0020] [3]

[0021] According to the resin composition described in [1] or the modified resin composition described in [2], the above-mentioned alkaline catalyst (B) satisfies the following conditions (1) and (2).

[0022] Condition (1): The force field is set to GAFF2, the charge is set to RESP(B3LYP / 6-31G(d) / / HF / 6-31G(d)), and molecular dynamics calculations are performed at 78℃ and 1 atmosphere. The coordination number of the basic catalyst (B) relative to glycidyl methacrylate, calculated using the radial distribution function of the obtained trajectory, is greater than 0.16.

[0023] Condition (2): In quantum chemical calculations, after optimizing the structure of the basic catalyst (B) using B3LYP as the generalized function and 6-31G(d) as the basis function, the calculated orbital energy (Hartley) is above -0.250.

[0024] [4]

[0025] According to the resin composition described in [1] or the modified resin composition described in [2], the alkaline catalyst (B) is selected from at least one of pyridine and pyridine derivatives, and phosphine derivatives.

[0026] [5]

[0027] According to any one of the resin compositions [1], [3] and [4] or any one of the modified resin compositions [2] to [4], the alkaline catalyst (B) is selected from at least one of 4-dimethylaminopyridine, tricyclohexylphosphine, tris(2,6-dimethoxyphenyl)phosphine and tris(p-tolyl)phosphine.

[0028] [6]

[0029] According to any one of [1] and [3] to [5], in all structural units of the copolymer precursor (PA) described above, The content of the structural unit (a-1) with the terminal isocyanate group is 5-40 mol%. The content of the above-mentioned hydroxyl-containing structural unit (a-2) is 1 to 35 mol%. The content of the above-mentioned structural unit (a-3) with acid groups is 5-70 mol%. Relative to 100 moles of the structural units of the aforementioned copolymer precursor (PA), The amount of the above-mentioned olefinic unsaturated compound (e) is 1 to 60 moles. Relative to 100 moles of the above-mentioned acid-containing structural unit (a-3) of the copolymer precursor (PA), The amount of the above-mentioned olefinic unsaturated compound (e) is 5 to 90 moles.

[0030] [7]

[0031] According to any one of [2] to [5], in all structural units of the above copolymer precursor (PA), The content of the structural unit (a-1) with the terminal isocyanate group is 5-40 mol%. The content of the above-mentioned hydroxyl-containing structural unit (a-2) is 1 to 35 mol%. The content of the above-mentioned structural unit (a-3) with acid groups is 5-70 mol%. Relative to 100 moles of the structural units of the aforementioned copolymer precursor (PA), The addition amount of the above-mentioned olefinic unsaturated compound (e) is 1 to 55 moles. Relative to 100 moles of the above-mentioned acid-containing structural unit (a-3) of the copolymer precursor (PA), The addition amount of the above-mentioned olefinic unsaturated compound (e) is 1 to 85 moles.

[0032] [8]

[0033] According to any one of [2] to [5] and [7], the modified resin composition of the copolymer (A) has an olefinic unsaturated group equivalent of 200 to 4,000 g / mol.

[0034] [9]

[0035] According to any one of [2] to [5], [7] and [8], the modified resin composition of the above copolymer (A) has an acid value of 10 to 300 KOH mg / g.

[0036]

[10]

[0037] According to any one of [2] to [5] and [7] to [9], the copolymer (A) has a capped isocyanate equivalent of 300 to 6,000 g / mol and a hydroxyl equivalent of 200 to 10,000 g / mol.

[0038]

[11]

[0039] According to any one of [2] to [5] and [7] to

[10] , the copolymer (A) has a weight-average molecular weight (Mw) of 1,000 to 50,000 and a molecular weight distribution (Mw / Mn) of 1.3 to 5.0.

[0040]

[12]

[0041] According to any one of the resin compositions [1] and [3] to [6] or any one of the modified resin compositions [2] to [5] and [7] to

[11] , the terminated isocyanate group of the structural unit (a-1) having the terminated isocyanate group is a group represented by formula (1) or formula (2) below.

[0042]

[0043] (In equation (1), R) 1 and R 2 Each of these groups independently represents an alkyl group having 1 to 10 carbon atoms. * indicates a site where a residue is attached to a structural unit (a-1) having its terminal isocyanate group removed.

[0044] (In equation (2), R) 3 This indicates an alkyl group with 1 to 10 carbon atoms. * indicates a site where the residue is attached to a structural unit (a-1) having its terminal isocyanate group removed.

[0045]

[13]

[0046] According to any one of the resin compositions [1] and [3] to [6] or any one of the modified resin compositions [2] to [5] and [7] to

[11] , the capping agent of the above-mentioned capping isocyanate group constituting the above-mentioned structural unit (a-1) having a capping isocyanate group is selected from at least one of pyrazole compounds, oxime compounds and phenolic compounds.

[0047]

[14]

[0048] According to any one of the resin compositions [1], [3] to [6],

[12] and

[13] or any one of the modified resin compositions [2] to [5] and [7] to

[13] , the above-mentioned structural unit (a-2) having a hydroxyl group is a structural unit having a group represented by -CH2-OH.

[0049]

[15]

[0050] The resin composition according to any one of [1], [3] to [6] and

[12] to

[14] or the modified resin composition according to any one of [2] to [5] and [7] to

[14] , wherein the hydroxyl-containing structural unit (a-2) is selected from those having -(CH2). n The structural units of the -OH group (n is an integer from 2 to 6) and those with -(OC) x H 2x ) m At least one of the structural units of the group represented by -OH (x is an integer from 2 to 4, and m is an integer from 2 to 6).

[0051]

[16]

[0052] The resin composition according to any one of [1], [3] to [6] and

[12] to

[15] or the modified resin composition according to any one of [2] to [5] and [7] to

[15] , wherein the olefinic unsaturated compound (e) is an epoxy-containing (meth)acrylate.

[0053]

[17]

[0054] A photosensitive resin composition comprising: The modified resin composition as described in any one of [2] to [5] and [7] to

[16] ; Reactive diluent (D); and Photopolymerization initiator (E).

[0055]

[18]

[0056] According to the photosensitive resin composition described in

[17] , relative to the total of the copolymer (A) and the reactive diluent (D) described above, The content of the above copolymer (A) is 10-90% by mass. The content of the above reactive diluent (D) is 90-10% by mass. Relative to a total of 100 parts by mass of the copolymer (A) and the reactive diluent (D), The content of the above-mentioned photopolymerization initiator (E) is 0.1 to 30 parts by weight. Relative to 100 parts by mass of the total components excluding solvent (C) mentioned above, The content of the solvent (C) is 30 to 1,000 parts by mass.

[0057]

[19]

[0058] According to any one of the resin compositions [1], [3] to [6] and

[12] to

[16] or any one of the modified resin compositions [2] to [5] and [7] to

[16] , the dissociation rate of the end-capped isocyanate group of the above-mentioned structural unit (a-1) having the end-capped isocyanate group is 5 to 99% when heated at 100°C for 30 minutes.

[0059]

[20]

[0060] A photosensitive coloring composition comprising: The modified resin composition as described in any one of [2] to [5] and [7] to

[16] ; Reactive diluent (D); Photopolymerization initiator (E); and Colorant (F).

[0061] [twenty one]

[0062] According to the photosensitive coloring composition described in

[20] , relative to a total of 100 parts by mass of the copolymer (A) and the reactive diluent (D) described above, The content of the above colorant (F) is 0.1 to 80 parts by mass.

[0063] [twenty two]

[0064] A resin-cured film, which is a cured product of the photosensitive resin composition described in

[17] or

[18] .

[0065] [twenty three]

[0066] A resin-cured film, which is a cured product of the photosensitive coloring composition described in

[20] or

[21] .

[0067] [twenty four]

[0068] A color filter having a color pattern as a cured product of the photosensitive coloring composition described in

[20] or

[21] .

[0069]

[25]

[0070] An image display element having the color filter described in

[24] .

[0071]

[26]

[0072] A method for manufacturing a resin composition includes a step (I) of preparing the resin composition, wherein the resin composition contains a copolymer precursor (PA), an olefinic unsaturated compound (e) having functional groups that react with acid groups, a basic catalyst (B), and a solvent (C). The above copolymer precursor (PA) contains: Structural units with terminal isocyanate groups (a-1); Structural units containing hydroxyl groups (a-2); and Structural units containing acid groups (a-3), The content of the alkaline catalyst (B) is 0.5 to 12 parts by mass relative to the total of 100 parts by mass of the copolymer precursor (PA) and the olefinic unsaturated compound (e).

[0073]

[27]

[0074] A method for manufacturing a modified resin composition, comprising a heating step (II) of holding the resin composition obtained by the manufacturing method described in

[26] at 50 to 120°C for 30 to 500 minutes. In the above heating process (II), the olefinic unsaturated compound (e) having a functional group that is reactive with an acid group adds to the acid group of the above-mentioned structural unit (a-3) having an acid group in the copolymer precursor (PA), and the copolymer precursor (PA) is transformed into copolymer (A).

[0075] The effects of the invention

[0076] According to this disclosure, a resin composition can be provided that can efficiently introduce olefinic unsaturated groups into a resin having capped isocyanate groups and hydroxyl groups, and can be transformed into a modified resin composition that helps improve developability. Furthermore, a modified resin composition that helps improve developability, a photosensitive resin composition that yields a resin-cured film with excellent solvent resistance, and a photosensitive coloring composition can be provided. In addition, a resin-cured film with excellent solvent resistance, a color filter, and an image display element equipped with the color filter can be provided, formed by curing the above-mentioned photosensitive resin composition and photosensitive coloring composition. Detailed Implementation

[0077] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the embodiments shown below.

[0078] In this specification, when "~" is used to refer to a numerical range, the values ​​at both ends are the upper and lower limits, respectively, and are included within the numerical range. When multiple upper or lower limits are specified, a numerical range can be created from all combinations of the upper and lower limits. Similarly, when multiple numerical ranges are specified, another numerical range can be created by individually selecting and combining the upper and lower limits from these ranges.

[0079] In this specification, "(meth)acrylic acid" refers to methacrylic acid or acrylic acid, "(meth)acrylate" refers to acrylate or methacrylate, and "(meth)acryloyloxy" refers to acryloyloxy or methacryloyloxy. In this specification, "(poly)alkylene glycol" refers to alkylene glycol or polyalkylene glycol.

[0080] In this specification, "olefin unsaturated bond" refers to a double bond formed between carbon atoms other than the carbon atoms forming the aromatic ring, "olefin unsaturated group" refers to a group having olefin unsaturated bonds, and "olefin unsaturated compound" refers to a compound having olefin unsaturated bonds.

[0081] In this specification, the term "structural unit" refers to a unit derived from the polymeric compound itself used as a monomer, or a unit obtained by further modifying a unit derived from the polymeric compound itself used as a monomer after polymerization.

[0082] In this specification, the acid value of the resin is the acid value of the cured polymer as measured according to JIS K6901:2008 5.3. That is, the acid value refers to the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1g of the resin.

[0083] In this specification, the term "resin-terminated isocyanate equivalent" refers to the mass of resin relative to the number of terminal isocyanate groups in each mole of resin. The terminology for terminal isocyanate equivalent can be determined by dividing the mass of the resin by the number of terminal isocyanate groups in the resin (g / mol). In this specification, the terminology for terminal isocyanate equivalent is a theoretical value calculated from the amount of raw materials added during the manufacture of the resin.

[0084] In this specification, the term "hydroxyl equivalent" of a resin refers to the mass of resin relative to the hydroxyl groups in one mole of resin. The hydroxyl equivalent is calculated based on the hydroxyl value measured using a mixture of bromothymol blue and phenol red indicators according to JIS K0070:1992. The hydroxyl value of a resin refers to the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl groups when 1 g of resin is acetylated. The hydroxyl equivalent of a resin can be calculated by converting the number of mg of potassium hydroxide required for neutralization into moles, and then determining the mass of one mole of resin.

[0085] In this specification, the term "ene unsaturated group equivalent" of copolymer (A) refers to the mass of copolymer (A) relative to the number of ene unsaturated groups in each mole of copolymer (A). The ene unsaturated group equivalent can be determined (g / mol) by dividing the mass of copolymer (A) by the number of ene unsaturated groups in copolymer (A). In this specification, the term "ene unsaturated group equivalent" of copolymer (A) is a value calculated from the amount of raw material added during the manufacture of copolymer (A) and the addition reaction rate of compound (e). The addition reaction rate of compound (e) is calculated using the method described in the examples.

[0086] In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​obtained by gel permeation chromatography (GPC) under the following conditions using a standard polystyrene standard curve.

[0087] Column: Two columns of Setontronix (trademark) LF-804 (Russell Co., Ltd.) were connected in series and used.

[0088] Column temperature: 40℃

[0089] Sample: 0.2% (w / w) tetrahydrofuran solution of the analyte being tested

[0090] Developing solvent: Tetrahydrofuran

[0091] Detector: Differential refractometer (ショウデックス (trademark) RI-71S) (Ryosun Co., Ltd.)

[0092] Flow rate: 1 mL / min

[0093] [Resin Composition]

[0094] One embodiment of the resin composition contains a copolymer precursor (PA), an olefinic unsaturated compound (e) having a functional group reactive with an acid group (also simply referred to as "compound (e)"), a basic catalyst (B), and a solvent (C). In the resin composition, the content of the basic catalyst (B) is 0.5 to 12 parts by mass relative to a total of 100 parts by mass of the copolymer precursor (PA) and compound (e).

[0095] <Copolymer Precursor (PA)>

[0096] The copolymer precursor (PA) contains structural units (a-1) with terminal isocyanate groups (also simply referred to as "structural unit (a-1)"), structural units (a-2) with hydroxyl groups (also simply referred to as "structural unit (a-2)"), and structural units (a-3) with acid groups (also simply referred to as "structural unit (a-3)"). The copolymer precursor (PA) may, as needed, contain other structural units (a-4) besides structural units (a-1) to (a-3).

[0097] The acid value of the copolymer precursor (PA) is preferably 30 KOH mg / g or more, more preferably 60 KOH mg / g or more, and even more preferably 90 KOH mg / g or more. The acid value of the copolymer precursor (PA) is preferably 300 KOH mg / g or less, more preferably 260 KOH mg / g or less, and even more preferably 220 KOH mg / g or less. If the acid value of the copolymer precursor (PA) is 30 KOH mg / g or more, the developability is better when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions. If the acid value of the copolymer precursor (PA) is 300 KOH mg / g or less, the storage stability is good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions.

[0098] The equivalent amount of end-capped isocyanate groups in the copolymer precursor (PA) is preferably 300 g / mol or more, more preferably 350 g / mol or more, and even more preferably 400 g / mol or more. The equivalent amount of end-capped isocyanate groups in the copolymer precursor (PA) is preferably 6,000 g / mol or less, more preferably 4,000 g / mol or less, even more preferably 2,000 g / mol or less, and particularly preferably 1,000 g / mol or less. If the equivalent amount of end-capped isocyanate groups in the copolymer precursor (PA) is 300 g / mol or more, the storage stability is good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions. If the equivalent amount of end-capped isocyanate groups in the copolymer precursor (PA) is 6,000 g / mol or less, the low-temperature curing properties are good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions, and the solvent resistance of the cured product is even better.

[0099] The hydroxyl equivalent of the copolymer precursor (PA) is preferably 400 g / mol or more, more preferably 550 g / mol or more, further preferably 700 g / mol or more, and particularly preferably 1,000 g / mol or more. The hydroxyl equivalent of the copolymer precursor (PA) is preferably 10,000 g / mol or less, more preferably 7,000 g / mol or less, further preferably 5,000 g / mol or less, and particularly preferably 3,000 g / mol or less. If the hydroxyl equivalent of the copolymer precursor (PA) is 400 g / mol or more, the storage stability is good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions. If the hydroxyl equivalent of the copolymer precursor (PA) is 10,000 g / mol or less, the low-temperature curing properties are good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions, and the solvent resistance of the cured product is even better.

[0100] The weight-average molecular weight (Mw) of the copolymer precursor (PA) is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. The weight-average molecular weight of the copolymer precursor (PA) is preferably 60,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. If the weight-average molecular weight of the copolymer precursor (PA) is 2,000 or more, the low-temperature curability is good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions. If the weight-average molecular weight of the copolymer precursor (PA) is 60,000 or less, the storage stability is good when the copolymer precursor (PA) is converted into copolymer (A) and used in photosensitive resin compositions or photosensitive coloring compositions.

[0101] The molecular weight distribution (Mw / Mn) of the copolymer precursor (PA) is preferably 1.3 or more, more preferably 1.5 or more, further preferably 1.7 or more, and particularly preferably 1.9 or more. The molecular weight distribution (Mw / Mn) of the copolymer precursor (PA) is preferably 5.0 or less, more preferably 4.5 or less, further preferably 4.0 or less, and particularly preferably 3.5 or less. If the molecular weight distribution (Mw / Mn) of the copolymer precursor (PA) is 1.3 or more, the manufacturing conditions, etc., during the synthesis of the copolymer precursor (PA) are easier to control. If the molecular weight distribution (Mw / Mn) of the copolymer precursor (PA) is 5.0 or less, the storage stability is good.

[0102] (Structural unit with terminal isocyanate group (a-1))

[0103] The structural unit (a-1) with a capped isocyanate group is not particularly limited as long as it has a structure in which the isocyanate group is blocked by the addition of a capping agent. The structural unit (a-1) can be only one type or two or more types. The structural unit (a-1) is a structural unit derived from a monomer (ma-1) containing a capped isocyanate group (hereinafter also simply referred to as "monomer (ma-1)"). The copolymer precursor (PA) has the structural unit (a-1), thereby crosslinking with the structural unit (a-2) having a hydroxyl group occurs when a photosensitive resin composition or photosensitive coloring composition containing a copolymer (A) obtained by modifying the copolymer precursor (PA) is heated. As a result, the cured product also exhibits good solvent resistance under low-temperature curing conditions. Crosslinking is formed, for example, by the reaction of isocyanate groups generated by the dissociation of the capping agent with hydroxyl groups. When the capping agent is a compound having an alkyloxycarbonyl group, cross-linking can be formed through transesterification of the alkyl group of the alkyloxycarbonyl group with the structural unit (a-2) having a hydroxyl group, even without the dissociation of the capping agent.

[0104] In one embodiment, the monomer (ma-1) has an olefinic unsaturated bond and a capped isocyanate group. The monomer (ma-1) can be used alone or in combination of two or more. Examples of monomers (ma-1) include compounds in which the isocyanate group of an isocyanate compound having an olefinic unsaturated bond and an isocyanate group has been capped with a capping agent. Examples of olefinic unsaturated groups included in the monomer (ma-1) include, for example, vinyl groups, (meth)acryloyloxy groups, etc.

[0105] The isocyanate compound and capping agent blocking reaction during the manufacture of monomer (ma-1) can be carried out regardless of the presence or absence of a solvent. When using a solvent for the above blocking reaction, any solvent that is inactive with the isocyanate group can be used; known solvents can be employed. During the blocking reaction, organometallic salts containing metals such as tin, zinc, and lead, or tertiary amines, can be used as catalysts. The blocking reaction can generally be carried out at temperatures ranging from -20 to 150°C, preferably from 0 to 100°C.

[0106] Examples of the isocyanate compounds used as raw materials for monomers (ma-1) include, for example, the compounds shown in formula (3) below.

[0107]

[0108] (In equation (3), R) 4 Represents a hydrogen atom or a methyl group; R 5 Indicates -CO-, -COOR 6 -(Here, R) 6 It is an alkylene group having 1 to 6 carbon atoms. (or -COO-R)7 O-CONH-R 8 -(Here, R) 7 R is an alkylene group having 2 to 6 carbon atoms. 8 It can be an alkylene group with 2 to 12 carbon atoms or an aryl group with 6 to 12 carbon atoms, which may have substituents.

[0109] Among the isocyanate compounds shown in formula (3), considering the good reactivity of the unblocked isocyanate group and the ease of preparation of the isocyanate compound, R 5 Preferred -COOR 6 -, better R 6 It is an alkylene group having 1 to 4 carbon atoms.

[0110] Specifically, examples of isocyanate compounds represented by formula (3) above include 2-isocyanate-ethyl (meth) acrylate, 2-isocyanate-propyl (meth) acrylate, 3-isocyanate-propyl (meth) acrylate, 2-isocyanate-1-methylethyl (meth) acrylate, 2-isocyanate-1,1-dimethylethyl (meth) acrylate, 4-isocyanate-cyclohexyl (meth) acrylate, and methacryloyl isocyanate.

[0111] The isocyanate compound used as a raw material for the monomer (ma-1) can be a reaction product of reacting (meth)acrylate hydroxyalkyl ester with a diisocyanate compound in equimolar amounts ((meth)acrylate hydroxyalkyl ester: diisocyanate compound = 1 mole: 1 mole).

[0112] Considering the good reactivity of the unblocked isocyanate group and the simplicity of the reaction, the alkyl group of the above-mentioned (meth)acrylate hydroxyalkyl ester is preferably ethyl or n-propyl, more preferably ethyl.

[0113] Examples of the aforementioned diisocyanate compounds include, for example, 1,6-hexane diisocyanate, 2,4-(or 2,6-)toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanate-methylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanate-methyl)cyclohexane, lysine diisocyanate, etc.

[0114] Other isocyanate compounds mentioned above that are used as raw materials for monomers (ma-1) include 1,1-bis(methacryloyloxymethyl)methyl isocyanate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 1,1-bis(acryloyloxymethyl)methyl isocyanate and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0115] From the viewpoint of low-temperature curability of the photosensitive resin composition or photosensitive coloring composition containing copolymer (A), the structural unit (a-1) having a capped isocyanate group is preferably derived from a (meth)acrylate containing a capped isocyanate group. In the case where the monomer (ma-1) is a (meth)acrylate containing a capped isocyanate group, the isocyanate compound used as a raw material therefrom is a (meth)acrylate containing an isocyanate group.

[0116] Examples of (meth)acrylates containing isocyanate groups include, for example, 2-isocyanate-ethyl (meth)acrylate, 2-isocyanate-propyl (meth)acrylate, 3-isocyanate-propyl (meth)acrylate, 2-isocyanate-1-methylethyl (meth)acrylate, 2-isocyanate-1,1-dimethylethyl (meth)acrylate, 4-isocyanate-cyclohexyl (meth)acrylate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate. Among these, 2-isocyanate-ethyl (meth)acrylate, 2-isocyanate-propyl (meth)acrylate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate are preferred.

[0117] Examples of end-capping agents for blocking isocyanate groups include, for example, lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds such as methanol, ethanol, propanol, 1-methoxy-2-propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol, 2,6-dimethylphenol, cresol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styreneated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, 1-naphthol, and p- Phenolic compounds such as nitrophenol and p-chlorophenol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; thiols such as butanethiol, thiophene, and tert-dodecylthiol; amine compounds such as diisopropylamine, diphenylamine, phenylnaphthylamine, aniline, and carbazole; acid amide compounds such as acetanilide, methoxyacetanilide, acetamide, and benzamide; imide compounds such as succinic imide and maleic imide; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethylimidazole; pyrazole compounds such as pyrazole and 3,5-dimethylpyrazole; urea compounds such as urea, thiourea, and ethylidene urea; and N-phenylcarbamate, 2- Carbamic acid compounds such as azole ketones; imine compounds such as aproidine and polyethyleneimine; oxime compounds such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, and cyclohexanone oxime; and bisulfite salts such as sodium bisulfite and potassium bisulfite. Capping agents can be used alone or in combination of two or more.

[0118] In one embodiment, as a capping agent, from the viewpoint of the low-temperature curability of the photosensitive resin composition or the photosensitive coloring composition, it is preferably selected from at least one of pyrazole compounds, oxime compounds and phenolic compounds, more preferably from at least one of 3,5-dimethylpyrazole, methyl 4-hydroxybenzoate and methyl ethyl ketone oxime, and even more preferably from at least one of 3,5-dimethylpyrazole and methyl ethyl ketone oxime.

[0119] In the structural unit (a-1) with end-capped isocyanate groups, the highly reactive isocyanate groups are protected by an end-capping agent. By heating a photosensitive resin composition or photosensitive coloring composition containing a copolymer (A) comprising structural unit (a-1), the end-capped isocyanate groups in structural unit (a-1) can be dissociated, thereby regenerating the isocyanate groups. The regenerated isocyanate groups react with the reactive functional groups contained in copolymer (A) to form a cured product with high crosslinking density. Examples of reactive functional groups contained in copolymer (A) include hydroxyl groups contained in structural unit (a-2), acid groups contained in structural unit (a-3), and amino groups contained in other structural units (a-4) as needed.

[0120] In the structural unit (a-1) having end-capped isocyanate groups, the dissociation rate of the end-capped isocyanate groups after heating at 100°C for 30 minutes is preferably 5-99%, more preferably 10-90%, and most preferably 15-80%. The above dissociation rate can be, for example, 8-70%, 15-60%, or 30-50% as needed. If the above dissociation rate of the end-capped isocyanate groups in the structural unit (a-1) is 99% or less, then during the synthesis of the copolymer precursor (PA) and copolymer (A) and when storing the photosensitive resin composition or photosensitive coloring composition containing copolymer (A), the regeneration of isocyanate groups in the structural unit (a-1) and the occurrence of undesirable crosslinking reactions can be suppressed, thus ensuring the stability of the copolymer precursor (PA) and copolymer (A). If the dissociation rate of the end-capped isocyanate group of the structural unit (a-1) is 5% or more, good curability can be obtained even if the heating temperature used to cure the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is sufficiently low, and a cured product with superior solvent resistance can be obtained.

[0121] Examples of suitable end-capping agents, considering the stability of the copolymer precursor (PA) and copolymer (A) and the low-temperature curability of the photosensitive resin composition or photosensitive coloring composition, include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketone oxime, and 3,5-dimethylpyrazole. Among these end-capping agents, 3,5-dimethylpyrazole and methyl ethyl ketone oxime are more preferred from the viewpoint of the low-temperature curability of the photosensitive resin composition or photosensitive coloring composition containing copolymer (A).

[0122] The dissociation rate of the isocyanate-terminated structural unit (a-1) when heated at 100°C for 30 minutes can be considered to be the same as the dissociation rate of the isocyanate-terminated monomer (ma-1) containing the isocyanate-terminated group when heated at 100°C for 30 minutes, and is calculated by the method shown below.

[0123] Specifically, a n-octanol solution with a monomer (ma-1) concentration of 20% by mass was prepared. To the resulting n-octanol solution, 1% by mass of dibutyltin laurylate was added as a catalyst and 3% by mass of phenothiazine was added as a polymerization inhibitor, and the solution was heated at 100°C for 30 minutes. The heated n-octanol solution was analyzed by high-performance liquid chromatography (HPLC) to determine the mass of the monomer (ma-1) in the n-octanol solution. Using the results, the percentage reduction in the mass of the monomer (ma-1) caused by heating at 100°C for 30 minutes was calculated and determined as the dissociation rate at 100°C for 30 minutes.

[0124] The dissociation temperature at which the dissociation rate of the isocyanate groups in the structural unit (a-1) with end-capped isocyanate groups reaches 80% or more within 30 minutes is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. If the dissociation temperature of the isocyanate groups in the structural unit (a-1) is 80°C or higher, then during the synthesis of the copolymer precursor (PA) and copolymer (A) and during the storage of photosensitive resin compositions or photosensitive coloring compositions containing copolymer (A), the regeneration of isocyanate groups in the structural unit (a-1) and the occurrence of undesirable crosslinking reactions can be suppressed, thus ensuring the stability of the copolymer precursor (PA) and copolymer (A). The dissociation temperature at which the dissociation rate of the isocyanate groups in the structural unit (a-1) with end-capped isocyanate groups reaches 80% or higher within 30 minutes can be 160°C or lower. If the dissociation temperature of the end-capped isocyanate group of the structural unit (a-1) is below 160°C, good curability can be obtained even if the heating temperature used to cure the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is sufficiently low, and a cured product with superior solvent resistance can be obtained.

[0125] The dissociation temperature at which the dissociation rate of the isocyanate-terminated structural unit (a-1) reaches 80% or more after 30 minutes was calculated using the method described below. Specifically, a n-octanol solution with a monomer (ma-1) concentration of 20% by mass was prepared. To the resulting n-octanol solution, 1% by mass of dibutyltin laurylate was added as a catalyst and 3% by mass of phenothiazine was added as a polymerization inhibitor, and the solution was heated for 30 minutes under various different temperatures. The n-octanol solutions heated at different temperatures were analyzed by high-performance liquid chromatography (HPLC) to determine the mass of the monomer (ma-1) in the n-octanol solution. Using the results, the temperature at which the mass reduction of the monomer (ma-1) caused by heating for 30 minutes reached 80% or more was extracted. The lowest of these temperatures was determined as the dissociation temperature at which the dissociation rate of the isocyanate-terminated group reached 80% or more after 30 minutes.

[0126] The structural unit (a-1) having a capped isocyanate group is preferably selected from at least one of the structural units derived from the compound shown in formula (4) below, which has been capped with 3,5-dimethylpyrazole (dissociation temperature at which the dissociation rate of the capped isocyanate group reaches 80% or more after 30 minutes: 120°C, dissociation rate at 100°C for 30 minutes: 35%) and the compound shown in formula (5) below, which has been capped with methyl ethyl ketone oxime (dissociation temperature at which the dissociation rate of the capped isocyanate group reaches 80% or more after 30 minutes: 130°C, dissociation rate at 100°C for 30 minutes: 18%).

[0127]

[0128] In one embodiment, an active methylene compound is preferred as a capping agent from the viewpoint of the low-temperature curability of the photosensitive resin composition or the photosensitive coloring composition.

[0129] In one embodiment, from the viewpoint of low-temperature curability of the photosensitive resin composition or photosensitive coloring composition, compounds having alkyloxy carbonyl groups are preferred as end-capping agents. In this case, the structural unit (a-1) having end-capped isocyanate groups has alkyloxy carbonyl groups. The alkyloxy carbonyl groups are cross-linked by heat treatment of the photosensitive resin composition or photosensitive coloring composition containing copolymer (A), thereby undergoing transesterification with the structural unit (a-2) having hydroxyl groups. Therefore, the photosensitive resin composition or photosensitive coloring composition using copolymer (A) with structural unit (a-1) having alkyloxy carbonyl groups can obtain a cured film with excellent solvent resistance even when cured at low temperatures of 50°C to 150°C. As the compound having alkyloxy carbonyl groups, an active methylene compound having alkyloxy carbonyl groups is preferred.

[0130] As a structural unit (a-1) that uses an active methylene compound having an alkyloxy carbonyl group as a capping agent, examples include structural units having groups shown in formula (1) or formula (2) below.

[0131]

[0132] (In equation (1), R) 1 and R 2 Each of these groups independently represents an alkyl group having 1 to 10 carbon atoms. * indicates a site where a residue is attached to a structural unit (a-1) having its terminal isocyanate group removed.

[0133] (In equation (2), R) 3 This indicates an alkyl group with 1 to 10 carbon atoms. * indicates a site where the residue is attached to a structural unit (a-1) having its terminal isocyanate group removed.

[0134] When the structural unit (a-1) is a structural unit having a group shown in formula (1) or formula (2), if the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is cured at a low temperature of 50°C to 150°C, transesterification with the structural unit (a-2) having a hydroxyl group occurs, resulting in a cross-linked structure. Therefore, the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) can obtain a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.

[0135] R in the above formula (1) 1 and R 2 Each is an alkyl group having 1 to 10 carbon atoms. R 1 and R 2Preferably, each alkyl group is an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and most preferably R. 1 and R 2 Both are ethyl. In R 1 and R 2 In the case of ethyl, if the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is thermocured, then R 1 and R 2 Ethanol is generated by transesterification with a structural unit (a-2) containing a hydroxyl group. It is preferred that the ethanol generated during the thermosetting of the photosensitive resin composition or photosensitive coloring composition is easily removed by evaporation during heating used to thermoset the photosensitive resin composition or photosensitive coloring composition.

[0136] R in equation (2) above 3 It is an alkyl group having 1 to 10 carbon atoms. R 3 Preferably, it is an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and even more preferably an ethyl group. In R 3 In the case of ethyl, if the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is thermocured, then R 3 Ethanol is generated by transesterification with a structural unit (a-2) containing a hydroxyl group. It is preferred that the ethanol generated during the thermosetting of the photosensitive resin composition or photosensitive coloring composition is easily removed by evaporation during heating used to thermoset the photosensitive resin composition or photosensitive coloring composition.

[0137] In this embodiment, the modification rate of the isocyanate-terminated structural unit (a-1) having a terminal isocyanate group after heating at 100°C for 30 minutes is the same as the modification rate of the terminal isocyanate-terminated monomer (ma-1) containing a terminal isocyanate group after heating at 100°C for 30 minutes, and is calculated in the same manner as the method for calculating the dissociation rate described above. That is, a catalyst and a polymerization inhibitor are added to a n-octanol solution with a monomer (ma-1) concentration of 20% by mass, and the mass reduction ratio of the monomer (ma-1) caused by heating at 100°C for 30 minutes is calculated and determined as the modification rate after heating at 100°C for 30 minutes. In the structural unit (a-1) having a terminal isocyanate group, the modification rate of the terminal isocyanate group after heating at 100°C for 30 minutes is preferably 5-99%, more preferably 10-90%, and most preferably 15-80%.

[0138] The content of structural unit (a-1) in the copolymer precursor (PA) can be appropriately determined according to the application. The content of structural unit (a-1) in all structural units of the copolymer precursor (PA) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. The content of structural unit (a-1) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less. If the content of structural unit (a-1) is 5 mol% or more, the photosensitive resin composition or photosensitive coloring composition containing the copolymer (A) obtained by modifying the copolymer precursor (PA) exhibits good low-temperature curability and better solvent resistance of the cured product. If the content of structural unit (a-1) is 40 mol% or less, the content of structural units (a-2) and (a-3) can be sufficiently ensured, resulting in better developability of the photosensitive resin composition or photosensitive coloring composition containing the copolymer (A) obtained by modifying the copolymer precursor (PA).

[0139] (Structural unit with hydroxyl group (a-2))

[0140] The hydroxyl-containing structural unit (a-2) is a structural unit that has hydroxyl groups but not end-capped isocyanate groups. There can be only one type of structural unit (a-2) or two or more types. The structural unit (a-2) is derived from a monomer (ma-2) containing hydroxyl groups (hereinafter also simply referred to as "monomer (ma-2)"). By having the structural unit (a-2) in the copolymer precursor (PA), crosslinking occurs with the structural unit (a-1) having end-capped isocyanate groups when a photosensitive resin composition or photosensitive coloring composition containing a copolymer (A) obtained by modifying the copolymer precursor (PA) is heated. Therefore, even under low-temperature curing conditions, the resulting cured product exhibits good solvent resistance.

[0141] From the viewpoint of low-temperature curability, structural unit (a-2) is preferably a structural unit having a group represented by -CH2-OH, and more preferably a structural unit selected from those having -(CH2). n The structural units of the -OH group (n is an integer from 2 to 6) and those with -(OC) x H 2x ) m At least one of the structural units of the group represented by -OH (x is an integer from 2 to 4, and m is an integer from 2 to 6).

[0142] Examples of monomers (ma-2) include compounds that do not have a capped isocyanate group but have an olefinic unsaturated bond and a hydroxyl group. Examples of olefinic unsaturated groups contained in monomers (ma-2) include, for example, vinyl groups, (meth)acryloyloxy groups, etc.

[0143] Examples of monomers (ma-2) include compounds having hydroxyl and (meth)acryloyloxy groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl (meth)acrylate, hexaethylene glycol mono(meth)acrylate, and octaethylene glycol mono(meth)acrylate, etc. Monomers (ma-2) can be used alone or in combination of two or more.

[0144] As monomer (ma-2), from the viewpoint of reactivity during the synthesis of the copolymer precursor (PA), low-temperature curability of the photosensitive resin composition or photosensitive coloring composition containing the copolymer (A), and ease of acquisition, hydroxyalkyl methacrylate is preferred. As hydroxyalkyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate are preferred, and from the viewpoint of reducing the glass transition temperature of the copolymer (A), 2-hydroxyethyl methacrylate and 4-hydroxybutyl methacrylate are more preferred.

[0145] The content of structural unit (a-2) in the total structural units of the copolymer precursor (PA) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. The content of structural unit (a-2) in the total structural units of the copolymer precursor (PA) is preferably 35 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less. If the content of structural unit (a-2) is 1 mol% or more, sufficient crosslinking with the end-capped isocyanate groups of structural unit (a-1) can be ensured, resulting in good low-temperature curability of the photosensitive resin composition or photosensitive coloring composition. If the content of structural unit (a-2) is 35 mol% or less, the content of structural unit (a-1) can be sufficiently ensured, resulting in good low-temperature curability of the photosensitive resin composition or photosensitive coloring composition and better solvent resistance of the cured product. Furthermore, the content of structural unit (a-3) can be sufficiently ensured, resulting in better developability of the photosensitive resin composition or photosensitive coloring composition.

[0146] (Structural unit with acid group (a-3))

[0147] The structural unit (a-3) containing an acid group is not particularly limited as long as it is a structural unit containing an acid group but not a capped isocyanate group or a hydroxyl group. There can be only one type of structural unit (a-3) or two or more types. The structural unit (a-3) is derived from a monomer (ma-3) containing an acid group (hereinafter also simply referred to as "monomer (ma-3)"). Photosensitive resin compositions or photosensitive coloring compositions containing a copolymer (A) obtained by modifying the copolymer precursor (PA) and having the structural unit (a-3) in the copolymer precursor (PA) exhibit good developability.

[0148] Examples of acid groups present in structural unit (a-3) include carboxyl, sulfonyl, and phosphonyl groups. Among these acid groups, from the perspective of ease of acquisition, carboxyl is preferred as the acid group present in structural unit (a-3).

[0149] Examples of monomers (ma-3) include, for example, monomers that do not have capped isocyanate groups and hydroxyl groups but have olefinic unsaturated bonds and acid groups. Examples of monomers (ma-3) include, for example, unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, unsaturated phosphonic acids, etc.

[0150] Specifically, monomers (ma-3) can include (meth)acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, α-bromo(meth)acrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinonic 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; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p-styrenesulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid. Monomers (ma-3) can be used alone or in combination of two or more.

[0151] As a monomer (ma-3), in order to be readily available and to provide photosensitive resin compositions or photosensitive coloring compositions containing copolymer (A) with superior alkali developability, unsaturated carboxylic acids are preferred, and (meth)acrylic acid is more preferred.

[0152] The content of structural unit (a-3) in the copolymer precursor (PA) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. The content of structural unit (a-3) in the copolymer precursor (PA) is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less. If the content of structural unit (a-3) is 5 mol% or more, the developability of the photosensitive resin composition or photosensitive coloring composition is better. If the content of structural unit (a-3) is 70 mol% or less, the content of structural units (a-1) and (a-2) can be sufficiently ensured, resulting in good low-temperature curability of the photosensitive resin composition or photosensitive coloring composition and better solvent resistance of the cured product.

[0153] (Other structural units (a-4))

[0154] The copolymer precursor (PA) can, as needed, have other structural units (a-4) besides the structural units (a-1) to (a-3). These other structural units (a-4) are derived from other monomers (ma-4) (hereinafter also simply referred to as "monomer (ma-4)") that lack end-capped isocyanate groups, hydroxyl groups, and acid groups and are capable of copolymerizing with monomers (ma-1) to (ma-3). The desired physical properties or functions of the photosensitive resin composition or photosensitive coloring composition can be adjusted using the structural units (a-4).

[0155] Specific examples of monomers (ma-4) include aromatic vinyl compounds, cyclic alkenes with norbornene structures, dienes, (meth)acrylates, (meth)acrylamides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylate glycidyl esters, (meth)acrylic acid aniline, (meth)acrylonitrile, acrolein, etc.

[0156] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostrene, p-acetaminostyrene, and vinylpyridine.

[0157] Examples of cyclic olefins with a norbornene structure include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, and tetracyclo[4.4.0.1]. 2,5 .1 7,10 [Dodecyl-3-ene, 8-ethyltetracyclo[4.4.0.1]] 2, 5 .1 7,10 [Dodecyl-3-ene, dicyclopentadiene, tricyclo[5.2.1.0]]2,6 [Dec-8-ene, tricyclic [4.4.0.1]] 2,5 Undec-3-ene, tricyclic [6.2.1.0] 1,8 Undec-9-ene, tetracyclic [4.4.0.1] 2,5 .1 7,10 .0 1,6 [Dodecyl-3-ene, 8-ethylidene tetracyclo[4.4.0.1]] 2,5 .1 7,12 [Dodecyl-3-ene, pentacyclic [6.5.1.1]] 3,6 .0 2,7 .0 9,13 [Pentadec-4-ene, etc.]

[0158] Examples of dienes include butadiene, isoprene, and chloroprene.

[0159] Examples of (meth)acrylates include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, amyl methacrylate, benzyl methacrylate, isoamyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, rosin (meth)acrylate, norbornyl methacrylate, 5-ethyl norbornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isobornyl methacrylate, and adamantyl methacrylate. Tricyclodecyl methacrylate, tetrahydrofurfuryl methacrylate, 1,1,1-trifluoroethyl methacrylate, perfluoroethyl methacrylate, perfluoro-n-propyl methacrylate, 3-(N,N-dimethylamino)propyl methacrylate, triphenylmethyl methacrylate, phenyl methacrylate, cumyl methacrylate, 4-phenoxyphenyl methacrylate, phenoxyethyl methacrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, biphenoxyethyl methacrylate, naphthyl methacrylate, anthracene methacrylate, ethoxylated phenyl methacrylate, etc.

[0160] Examples of (meth)acrylic amides include (meth)acrylamide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, (meth)acrylic acid anthraquinone amide, etc.

[0161] Examples of vinyl compounds include vinyl chloride, 1,1-dichloroethylene, vinyl fluoride, 1,1-difluoroethylene, N-vinylpyrrolidone, and vinyl acetate.

[0162] Examples of unsaturated dicarboxylic acid diesters include diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

[0163] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.

[0164] The monomer (ma-4) can be used alone or in combination of two or more.

[0165] When the copolymer precursor (PA) contains structural unit (a-4), the content of structural unit (a-4) in all structural units of the copolymer precursor (PA) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. The content of structural unit (a-4) in all structural units of the copolymer precursor (PA) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. If the content of structural unit (a-4) is 1 mol% or more, the desired function can be imparted to the photosensitive resin composition or photosensitive coloring composition. If the content of structural unit (a-4) is 70 mol% or less, the content of structural units (a-1) to (a-3) can be sufficiently ensured, thus the developability and low-temperature curing properties of the photosensitive resin composition or photosensitive coloring composition are better, and the solvent resistance of the cured product is better.

[0166] <Alkene unsaturated compounds having functional groups that react with acid groups (e)>

[0167] Compound (e) has functional groups reactive with acid groups and olefinic unsaturated groups. Compound (e) can be one or more types. The olefinic unsaturated groups are introduced by adding compound (e) to the copolymer precursor (PA). As a result, the photosensitive resin composition or photosensitive coloring composition exhibits good photocurability, and the solvent resistance of the cured product is improved.

[0168] Examples of functional groups that are reactive with acid groups include epoxy groups, oxetyl groups, hydroxyl groups, and isocyanate groups. Among these, epoxy groups are preferred from the viewpoint of ease of synthesis of copolymer (A).

[0169] Examples of epoxy-containing olefinic unsaturated compounds include, for instance, epoxy ethylene acrylate, glycidyl acrylate, 2-methylglycidyl acrylate, 2-ethylglycidyl acrylate, 2-epoxy ethylene ethyl acrylate, 2-glycidyloxyethyl acrylate, 3-glycidyloxypropyl acrylate, 4-glycidyloxybutyl acrylate, glycidyloxyphenyl acrylate, and other epoxy-containing (meth)acrylate derivatives; and (Meth)acrylates containing epoxy groups include (meth)acrylate derivatives such as 3,4-epoxycyclohexyl ester, 3,4-epoxycyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl)ethyl ester, 2-(3,4-epoxycyclohexylmethyloxy)ethyl ester, and 3-(3,4-epoxycyclohexylmethyloxy)propyl ester; vinyl ether compounds containing epoxy groups; and allyl ether compounds containing epoxy groups. From the viewpoint of polymerizability and ease of acquisition, epoxy acrylates containing epoxy groups are preferred, such as glycidyl acrylate, 2-methylglycidyl acrylate, 2-ethylglycidyl acrylate, 2-epoxyethylene ethyl acrylate, 2-glycidyloxyethyl acrylate, 4-glycidyloxybutyl acrylate, glycidyloxyphenyl acrylate, and 3,4-epoxycyclohexylmethyl acrylate. More preferably, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, and 4-glycidyloxybutyl acrylate are preferred.

[0170] Compound (e) can be used alone or in combination of two or more.

[0171] The amount of compound (e) in the resin composition relative to 100 moles of the structural units of the copolymer precursor (PA) is preferably 1 mole or more, more preferably 5 moles or more, and even more preferably 10 moles or more. The amount of compound (e) in the resin composition relative to 100 moles of the structural units of the copolymer precursor (PA) is preferably 60 moles or less, more preferably 50 moles or less, and even more preferably 40 moles or less. If the amount of compound (e) in the resin composition is 1 mole or more relative to 100 moles of the structural units of the copolymer precursor (PA), the photocurability of the photosensitive resin composition or photosensitive coloring composition containing the copolymer (A) obtained by modifying the copolymer precursor (PA) is good. If the amount of compound (e) in the resin composition is 60 moles or less relative to 100 moles of the structural units of the copolymer precursor (PA), the content of acid groups in the structural unit (a-3) can be sufficiently ensured, and the developability of the photosensitive resin composition or photosensitive coloring composition containing the copolymer (A) obtained by modifying the copolymer precursor (PA) is better.

[0172] The amount of compound (e) in the resin composition relative to 100 moles of structural unit (a-3) of the copolymer precursor (PA) is preferably 5 moles or more, more preferably 10 moles or more, and even more preferably 20 moles or more. The amount of compound (e) in the resin composition relative to 100 moles of structural unit (a-3) of the copolymer precursor (PA) is preferably 90 moles or less, more preferably 80 moles or less, and even more preferably 70 moles or less. If the amount of compound (e) in the resin composition is 5 moles or more relative to 100 moles of structural unit (a-3) of the copolymer precursor (PA), the photocurability of the photosensitive resin composition or photosensitive coloring composition is good. If the amount of compound (e) in the resin composition is 90 moles or less relative to 100 moles of structural unit (a-3) of the copolymer precursor (PA), the acid group content of structural unit (a-3) can be sufficiently ensured, and the developability of the photosensitive resin composition or photosensitive coloring composition is good.

[0173] <Alkaline Catalyst (B)>

[0174] Specific examples of alkaline catalysts (B) include quaternary ammonium salts such as triethylbenzylammonium chloride; triphenylphosphine, Phosphorus compounds such as salts; organometallic compounds containing metals such as chromium and tin, etc. Alkaline catalysts (B) can be used alone or in combination of two or more.

[0175] Specific examples of the basic catalyst (B) include phosphine derivatives such as tris(2,6-dimethoxyphenyl)phosphine, tris(p-tolyl)phosphine, and tricyclohexylphosphine, and pyridine derivatives such as 4-dimethylaminopyridine. In one embodiment, the basic catalyst (B) is at least one selected from pyridine and pyridine derivatives, and phosphine derivatives. A phosphine derivative is a compound in which the hydrogen atom of phosphine is substituted by one or more substituents. A pyridine derivative is a compound in which the hydrogen atom of pyridine is substituted by one or more substituents.

[0176] Examples of basic catalysts (B) include compounds represented by the following formula (6).

[0177] R 9 N=CR 10 -NR 11 R 12 ···(6)

[0178] (In equation (6), R) 9 R 11 and R 12 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 10 Hydrogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, or -N(R) 13 The group shown in )2 (R in the formula) 13 It consists of a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and two R atoms. 13 They can be the same or different. 9 R 10 R 11 R 12 and 2 R 13 Any two or more groups within it can combine to form a ring structure.

[0179] Examples of basic catalysts (B) include compounds represented by formula (7).

[0180] R 14 N=CR 15 -NR 16 R 17 ···(7)

[0181] (In equation (7), R) 14 R 15 R 16 and R 17 It is a hydrocarbon group, R 14 With R 17 They combine to form a ring structure, R 14 With R 17 The sum of the number of carbon atoms is 3 to 20, R 15 With R 16They combine to form a ring structure, R 15 With R 16 The sum of the carbon atoms in the sample ranges from 3 to 20.

[0182] In the compound shown in formula (7), R forms a cyclic structure. 14 With R 17 The sum of the number of carbon atoms is 3 to 20, and from the viewpoint of ease of acquisition, it is preferably 3 to 10.

[0183] In the compound shown in formula (7), R forms a cyclic structure. 15 With R 16 The sum of the number of carbon atoms is 3 to 20, and from the viewpoint of ease of acquisition, it is preferably 3 to 10.

[0184] Specifically, examples of compounds represented by formula (6) or (7) include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene, and 1,1,3,3-tetramethylguanidine. In particular, from the viewpoints of the strength of catalytic activity, compatibility with solvents, and ease of acquisition, 1,8-diazabicyclo[5.4.0]-7-undecene is preferred.

[0185] Examples of alkaline catalysts (B) include alkylamines and cyclic diamines.

[0186] Examples of alkylamines include diisopropylamine, trimethylamine, and triethylamine.

[0187] Examples of cyclic diamines include 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0188] From the viewpoint of efficiently carrying out the addition reaction of compound (e), the basic catalyst (B) is preferably selected from at least one of pyridine and pyridine derivatives, and imidazole compounds. Although not bound by any theory, pyridine and pyridine derivatives, and imidazole compounds maintain their activity by not forming salts with the acid groups of the structural unit (a-3) due to their low pKa, and also have high nucleophilicity due to resonance stabilization. Therefore, by using at least one of pyridine and pyridine derivatives, and imidazole compounds, the addition reaction of compound (e) can be carried out efficiently to introduce an olefinic unsaturated group.

[0189] Specific examples of pyridine and pyridine derivatives include pyridine; C1-4 alkylpyridines such as methylpyridine (picolin) and ethylpyridine; diC1-4 alkylpyridines such as dimethylpyridine (rutidine); triC1-4 alkylpyridines such as trimethylpyridine (corridin); and 4-aminopyridine derivatives having an amino group at the 4-position, such as 4-aminopyridine, 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-pyrrolidinylpyridine, 4-piperidinylpyridine, and 2-methyl-4-dimethylaminopyridine. From a reactivity point of view, 4-aminopyridine derivatives are preferred, more preferably 4-aminopyridine derivatives having a tertiary amino group at the 4-position, even more preferably 4-dialkylaminopyridine, and particularly preferably 4-dimethylaminopyridine. Furthermore, "C1-4 alkyl" refers to an alkyl group having 1 to 4 carbon atoms.

[0190] Examples of imidazole compounds include 2-methylimidazole and 1,2-dimethylimidazole.

[0191] The alkaline catalyst (B) preferably satisfies the following conditions (1) and (2).

[0192] Condition (1): The force field is set to GAFF2, the charge is set to RESP(B3LYP / 6-31G(d) / / HF / 6-31G(d)), and molecular dynamics calculations are performed at 78℃ and 1 atmosphere. The coordination number of the basic catalyst (B) relative to glycidyl methacrylate, calculated using the radial distribution function of the obtained trajectory, is greater than 0.16.

[0193] Condition (2): In quantum chemical calculations, after optimizing the structure of the basic catalyst (B) using B3LYP as the generalized function and 6-31G(d) as the basis function, the calculated orbital energy (Hartley) is above -0.250.

[0194] The coordination number of the basic catalyst (B) in condition (1) is preferably 0.16 or more, more preferably 0.20 or more, and even more preferably 0.24 or more. If the coordination number is 0.16 or more, the catalyst is more readily accessible to the substrate, and therefore the reaction between compound (e) and the acid group proceeds more smoothly. There is no particular upper limit to the coordination number of the basic catalyst (B) in condition (1), for example, it can be 1.1 or 1.5.

[0195] The orbital energy (Hartley) value of condition (2) is preferably -0.250 or higher, more preferably -0.245 or higher, and even more preferably -0.240 or higher. The orbital energy (Hartley) value of condition (2) is preferably -0.140 or lower, more preferably -0.150 or lower, and even more preferably -0.160 or lower. If the orbital energy (Hartley) value is -0.250 or higher, sufficient catalytic effect can be obtained. If the orbital energy (Hartley) value is -0.140 or lower, the storage stability of the basic catalyst (B) is good.

[0196] Specific examples of catalysts satisfying conditions (1) and (2) include tris(2,6-dimethoxyphenyl)phosphine (coordination number: 0.967, orbital energy (Hartley): -0.169), tris(p-tolyl)phosphine (coordination number: 0.305, orbital energy (Hartley): -0.204), tricyclohexylphosphine (coordination number: 0.266, orbital energy (Hartley): -0.202), 4-dimethylaminopyridine (coordination number: 1.018, orbital energy (Hartley): -0.239), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) (coordination number: 0.936, orbital energy (Hartley): -0.221), and 1,5-diazabicyclo[4.3.0]-5-nonene (coordination number: 0.8). 36, orbital energy (Hartley): -0.224), 1,1,3,3-tetramethylguanidine (coordination number: 0.934, orbital energy (Hartley): -0.219), diisopropylamine (coordination number: 0.246, orbital energy (Hartley): -0.212), 1,4-diazabicyclo[2.2.2]octane (DABCO) (coordination number: 0.518, orbital energy (Hartley): -0.182), 4-aminopyridine (coordination number: 1.059, orbital energy (Hartley): -0.250), 4-dimethylaminopyridine (coordination number: 1.018, orbital energy (Hartley): -0.239), 4-diethylaminopyridine, 4-pyrrolylpyridine, 4-piperidinylpyridine and 2-methyl-4-dimethylaminopyridine. Preferably, it is selected from at least one of 4-dimethylaminopyridine, tricyclohexylphosphine, tris(2,6-dimethoxyphenyl)phosphine and tris(p-tolyl)phosphine.

[0197] The content of the alkaline catalyst (B) in the resin composition is 0.5 parts by mass or more, preferably 0.7 parts by mass or more, and more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the copolymer precursor (PA) and compound (e). The content of the alkaline catalyst (B) is 12 parts by mass or less, preferably 9.0 parts by mass or less, and more preferably 6.0 parts by mass or less, relative to 100 parts by mass of the copolymer precursor (PA) and compound (e). If the content of the alkaline catalyst (B) is 0.5 parts by mass or more, the reaction rate during the addition of compound (e) is high, which is preferred. If the content of the alkaline catalyst (B) is 12 parts by mass or less, even when the photosensitive resin composition or photosensitive coloring composition is manufactured by directly using the reaction solution used to manufacture the copolymer (A), the influence of the alkaline catalyst (B) during the curing of the photosensitive resin composition or photosensitive coloring composition can be suppressed.

[0198] <Solvent (C)>

[0199] Examples of solvents (C) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other ethylene glycol monoalkyl ethers, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether and other diethylene glycol monoalkyl ethers, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other propylene glycol monoalkyl ethers, dipropylene glycol monomethyl ether and other dipropylene glycol monoalkyl ethers, tripropylene glycol monoethyl ether and other tripropylene glycol monoalkyl ethers, 3-methoxy-1-butanol and other (poly)alkylene glycol monoalkyl ethers; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate and other carboxylic acid esters containing hydroxyl groups; and organic solvents containing hydroxyl groups such as diethylene glycol; as well as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Esters such as (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxylate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; and carboxylic amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc., which are organic solvents that do not contain hydroxyl groups. Solvent (C) can be used alone or in combination of two or more.

[0200] Among these solvents (C), from the viewpoint of ease of acquisition, cost and stability in the production of resists, compounds having an ether structure are preferred, and more preferably, at least one selected from propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether and 3-methoxy-1-butanol.

[0201] The content of solvent (C) in the resin composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the total components excluding solvent (C). The content of solvent (C) in the resin composition is preferably 900 parts by mass or less, more preferably 400 parts by mass or less, relative to 100 parts by mass of the total components excluding solvent (C). If the content of solvent (C) is 30 parts by mass or more, the viscosity of the resin composition can be within a suitable range.

[0202] <Method for manufacturing copolymer precursor (PA)>

[0203] The copolymer precursor (PA) can be manufactured by copolymerizing monomers containing terminal isocyanate groups (ma-1), hydroxyl groups (ma-2), acid groups (ma-3), and other monomers (ma-4) as needed. The proportions of structural units (a-1), (a-2), (a-3), and (a-4) in the copolymer precursor (PA) are equal to the proportions of each monomer (ma-1), monomer (ma-2), monomer (ma-3), and monomer (ma-4) in the total number of monomers used as raw materials for the copolymer precursor (PA).

[0204] There are no particular limitations on the proportions of the monomers used in the copolymerization reaction to form the copolymer precursor (PA). Preferably, monomer (ma-1) is 5 to 40 mol%, monomer (ma-2) is 1 to 35 mol%, and monomer (ma-3) is 5 to 70 mol%. More preferably, monomer (ma-1) is 10 to 30 mol%, monomer (ma-2) is 5 to 25 mol%, and monomer (ma-3) is 10 to 65 mol%. More preferably, monomer (ma-1) is 15 to 25 mol%, monomer (ma-2) is 10 to 20 mol%, and monomer (ma-3) is 15 to 60 mol%. When further using other monomers (ma-4), it is preferred that monomer (ma-1) is 5 to 40 mol%, monomer (ma-2) is 1 to 35 mol%, monomer (ma-3) is 5 to 70 mol%, and monomer (ma-4) is 1 to 70 mol%. More preferably, monomer (ma-1) is 10 to 30 mol%, monomer (ma-2) is 5 to 25 mol%, monomer (ma-3) is 10 to 65 mol%, and monomer (ma-4) is 5 to 60 mol%. More preferably, monomer (ma-1) is 15 to 25 mol%, monomer (ma-2) is 10 to 20 mol%, monomer (ma-3) is 15 to 60 mol%, and monomer (ma-4) is 10 to 50 mol%.

[0205] The copolymerization reaction can be carried out using free radical polymerization methods known in the art, with or without solvent. For example, the polymerization reaction can be carried out by dissolving the monomer in an organic solvent, adding a polymerization initiator to the solution, and then carrying out the polymerization reaction at 50–100°C for 1–20 hours. However, if the polymerization reaction is carried out at the temperature at which the isocyanate groups of the monomer (ma-1) containing the isocyanate groups dissociate, the isocyanate groups generated from the dissociation of the isocyanate groups may react with the acid groups of the monomer (ma-3) to form a gel. Therefore, polymerization is preferably carried out at a temperature lower than the dissociation temperature of the isocyanate groups, preferably at a temperature approximately 20–50°C lower than the dissociation temperature of the isocyanate groups.

[0206] As the solvent used in the copolymerization reaction, the same substance as solvent (C) described above can be used. Other examples include propylene glycol monoaryl ethers, 1,3-propanediol monoalkyl ethers, 1,3-butanediol monoalkyl ethers, 1,4-butanediol monoalkyl ethers, glycerol monoalkyl ethers, glycerol dialkyl ethers, methanol, ethanol, propanol, C5-6 cycloalkane diols, C5-6 cycloalkane diethanol, ethyl lactate, and diacetone alcohol, etc., which contain hydroxyl groups. Furthermore, "C5-6 cycloalkane" refers to cycloalkyl groups having 5-6 carbon atoms. From the viewpoint of preventing abnormal polymerization and ensuring stable polymerization, the copolymerization reaction is preferably carried out in the presence of an organic solvent containing hydroxyl groups. By conducting the copolymerization reaction in the presence of an organic solvent containing hydroxyl groups, even if the end-capped isocyanate groups dissociate to generate isocyanate groups, abnormal polymerization is prevented by the reaction of the isocyanate groups with the hydroxyl groups of the organic solvent containing hydroxyl groups. For the copolymer precursor (PA) obtained through this operation, it can be considered that a portion of the isocyanate-blocking end-capping agent has been replaced by an organic solvent containing hydroxyl groups. The solvent can be used alone or in combination of two or more.

[0207] There are no particular limitations on polymerization initiators that can be used for copolymerization reactions, and examples include azobisisobutyronitrile, azobisisovalerate, 2,2'-azobis(2,4-dimethylvalerate), benzoyl peroxide, and tert-butylperoxide-2-ethylhexanoate. Polymerization initiators can be used alone or in combination of two or more. The amount of polymerization initiator used relative to 100 parts by weight of the total monomer content is generally 0.5 to 20 parts by weight, preferably 1.0 to 18 parts by weight.

[0208] When manufacturing the copolymer precursor (PA), additives such as polymerization inhibitors, chain transfer agents, photosensitizers, fillers, and plasticizers may be used as needed, without impairing the effects of the present invention.

[0209] [Method for manufacturing the resin composition]

[0210] One embodiment of the method for manufacturing a resin composition includes a step (I) of preparing a resin composition, wherein the resin composition contains a copolymer precursor (PA), an olefinic unsaturated compound (e) having functional groups reactive with acid groups, a basic catalyst (B), and a solvent (C). The content of the basic catalyst (B) in the resin composition is 0.5 parts by mass or more, preferably 0.7 parts by mass or more, and more preferably 1.0 parts by mass or more, relative to a total of 100 parts by mass of the copolymer precursor (PA) and the compound (e). The content of the basic catalyst (B) in the resin composition is 12 parts by mass or less, preferably 9.0 parts by mass or less, and more preferably 6.0 parts by mass or less, relative to a total of 100 parts by mass of the copolymer precursor (PA) and the compound (e). The resin composition can be manufactured by mixing the copolymer precursor (PA), the olefinic unsaturated compound (e) having functional groups reactive with acid groups, the basic catalyst (B), and the solvent (C) using a known mixing apparatus.

[0211] When manufacturing the resin composition, the reaction solution used in manufacturing the copolymer precursor (PA) can be used directly as a raw material. In this case, the solvent contained in the reaction solution can be used as part or all of the solvent (C) contained in the resin composition.

[0212] When manufacturing the resin composition, the copolymer precursor (PA) obtained by separation from a reaction solution containing the copolymer precursor (PA) by a known method can be used as a raw material.

[0213] [Modified Resin Composition]

[0214] One embodiment of the modified resin composition contains a copolymer (A), an alkaline catalyst (B), and a solvent (C).

[0215] As an alkaline catalyst (B) and solvent (C), the same compounds and suitable ranges used in the resin composition can be applied.

[0216] <Copolymer (A)>

[0217] The copolymer (A) is a copolymer obtained by addition reaction of an olefinic unsaturated compound (e) having a functional group that is reactive with an acid group to a portion of the acid group of a structural unit (a-3) of a copolymer precursor (PA). The copolymer precursor (PA) contains a structural unit (a-1) having a terminal isocyanate group, a structural unit (a-2) having a hydroxyl group, and a structural unit (a-3) having an acid group. The copolymer precursor (PA) may contain other structural units (a-4) besides structural units (a-1) to (a-3) as needed.

[0218] The olefin unsaturated group equivalent of copolymer (A) is preferably 200 g / mol or more, more preferably 400 g / mol or more, and even more preferably 500 g / mol or more. The olefin unsaturated group equivalent of copolymer (A) is preferably 4,000 g / mol or less, more preferably 3,000 g / mol or less, even more preferably 2,000 g / mol or less, and particularly preferably 1,500 g / mol or less. If the olefin unsaturated group equivalent of copolymer (A) is 200 g / mol or more, the photosensitive resin composition or photosensitive coloring composition exhibits good storage stability. If the olefin unsaturated group equivalent of copolymer (A) is 4,000 g / mol or less, the cured photosensitive resin composition or photosensitive coloring composition exhibits even better solvent resistance.

[0219] The acid value of copolymer (A) is preferably 10 KOH mg / g or more, more preferably 20 KOH mg / g or more, and even more preferably 30 KOH mg / g or more. The acid value of copolymer (A) is preferably 300 KOH mg / g or less, more preferably 200 KOH mg / g or less, and even more preferably 100 KOH mg / g or less. If the acid value of copolymer (A) is 10 KOH mg / g or more, the developability of the photosensitive resin composition or photosensitive coloring composition is better. If the acid value of copolymer (A) is 300 KOH mg / g or less, the storage stability of the photosensitive resin composition or photosensitive coloring composition is good.

[0220] The isocyanate equivalent of the copolymer (A) is preferably 300 g / mol or more, more preferably 400 g / mol or more, and even more preferably 500 g / mol or more. The isocyanate equivalent of the copolymer (A) is preferably 6,000 g / mol or less, more preferably 5,000 g / mol or less, even more preferably 4,000 g / mol or less, and particularly preferably 2,000 g / mol or less. If the isocyanate equivalent of the copolymer (A) is 300 g / mol or more, the photosensitive resin composition or photosensitive coloring composition exhibits good storage stability. If the isocyanate equivalent of the copolymer (A) is 6,000 g / mol or less, the photosensitive resin composition or photosensitive coloring composition exhibits good low-temperature curability, and the cured product has better solvent resistance.

[0221] The hydroxyl equivalent of copolymer (A) is preferably 200 g / mol or more, more preferably 300 g / mol or more, and even more preferably 400 g / mol or more. The hydroxyl equivalent of copolymer (A) is preferably 10,000 g / mol or less, more preferably 6,000 g / mol or less, even more preferably 3,000 g / mol or less, and particularly preferably 1,000 g / mol or less. If the hydroxyl equivalent of copolymer (A) is 200 g / mol or more, the photosensitive resin composition or photosensitive coloring composition exhibits good storage stability. If the hydroxyl equivalent of copolymer (A) is 10,000 g / mol or less, the photosensitive resin composition or photosensitive coloring composition exhibits good low-temperature curability, and the cured product has better solvent resistance.

[0222] The weight-average molecular weight (Mw) of copolymer (A) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 4,000 or more. The weight-average molecular weight of copolymer (A) is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 15,000 or less. If the weight-average molecular weight of copolymer (A) is 1,000 or more, the photosensitive resin composition or photosensitive coloring composition exhibits good low-temperature curability. If the weight-average molecular weight of copolymer (A) is 50,000 or less, the photosensitive resin composition or photosensitive coloring composition exhibits good storage stability.

[0223] The molecular weight distribution (Mw / Mn) of copolymer (A) is preferably 1.3 or more, more preferably 1.5 or more, even more preferably 1.7 or more, and particularly preferably 1.9 or more. The molecular weight distribution (Mw / Mn) of copolymer (A) is preferably 5.0 or less, more preferably 4.5 or less, even more preferably 4.0 or less, and particularly preferably 3.5 or less. If the molecular weight distribution (Mw / Mn) of copolymer (A) is 1.3 or more, the manufacturing conditions during the synthesis of copolymer (A) are easier to control. If the molecular weight distribution (Mw / Mn) of copolymer (A) is 5.0 or less, the storage stability is good.

[0224] The preferred ranges for the structural units having terminal isocyanate groups (a-1), structural units having hydroxyl groups (a-2), structural units having acid groups (a-3), other structural units (a-4), and olefinic unsaturated compounds (e) having functional groups reactive with acid groups are the same as those described for the copolymer precursor (PA). The content of each structural unit is also the same as that described for the resin composition above.

[0225] The amount of compound (e) added to copolymer (A) relative to 100 moles of structural units of copolymer precursor (PA) is preferably 1 mole or more, more preferably 3 moles or more, and even more preferably 5 moles or more. The amount of compound (e) added to copolymer (A) relative to 100 moles of structural units of copolymer precursor (PA) is preferably 55 moles or less, more preferably 45 moles or less, and even more preferably 35 moles or less. If the amount of compound (e) added to copolymer (A) is 1 mole or more relative to 100 moles of structural units of copolymer precursor (PA), the photocurability of the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is good. If the amount of compound (e) added to copolymer (A) is 55 moles or less relative to 100 moles of structural units of copolymer precursor (PA), the content of acid groups in structural unit (a-3) can be sufficiently ensured, and the developability of the photosensitive resin composition or photosensitive coloring composition containing copolymer (A) is better.

[0226] The amount of compound (e) added to copolymer (A) relative to 100 moles of structural unit (a-3) of copolymer precursor (PA) is preferably 1 mole or more, more preferably 5 moles or more, and even more preferably 10 moles or more. The amount of compound (e) added to copolymer (A) relative to 100 moles of structural unit (a-3) of copolymer precursor (PA) is preferably 85 moles or less, more preferably 75 moles or less, and even more preferably 65 moles or less. If the amount of compound (e) added relative to 100 moles of structural unit (a-3) of copolymer precursor (PA) is 1 mole or more, the photocurability of the photosensitive resin composition or photosensitive coloring composition is good. If the amount of compound (e) added relative to 100 moles of structural unit (a-3) of copolymer precursor (PA) is 85 moles or less, the acid group content of structural unit (a-3) can be sufficiently ensured, and the developability of the photosensitive resin composition or photosensitive coloring composition is better.

[0227] The content of the alkaline catalyst (B) in the modified resin composition is 0.5 parts by mass or more, preferably 0.7 parts by mass or more, and more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the copolymer (A). The content of the alkaline catalyst (B) is 12 parts by mass or less, preferably 9.0 parts by mass or less, and more preferably 6.0 parts by mass or less, relative to 100 parts by mass of the copolymer (A). If the content of the alkaline catalyst (B) is 0.5 parts by mass or more, the reaction rate during the addition of compound (e) is high, which is preferred. If the content of the alkaline catalyst (B) is 12 parts by mass or less, even when the photosensitive resin composition or photosensitive coloring composition is manufactured by directly using the reaction solution used to manufacture the copolymer (A), the influence of the alkaline catalyst (B) during the curing of the photosensitive resin composition or photosensitive coloring composition can be suppressed.

[0228] The content of solvent (C) in the modified resin composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the total components excluding solvent (C). The content of solvent (C) in the modified resin composition is preferably 900 parts by mass or less, more preferably 400 parts by mass or less, relative to 100 parts by mass of the total components excluding solvent (C). If the content of solvent (C) is 30 parts by mass or more, the viscosity of the modified resin composition can be within an appropriate range.

[0229] <Method for manufacturing copolymer (A)>

[0230] The copolymer (A) can be manufactured, for example, by a method comprising the following steps: a step (I) of preparing a resin composition, wherein the resin composition contains a copolymer precursor (PA), an olefinic unsaturated compound (e) having a functional group that is reactive with an acid group, a basic catalyst (B) and a solvent (C), wherein the content of the basic catalyst (B) is 0.5 to 12 parts by mass relative to a total of 100 parts by mass of the copolymer precursor (PA) and the compound (e), wherein the copolymer precursor (PA) contains a structural unit (a-1) having a capped isocyanate group, a structural unit (a-2) having a hydroxyl group and a structural unit (a-3) having an acid group; and a step of adding the compound (e) to a portion of the acid group of the structural unit (a-3) of the copolymer precursor (PA) to obtain the copolymer (A).

[0231] As a method for adding compound (e) to a portion of the acid group of the structural unit (a-3) of the copolymer precursor (PA), a known addition reaction can be used. For example, after adding an inhibitor and a basic catalyst (B) to a reaction solution for a copolymerization reaction to obtain the copolymer precursor (PA), compound (e) is added, and the addition reaction is carried out at room temperature (23°C) to 120°C, preferably at 50 to 100°C, and more preferably at 50 to 80°C. The time for the addition reaction is, for example, 30 to 500 minutes or 30 to 300 minutes. The inhibitor is added to prevent side reactions of the introduced unsaturated group.

[0232] Specific examples of polymerization inhibitors include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, and butylated hydroxytoluene.

[0233] [Method for manufacturing the modified resin composition]

[0234] One embodiment of the method for manufacturing the modified resin composition includes a heating step (II) in which the resin composition obtained in step (I) is held at 50 to 120°C, preferably at 50 to 100°C, for 30 to 500 minutes. In the heating step (II), compound (e) undergoes acid addition with the acidic structural unit (a-3) of the copolymer precursor (PA), and the copolymer precursor (PA) is transformed into copolymer (A).

[0235] [Photosensitive resin composition]

[0236] One embodiment of the photosensitive resin composition contains a copolymer (A), an alkaline catalyst (B), a solvent (C), a reactive diluent (D), and a photopolymerization initiator (E). The photosensitive resin composition can be polymerized and cured by light irradiation to form a resin-cured film.

[0237] As copolymer (A), alkaline catalyst (B), and solvent (C), the same compounds and suitable ranges used in the modified resin composition can be applied.

[0238] The content of copolymer (A) in the photosensitive resin composition or photosensitive coloring composition, relative to the total of copolymer (A) and reactive diluent (D), is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. The content of copolymer (A) in the photosensitive resin composition or photosensitive coloring composition, relative to the total of copolymer (A) and reactive diluent (D), is preferably 90% by mass or less, more preferably 75% by mass or less, and even more preferably 60% by mass or less. When the content of copolymer (A) is within the above range, the viscosity of the photosensitive resin composition or photosensitive coloring composition becomes suitable for operation, and furthermore, the photocurability becomes better.

[0239] The content of the alkaline catalyst (B) in the photosensitive resin composition or photosensitive coloring composition is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and even more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the copolymer (A). The content of the alkaline catalyst (B) in the photosensitive resin composition or photosensitive coloring composition is preferably 12 parts by mass or less, more preferably 9.0 parts by mass or less, and even more preferably 6.0 parts by mass or less, relative to 100 parts by mass of the copolymer (A). If the content of the alkaline catalyst (B) in the photosensitive resin composition or photosensitive coloring composition is 12 parts by mass or less, the influence of the alkaline catalyst (B) during the curing of the photosensitive resin composition or photosensitive coloring composition can be suppressed.

[0240] The content of solvent (C) in the photosensitive resin composition or photosensitive coloring composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the total components excluding solvent (C). The content of solvent (C) in the photosensitive resin composition or photosensitive coloring composition is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, relative to 100 parts by mass of the total components excluding solvent (C). If the content of solvent (C) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or photosensitive coloring composition can be within an appropriate range. If the content of solvent (C) is 1,000 parts by mass or less, the solvent (C) can be easily removed when removing solvent (C) from the coating film formed by applying the photosensitive resin composition or photosensitive coloring composition to a substrate.

[0241] <Reactive diluent (D)>

[0242] The reactive diluent (D) is any low molecular weight compound having at least one olefin unsaturated group, and is not particularly limited. In this specification, a low molecular weight compound is defined as a compound with a molecular weight of less than 1,000. Examples of olefin unsaturated groups include vinyl, allyl, and (meth)acryloyloxy groups. From the viewpoint of improving curability, a multifunctional reactive diluent having multiple olefin unsaturated groups is preferred. Specific examples of reactive diluents (D) include aromatic vinyl compounds; aromatic allyl compounds such as diallyl phthalate and diallyl phenylphosphonate; vinyl carboxylic acid esters such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; and triallyl cyanurate.

[0243] Specific examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene.

[0244] Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0245] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0246] Among them, as a reactive diluent (D), in order to improve reactivity, a polyfunctional (meth)acrylate is preferred, and particularly preferred is at least one selected from dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0247] Reactive diluents (D) can be used alone or in combination of two or more.

[0248] The content of reactive diluent (D) in the photosensitive resin composition or photosensitive coloring composition, relative to the total of copolymer (A) and reactive diluent (D), is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more. The content of reactive diluent (D) in the photosensitive resin composition or photosensitive coloring composition, relative to the total of copolymer (A) and reactive diluent (D), is preferably 90% by mass or less, more preferably 75% by mass or less, and even more preferably 60% by mass or less. When the content of reactive diluent (D) is within the above range, the viscosity of the photosensitive resin composition or photosensitive coloring composition becomes suitable for operation, and furthermore, the photocurability becomes better.

[0249] <Photopolymerization Initiator (E)>

[0250] As a photopolymerization initiator (E), there are no particular limitations, but examples include, for instance, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,-1-(O-acetyl oxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, and other benzoin and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4'-(1-tert-butyldioxy-1-methylethyl)acetophenone, and other acetophenone compounds; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one; 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)butanone-1; anthraquinone compounds such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; xanthoxanone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzoyl dimethyl ketal; benzophenone compounds such as 4-(1-tert-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone; acylphosphine oxide photopolymerization initiators, etc. Photopolymerization initiators (E) can be used alone or in combination of two or more.

[0251] The content of photopolymerization initiator (E) in the photosensitive resin composition or photosensitive coloring composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the copolymer (A) and reactive diluent (D). The content of photopolymerization initiator (E) in the photosensitive resin composition or photosensitive coloring composition is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the copolymer (A) and reactive diluent (D). If the content of photopolymerization initiator (E) is 0.1 parts by mass or more, a photosensitive resin composition or photosensitive coloring composition with good photocurability can be obtained. If the content of photopolymerization initiator (E) is 30 parts by mass or less, adverse effects on the physical properties of the cured photosensitive resin composition or photosensitive coloring composition due to excessive photopolymerization initiator (E) can be prevented.

[0252] [Photosensitive coloring composition]

[0253] In addition to the above-mentioned photosensitive resin composition, the photosensitive coloring composition also contains a colorant (F).

[0254] <Coloring agent (F)>

[0255] Photosensitive coloring compositions containing colorant (F) can be used as materials for color filters.

[0256] There are no particular limitations on the colorant (F) as long as it is dissolved or dispersed in the solvent (C), for example, dyes, pigments, etc.

[0257] As dyes, considering factors such as solubility in solvents (C) and alkaline developing solutions, interaction with other components in the photosensitive coloring composition, and heat resistance, acidic dyes having acid groups such as carboxyl or sulfonyl groups, salts of acidic dyes and nitrogen compounds, and sulfonamide adducts of acidic dyes are preferred.

[0258] Examples of such dyes include 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; Solvent Blue 38, 44, 70; 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 their derivatives, etc. Among these, acid dyes of the azo, xanthones, anthraquinone, or phthalocyanine series are preferred. Dyes can be used alone or in combination of two or more.

[0259] Examples of pigments include CI pigments such as 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, and 214; CI pigments such as Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI pigments such as Red 9, 97, and 105. CI pigments include: 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265 (red pigments); CI pigments include: 15, 15:3, 15:4, 15:6, and 60 (blue pigments); CI pigments include: 1, 19, 23, 29, 32, 36, and 38 (purple pigments); CI pigments include: 7, 36, 58, and 59 (green pigments); CI pigments include: 23 and 25 (brown pigments); and CI pigments include: 1 and 7 (black pigments), carbon black, titanium black, and iron oxide pigments. Pigments can be used alone or in combination of two or more.

[0260] The colorant (F) can be appropriately determined, for example, based on the target coloring pattern, such as the color of the black matrix and pixels. The colorant (F) can be used alone or in combination of two or more substances. When using two or more substances as colorants (F), dyes and pigments can be used in combination.

[0261] When using pigments as colorants (F), from the viewpoint of improving the dispersibility of the pigments, known dispersants can be mixed into the photosensitive coloring composition. As a dispersant, a polymeric dispersant with excellent dispersion stability over time is preferred. Examples of polymeric dispersants include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitol aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As a polymeric dispersant, substances commercially available under trade names such as EFKA (EFKA CHEMICALS BV), Disperbyk (BICKKEMI), Disperon (Kusumoto Chemical Co., Ltd.), and SOLSPERSE (Robberies Ltd.) can be used. The content of the dispersant can be appropriately set according to the type and amount of pigment used as a colorant (F).

[0262] The content of colorant (F) in the photosensitive coloring composition is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the copolymer (A) and reactive diluent (D). The content of colorant (F) in the photosensitive coloring composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to 100 parts by mass of the copolymer (A) and reactive diluent (D). If the content of colorant (F) is 0.1 parts by mass or more, the effect of containing colorant (F) becomes significant, and a photosensitive coloring composition suitable as a coloring pattern for a color filter can be obtained. If the content of colorant (F) is 80 parts by mass or less, the colorant (F) does not hinder the curability of the photosensitive coloring composition, and a photosensitive coloring composition with good low-temperature curability can be obtained.

[0263] <Other Ingredients>

[0264] In one embodiment of the photosensitive resin composition or photosensitive coloring composition, in addition to the copolymer (A), basic catalyst (B), solvent (C), reactive diluent (D), photopolymerization initiator (E), and colorant (F) as needed, known additives such as coupling agents, leveling agents, and polymerization inhibitors may be mixed in as needed. The amount of additives mixed is not particularly limited as long as it does not impair the effects of the present invention.

[0265] <Method for manufacturing photosensitive resin compositions and photosensitive coloring compositions>

[0266] One embodiment of the photosensitive resin composition can be manufactured by mixing a copolymer (A), an alkaline catalyst (B), a solvent (C), a reactive diluent (D), and a photopolymerization initiator (E) using a known mixing apparatus. One embodiment of the photosensitive coloring composition can be manufactured by mixing a copolymer (A), an alkaline catalyst (B), a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F) using a known mixing apparatus.

[0267] When manufacturing a photosensitive resin composition or a photosensitive coloring composition, the reaction solution used in manufacturing the copolymer (A) can be used directly as a raw material. In this case, the solvent contained in the reaction solution can be used as part or all of the solvent (C) contained in the photosensitive resin composition or the photosensitive coloring composition.

[0268] When manufacturing a photosensitive resin composition or a photosensitive coloring composition, the copolymer (A) obtained by separation from a reaction solution containing the copolymer (A) by a known method can be used as a raw material.

[0269] The photosensitive resin composition or photosensitive coloring composition contains a copolymer (A) in which olefinic unsaturated groups are introduced through the addition of compound (e), a reactive diluent (D), and a photopolymerization initiator (E). Therefore, when exposed to light, the reactive diluent (D) polymerizes together with the olefinic unsaturated groups contained in the copolymer (A), exhibiting good photocurability.

[0270] Furthermore, the photosensitive resin composition or photosensitive coloring composition has good low-temperature curability because it contains a copolymer (A) containing structural units (a-1) with capped isocyanate groups and structural units (a-2) with hydroxyl groups.

[0271] Based on these conditions, when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, curing can be performed at a lower temperature compared to when using conventional resin compositions. Therefore, when the photosensitive resin composition or photosensitive coloring composition is baked after exposure of a coating film formed on a substrate, even at a low baking temperature, the crosslinking reaction proceeds sufficiently, thus forming a cured product with excellent solvent resistance.

[0272] Therefore, when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, the energy required for heating during curing is minimal. Furthermore, by using a photosensitive resin composition or a photosensitive coloring composition, a cured product can be formed on substrates with low heat resistance, such as resin substrates, without hindering the substrate. Moreover, regarding the photosensitive coloring composition, even when a substance with low heat resistance is used as the colorant (F), a cured product that exhibits the inherent properties of the colorant (F) can be formed.

[0273] Because photosensitive coloring compositions can produce cured products with excellent solvent resistance even at low baking temperatures, the colorant (F) is less likely to dissolve. Therefore, it is possible to have a high content of colorant (F) in the photosensitive coloring composition. When used as a material for coloring patterns, such as in color filters, photosensitive coloring compositions with a high colorant (F) content can form color filters with excellent color reproduction.

[0274] The copolymer (A) contained in the photosensitive resin composition or photosensitive coloring composition has good alkaline developability because it has structural units (a-3) with acid groups. Due to its excellent alkaline developability, such a photosensitive resin composition or photosensitive coloring composition can, for example, form a coated film by coating it onto a substrate, expose it via a photomask corresponding to a predetermined pattern shape, develop the unexposed portion with an alkaline aqueous solution, and then bake it at a sufficiently low temperature, thereby forming a cured product with excellent solvent resistance and a predetermined pattern shape.

[0275] Photosensitive resin compositions and photosensitive coloring compositions can be suitable for use as materials for color filters.

[0276] Based on these circumstances, photosensitive resin compositions and photosensitive coloring compositions are extremely useful as materials for forming components of image display elements such as color filters, pixels, black matrices, color filter protective films, light spacers, protrusions for liquid crystal alignment, microlenses, and insulating films for touch panels.

[0277] [Resin-cured film]

[0278] One embodiment of the resin-cured film is a cured product of a photosensitive resin composition or a photosensitive coloring composition.

[0279] Resin-cured films can be manufactured, for example, by coating a substrate with a photosensitive resin composition or a photosensitive coloring composition, allowing the solvent (C) to evaporate and be removed to form a coated film, exposing the coated film to light curing it, and then baking it.

[0280] When forming a resin-cured film with a predetermined pattern shape, the following method can be used, for example. Specifically, a photosensitive resin composition or a photosensitive coloring composition is coated onto a substrate, and the solvent (C) is evaporated and removed to form a coated film. Next, the coated film is exposed to a photomask with a predetermined pattern shape to photocur the exposed portions. Then, the unexposed portions of the coated film are developed with an alkaline aqueous solution. Finally, the developed coated film is baked to form a resin-cured film with a predetermined pattern shape.

[0281] Known methods can be used for coating methods, exposure methods, and development methods of the photosensitive resin composition or photosensitive coloring composition used in manufacturing resin-cured films.

[0282] The baking conditions during the manufacture of the resin-cured film can be appropriately determined based on the composition of the photosensitive resin composition or photosensitive coloring composition, the film thickness of the coating, the material of the substrate, etc. The baking process can be carried out at temperatures, for example, 70°C to 250°C. If the baking temperature is above 70°C, the terminal isocyanate groups in the structural unit (a-1) containing the copolymer (A) in the photosensitive resin composition or photosensitive coloring composition are sufficiently dissociated. This generates isocyanate groups, which undergo a crosslinking reaction with the hydroxyl groups in the structural unit (a-2). In the case where the structural unit (a-1) has an alkyloxycarbonyl group, crosslinking is formed through transesterification of the alkyl group of the alkyloxycarbonyl group with the hydroxyl group in the structural unit (a-2). As a result, good curing degree is obtained, and a cured product with excellent solvent resistance is obtained. In the case where the structural unit (a-1) has an alkyloxycarbonyl group, both deblocking and transesterification reactions can occur, but by adjusting the baking temperature, either reaction can be preferentially carried out. The baking temperature is preferably 75°C or higher, more preferably 80°C or higher. A baking temperature of 250°C or lower is preferred as it is a condition that materials with low heat resistance can tolerate, and can suppress discoloration of the photosensitive resin composition or photosensitive coloring composition. The photosensitive resin composition and photosensitive coloring composition have good low-temperature curing properties. Therefore, depending on the heat resistance of the substrate forming the resin-cured film, the baking temperature can be 160°C or lower; for example, when using a resin substrate as the substrate, it can be 150°C or lower, 120°C or lower, or 100°C or lower.

[0283] The baking process performed during the manufacture of the resin-cured film can be, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined according to the composition of the photosensitive resin composition or the photosensitive coloring composition, the baking temperature, the film thickness of the coating film, etc.

[0284] The resin-cured film is a cured product of a photosensitive resin composition or a photosensitive coloring composition. Therefore, the resin-cured film can be manufactured using a baking process at a low temperature and exhibits excellent solvent resistance.

[0285] Resin-cured films are preferably used as components of transparent films, protective films, insulating films, outer coatings, light spacers, black matrices, black columnar spacers, and color filters.

[0286] [Color Filter]

[0287] One embodiment of the color filter includes a color pattern as a cured product of a photosensitive coloring composition. Preferably, the color filter includes a color pattern as a cured product of the photosensitive coloring composition, wherein, relative to the total amount of copolymer (A) and reactive diluent (D), the content of copolymer (A) is 10-90% by mass, the content of reactive diluent (D) is 10-90% by mass, the content of reactive diluent (D) is 10-90% by mass, the content of photopolymerization initiator (E) is 0.1-30% by mass, the content of colorant (F) is 0.1-80% by mass, and the content of solvent (C) is 30-1,000% by mass relative to the total amount of components other than solvent (C).

[0288] A color filter may include, for example, a substrate, RGB pixels formed on the substrate, a black matrix formed at the boundaries of each pixel, and a protective film formed on the pixels and the black matrix.

[0289] In the color filter, the pixels and black matrix form a color pattern that is a cured product of the aforementioned photosensitive coloring composition. In the color filter, the components other than the materials of the pixels and black matrix can employ known configurations.

[0290] There are no particular limitations on the substrate used for color filters. Depending on the application, glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, etc., can be used appropriately.

[0291] <Method for Manufacturing Color Filters>

[0292] Next, the manufacturing method of an example color filter will be described. First, a color pattern is formed on a substrate. Specifically, a color pattern that forms a black matrix at the boundaries of each pixel and a color pattern that forms RGB pixels are sequentially formed on the substrate using the method shown below.

[0293] The colored pattern is formed by photolithography. Specifically, a photosensitive coloring composition is coated onto a substrate to form a coating film. Then, the coating film is exposed to a photomask with a predetermined pattern shape to photocur the exposed portions. Next, the unexposed portions of the coating film are developed with an alkaline aqueous solution. Then, the developed coating film is baked to form a colored pattern with a predetermined pattern shape.

[0294] There are no particular limitations on the coating method of the photosensitive coloring composition. Known methods such as screen printing, roller coating, curtain coating, spraying, and spin coating can be used.

[0295] Furthermore, after coating the substrate with a photosensitive coloring composition, the substrate can be heated using a circulating oven, infrared heater, hot plate, or other heating method as needed, thereby causing the solvent (C) contained in the coating film to evaporate and be removed. There are no particular limitations on the conditions for heating the substrate to remove the solvent (C), as long as they are appropriately set according to the substrate material, the composition of the photosensitive coloring composition, and the thickness of the coating film. For example, the substrate can be heated at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0296] Next, the coated film formed in this way is partially exposed to active energy rays such as ultraviolet light or excimer laser light through a negative photomask, and the exposed portion is photocured. The amount of active energy rays irradiating the coated film can be appropriately selected according to the composition of the photosensitive coloring composition, for example, it can be 30 to 2000 mJ / cm. 2 There are no particular limitations on the light source used for exposure; low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc., can be used.

[0297] The alkaline aqueous solution used for developing the coated film is not particularly limited. It can be aqueous solutions of inorganic alkaline compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and their salts, such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, or p-toluenesulfonates; and aqueous solutions of p-phenylenediamine compounds and their salts. Additionally, additives such as defoamers and surfactants can be added to the alkaline aqueous solution as needed.

[0298] Preferably, after developing the coated film using the above-mentioned alkaline aqueous solution, the coated film is washed with water and then dried.

[0299] The baking conditions during the manufacture of the color filter can be appropriately determined based on the composition of the photosensitive coloring composition, the film thickness of the coating film, and the material of the substrate. The baking temperature can be, for example, 70°C to 210°C. If the baking temperature is 70°C or higher, good curability can be obtained, resulting in a cured product with excellent solvent resistance. The baking temperature is preferably 75°C or higher, more preferably 80°C or higher. If the baking temperature is 210°C or lower, materials with low heat resistance, such as substrates, can be used as the material for the color filter, which is therefore preferred.

[0300] When forming a color pattern for a color filter using conventional photosensitive coloring compositions, the solvent resistance of the color pattern is insufficient if the baking temperature is below 200°C. In contrast, the photosensitive coloring composition of one embodiment has excellent low-temperature curing properties, thus ensuring the solvent resistance of the color pattern, while allowing for a lower baking temperature compared to conventional photosensitive coloring compositions. Specifically, depending on the heat resistance of the substrate forming the resin-cured film, the baking temperature can be below 160°C; for example, when forming the color pattern using a resin substrate as the substrate, it can be below 150°C, below 120°C, or below 100°C.

[0301] The baking process performed during the manufacture of the color filter can be, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined according to the composition of the photosensitive coloring composition, the baking temperature, the film thickness of the coating film, etc.

[0302] The photosensitive coloring composition exhibits good photocurability and low-temperature curability. Therefore, when forming a coloring pattern using the photosensitive coloring composition of one embodiment, the baking time can be shortened and the color filter can be formed more efficiently if the baking temperature is the same as that used when forming a coloring pattern using a conventional photosensitive coloring composition.

[0303] After forming RGB pixel-by-pixel RGB color patterns and black matrix-by-black ...

[0304] The method for manufacturing the protective film is not particularly limited. It can be formed using the photosensitive resin composition of one embodiment, or using known materials and known methods.

[0305] The color filter is obtained through the above process.

[0306] The color filter has a color pattern that is a cured product of the aforementioned photosensitive coloring composition. Therefore, the color pattern in the color filter can be formed by baking at a low temperature. Thus, the energy required for the baking process can be reduced.

[0307] Furthermore, the colorant (F) contained in the photosensitive coloring composition used as the material for the color filter can be a substance with low heat resistance. Therefore, a wider selection of colorants (F) can be used. Thus, for example, it is possible to form a color filter having a coloring pattern that contains a colorant (F) with low heat resistance and exhibits the inherent properties of the colorant (F).

[0308] Furthermore, the color patterns in the color filter can be formed on substrates with low heat resistance, such as resin substrates, without hindering the substrate. Therefore, a wider range of substrate options can be used. Specifically, for example, since the color filter can be formed on substrates with low heat resistance, such as resin substrates, the flexibility of the display can be achieved. In addition, the color patterns in the color filter exhibit excellent solvent resistance, resulting in minimal color variation.

[0309] Here, an example is given of a case in which a photosensitive coloring composition containing a photopolymerization initiator (E) is used to cure the photosensitive coloring composition to create a color pattern. However, for example, a photosensitive coloring composition containing a curing accelerator and a known epoxy resin instead of the photopolymerization initiator (E) in the photosensitive coloring composition can be used to form a color pattern as a cured product of the photosensitive coloring composition containing a copolymer (A) by inkjet coating onto a substrate and then heating.

[0310] [Image display element]

[0311] One embodiment of the image display element includes a color filter. In the image display element, known configurations can be used as components other than the color filter. Specific examples of image display elements include solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements, and CMOS elements.

[0312] The components of an image display element, excluding the color filter, can be manufactured using known methods. For example, when manufacturing a liquid crystal display element as an image display element, it can be manufactured using the method described below. First, a color filter is formed on a substrate using the method described above. Then, electrodes, spacers, etc., are sequentially formed on the substrate having the color filter. Next, electrodes, etc., are formed on another substrate, which is then arranged opposite to and bonded to the substrate having the color filter. Finally, a predetermined amount of liquid crystal is injected between the opposing substrates, and sealing is performed.

[0313] Image display elements exhibit minimal color variation due to their color filters, which possess excellent solvent resistance.

[0314] Example

[0315] The present invention will be further described in detail below through examples and comparative examples, but the present invention is not limited to the following examples.

[0316] The following shows an example of the synthesis of copolymer (A).

[0317] [Example 1 (Synthesis Example 1)]

[0318] 113g of propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) as solvent (C) was added to a flask equipped with a stirring device, dropping funnel, condenser, thermometer and gas inlet tube. The mixture was stirred while being purged with nitrogen and heated to 78°C.

[0319] Next, 54 g (18 mol%) of 2-isocyanate-ethyl acrylate as monomer (ma-1) reacted with diethyl malonate to produce the product; 18 g (14 mol%) of 2-hydroxyethyl methacrylate as monomer (ma-2); 43 g (50 mol%) of methacrylic acid as monomer (ma-3); 33 g (18 mol%) of 2-ethylhexyl acrylate as monomer (ma-4); and 54 g (relative to the above monomers) of solvent (C) were used as solvent. A monomer solution was prepared by mixing propylene glycol monomethyl ether (36 parts by mass out of a total of 100 parts by mass of monomer components), 69 g (46 parts by mass out of a total of 100 parts by mass of propylene glycol monomethyl ether acetate) as solvent (C), and 18 g (12.1 parts by mass out of a total of 100 parts by mass of 2,2'-azobis(2,4-dimethylpentanonitrile) (Fuji Film & Television Co., Ltd.) as polymerization initiator.

[0320] The entire volume of the prepared monomer solution was added dropwise over 1 hour using a dropping funnel to a flask under a nitrogen atmosphere and atmospheric pressure to the solvent (C). After the addition was complete, the solution in the flask was stirred while a polymerization reaction was carried out at 78°C for 3 hours to obtain a liquid containing the copolymer precursor (PA) and solvent (C). The weight-average molecular weight, molecular weight distribution, hydroxyl equivalent, and acid value of the copolymer precursor (PA) were determined using the above method and are recorded in Table 1. The end-capped isocyanate equivalent of the copolymer precursor (PA) was calculated and is recorded in Table 1.

[0321] A resin composition was prepared by adding 0.6 g (0.3 parts by mass relative to 100 parts by mass of the monomer component of the copolymer precursor (PA) and the solvent (C) in a flask under a nitrogen atmosphere and at atmospheric pressure. The resin composition consisted of a copolymer precursor (PA) and a solvent (C). Additionally, 0.6 g (3.0 parts by mass relative to 100 parts by mass of the monomer component of the copolymer precursor (PA) and the compound (e)) of hydroquinone monomethyl ether (MEHQ) was added as an inhibitor; 5.8 g (3.0 parts by mass relative to 100 parts by mass of the monomer component of the copolymer precursor (PA) and the compound (e)) of 4-dimethylaminopyridine (DMAP) (Kanto Chemical Co., Ltd.) was added as a basic catalyst (B); and 43 g (30 mol relative to 100 mol of the monomer component of the copolymer precursor (PA)) of glycidyl methacrylate was added as compound (e). The resin composition was stirred and kept at 78°C for 300 minutes to obtain a reaction solution containing copolymer (A) and solvent (C). The weight-average molecular weight, molecular weight distribution, hydroxyl equivalent, and acid value of copolymer (A) were determined using the methods described above and are recorded in Table 1. The equivalent of the terminal isocyanate groups and the equivalent of the olefin unsaturated groups in copolymer (A) were calculated and recorded in Table 1. Regarding the addition reaction rate of compound (e), the amount of carboxyl group reduction (in moles) was calculated by taking the difference between the acid value of the reaction solution when compound (e) was added and the acid value of the reaction solution after the reaction. The ratio of the reduction to the number of moles of compound (e) added was determined as the addition reaction rate and is recorded in Table 1. The equivalent of the olefin unsaturated groups in copolymer (A) was calculated from the amount of raw material added and the addition reaction rate of compound (e).

[0322] In the reaction solution containing copolymer (A) and solvent (C) obtained by such operation, propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) as solvent (C) was added in such a way that the components other than solvent were 35% by mass, and a modified resin composition containing copolymer (A) of Synthetic Example 1 was obtained.

[0323] [Examples 2-27 (Synthetic Examples 2-27), Comparative Examples 2, 3 and 5-7 (Comparative Synthetic Examples 2, 3 and 5-7)]

[0324] Using the monomers, compounds (e), solvents (C), polymerization initiators, polymerization inhibitors, and basic catalysts (B) and their mixing amounts as described in Table 1, except that the same procedure was followed as in Synthesis Example 1, modified resin compositions comprising copolymers (A) of Synthesis Examples 2-27 and modified resin compositions comprising copolymers (cA) of Comparative Synthesis Examples 2, 3, and 5-7 were obtained. The weight-average molecular weight, molecular weight distribution, hydroxyl equivalent, and acid value of the copolymer precursors (PA) of Synthesis Examples 2-27 and the copolymer precursors (cPA) of Comparative Synthesis Examples 2, 3, and 5-7 were determined by the above method and are recorded in Table 1. The end-capped isocyanate equivalents of the copolymer precursors (PA) of Synthesis Examples 2-27 and the copolymer precursors (cPA) of Comparative Synthesis Examples 2, 3, and 5-7 were calculated and are recorded in Table 1. The weight-average molecular weight, molecular weight distribution, hydroxyl equivalent, and acid value of the copolymers (A) of Synthetic Examples 2-27 and the copolymers (cA) of Comparative Examples 2, 3, and 5-7 were determined using the above method and are recorded in Table 1. The end-capped isocyanate equivalent, olefin unsaturated group equivalent, and addition reaction rate of the copolymers (A) of Synthetic Examples 2-27 and the copolymers (cA) of Comparative Examples 2, 3, and 5-7 were calculated and are recorded in Table 1.

[0325] [Compare Examples 1 and 4 (Compare Composite Examples 1 and 4)]

[0326] Using the monomers, solvent (C), and polymerization initiator and their mixing amounts as listed in Table 1, liquids containing copolymers (cA) of Comparative Synthetic Examples 1 and 4 were obtained by operating in the same manner as obtaining the liquid containing copolymer precursor (PA) and solvent (C) of Synthetic Example 1. Furthermore, the concentration was adjusted by adding propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) as solvent (C) at a concentration of 35% by mass, excluding the solvent. The weight-average molecular weight, molecular weight distribution, hydroxyl equivalent, and acid value of the copolymers (cA) of Comparative Synthetic Examples 1 and 4 were determined by the above method and are recorded in Table 1. The end-capped isocyanate equivalents of the copolymers (cA) of Comparative Synthetic Examples 1 and 4 were calculated and are recorded in Table 1.

[0327] [Table 1-1]

[0328] [Table 1-2]

[0329] [Table 1-3]

[0330] [Table 1-4]

[0331] The following substances were used as the compounds listed in Table 1.

[0332] AOI-DEM: The product of the reaction between CARENZ (trademark) AOI (2-isocyanate ethyl acrylate, Rezonack Co., Ltd.) and diethyl malonate (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester)

[0333] MOI-DEM: A product of the reaction between CARENZ (trademark) MOI (2-isocyanate-ethyl methacrylate, Rezonack Co., Ltd.) and diethyl malonate (malonate-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester).

[0334] AOI-DMM: CARENZ (trademark) AOI (2-isocyanate ethyl acrylate, Rezonack Co., Ltd.) reacts with dimethyl malonate to form (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester).

[0335] AOI-BP: CARENZ (trademark) AOI (2-isocyanate-based ethyl acrylate, Rezonack Co., Ltd.) reacts with 3,5-dimethylpyrazole to form (2-[(3,5-dimethylpyrazole)carbonylamino]ethyl acrylate).

[0336] AOI-AM: CARENZ (trademark) AOI (2-isocyanate ethyl acrylate, Rezonack Co., Ltd.) reacts with methyl 4-hydroxybenzoate to form (4-[[[[2-[(1-oxo-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]-methyl benzoate)

[0337] HEMA: 2-hydroxyethyl methacrylate (Nippon Shokubai Co., Ltd.)

[0338] 4HBA: 4-Hydroxybutyl acrylate (Tokyo Chemical Industry Co., Ltd.)

[0339] 2-HPMA: 2-Hydroxypropyl Methacrylate (Tokyo Chemical Industry Co., Ltd.)

[0340] GLM: 2,3-Dihydroxypropyl Methacrylate (Nippon Oil Co., Ltd.)

[0341] MAA: methacrylic acid (Kurara Co., Ltd.)

[0342] AA: Acrylic acid (Tokyo Chemical Industry Co., Ltd.)

[0343] HOMS(N): 2-Methacryloxyethylsuccinic acid (Kyoeisha Chemical Co., Ltd.)

[0344] HOAMS(N): 2-Acryloyloxyethylsuccinic acid (Kyoeisha Chemical Co., Ltd.)

[0345] 2EHA: 2-Ethylhexyl acrylate (Toa Synthetic Co., Ltd.)

[0346] BZMA: Benzyl methacrylate (Tokyo Chemical Industry Co., Ltd.)

[0347] MMA: Methyl methacrylate (Tokyo Chemical Industry Co., Ltd.)

[0348] SM: Styrene (Tokyo Chemical Industry Co., Ltd.)

[0349] TCDMA: Tricyclodecyl methacrylate (Rezonac Co., Ltd.)

[0350] GMA: Glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.)

[0351] 4HBAGE: 4-Hydroxybutyl acrylate glycidyl ether (Mitsubishi Microelectronics Co., Ltd.)

[0352] TTA15: 3,4-Epoxycyclohexylmethyl methacrylate (Sankemica Co., Ltd.)

[0353] TTA16: 3,4-Epoxycyclohexylmethyl acrylate (Sankemica Co., Ltd.)

[0354] PGMEA: Propylene glycol methyl ether acetate (Kuraro Co., Ltd.)

[0355] PGME: Propylene Glycol Monomethyl Ether (Kurare Co., Ltd.)

[0356] MB: 3-Methoxy-1-Butanol (Tokyo Chemical Industry Co., Ltd.)

[0357] V-65B: 2,2'-Azobis(2,4-dimethylvaleronitrile) (Fuji Fiber and Kozumi Co., Ltd.)

[0358] MEHQ: Hydroquinone monomethyl ether (Seiko Chemical Co., Ltd.)

[0359] DMAP: 4-Dimethylaminopyridine (Kanto Chemical Co., Ltd.)

[0360] DMPP: Tris(2,6-dimethoxyphenyl)phosphine (Hokuko Sangyo Co., Ltd.)

[0361] TPTP: Tri(p-Tolyl)phosphine (Hokuko Sangyo Co., Ltd.)

[0362] TCHP: Tricyclohexylphosphine (Hokuko Sangyo Co., Ltd.)

[0363] (Maintain stability)

[0364] The storage stability of the modified resin compositions of Examples 1-27, the modified resin compositions of Comparative Examples 2, 3, and 6, and the liquids containing copolymers (cA) of Comparative Examples 1 and 4 were evaluated according to the following method. 10 g of each of the modified resin compositions of Examples 1-27, the modified resin compositions of Comparative Examples 2, 3, and 6, and the liquids containing copolymers (cA) of Comparative Examples 1 and 4, with a composition other than the solvent of 35% by mass, was measured in a 20 mL glass container, and the viscosity was determined. Viscosity was measured within 24 hours of synthesis and was determined as the viscosity before storage. Viscosity was measured using an E-type viscometer (RE-80, rotor 1°34'×R24, Toki Sangyo Co., Ltd.) at 25°C and 20 rpm. Each sample was then stored for 3 months in a thermostat maintained at 12°C. The viscosity was then measured again using the same method as described above to determine the viscosity after storage. Using the viscosity before and after storage, the thickening rate was calculated using the following formula and evaluated against the criteria shown below. The results are shown in Table 1.

[0365] Thickening rate (%) = (([viscosity after storage] - [viscosity before storage]) / [viscosity before storage]) × 100

[0366] (Evaluation criteria for thickening rate)

[0367] Excellent: Thickening rate less than 10%

[0368] Good: Thickening rate 10-20%

[0369] Undesirable: Thickening rate exceeds 20%.

[0370] [Examples 28-54, Comparative Examples 8-12]

[0371] The copolymers (A) of Synthetic Examples 1-27 shown in Table 2, or the copolymers (cA) of Comparative Synthetic Examples 1-4 or 6, alkaline catalyst (B), dipentaerythritol pentaacrylate (Toa Synthetic Co., Ltd.) as reactive diluent (D), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,-1-(O-acetyloxime) (Chiba Japan Co., Ltd.) as photopolymerization initiator (E), a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether as solvent (338 parts by mass and 257 parts by mass, respectively), and Valifast Blue 2620 (phthalocyanine dye, Original Chemical Industries Co., Ltd.) as colorant (F) were mixed in the proportions shown in Table 2 to prepare the photosensitive coloring compositions of Examples 28-54 and Comparative Examples 8-12. The amounts of copolymer (A) or (cA) shown in Table 2 do not include the amount of solvent. The amounts of solvent (C) shown in Table 2 are the sum of the amount of solvent contained in the modified resin composition obtained in the examples or comparative examples (for comparative synthesis examples 1 and 4, which are liquids containing copolymer (cA)) and the amount of solvent added when preparing the photosensitive coloring composition.

[0372] [Table 2-1]

[0373] [Table 2-2]

[0374] [Evaluation of solvent resistance]

[0375] Solvent resistance was evaluated using residual film yield.

[0376] (residual film rate)

[0377] The photosensitive coloring compositions of Examples 28-54 and Comparative Examples 8-12 were each coated onto a 5cm x 5cm square alkali-free glass substrate using spin coating to form a coating film with a thickness of 2.5μm after exposure. The coating film was then heated at 100°C for 3 minutes to evaporate and remove the solvent (C).

[0378] Next, the coated film is subjected to an energy radiation dose of 100 mJ / cm. 2 The coated film was exposed to ultraviolet light at a wavelength of 365 nm, causing photocuring. Then, it was baked at 85°C for 30 minutes to cure the coating, thus creating a cured film. The thickness of the cured film was measured using a profilometer. This thickness is designated as X.

[0379] The prepared cured film was then immersed in 20g of propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 15 minutes. After vacuum drying at 40°C for 30 minutes, the thickness of the coated film was measured using a step meter. This thickness is defined as Y.

[0380] The solvent resistance of the cured film was evaluated by calculating the residual film rate as the ratio of the thickness Y of the cured film after PGMEA impregnation to the thickness X of the cured film before PGMEA impregnation. That is, the closer the residual film rate is to 100%, the better the solvent resistance of the cured film. As an evaluation criterion, a residual film rate of 70% or higher was set as the passing grade. The residual film rates of the cured films are shown in Table 2.

[0381] Residual film rate = (Y / X) × 100 (%)

[0382] As shown in Table 2, the residual film rate (%) of the cured films of the photosensitive coloring compositions of Examples 28-54 after PGMEA impregnation is more than 70%, and the solvent resistance is good even at low temperatures such as 85°C during baking.

[0383] [Evaluation of radioactivity]

[0384] The developability was evaluated by the solubility and adhesion of the cured film.

[0385] (Solubility)

[0386] The photosensitive coloring compositions of Examples 28-54 and Comparative Examples 8-12 were coated onto 5 cm square alkali-free glass substrates using a spin coating method to achieve a thickness of 1.5 μm after exposure (coating process). The glass substrates coated with the photosensitive coloring compositions were heated at 100°C for 3 minutes to evaporate the solvent and dry the coating film (pre-baking process).

[0387] Next, an ultra-high pressure mercury lamp was used to achieve 100 mJ / cm². 2 Light was irradiated onto the surface of the dried coated film through a photomask (exposure process). The photomask was positioned 100 μm away from the coated film during the exposure process. A photomask with a line and gap pattern of 3–100 μm width was used. Next, Semiclean DL-A10 developer (Yokohama Yushi Kogyo Co., Ltd.) (300-fold dilution) was sprayed onto the surface of the coated film for 60 seconds at 23°C and 0.1 MPa to remove unexposed areas (development process). The dissolution morphology of the coated film after spraying the developer was observed, and the solubility was evaluated using the following criteria. The results are shown in Table 2.

[0388] 1. No residue was found in the unexposed areas, no powder was observed in the developer, and the pattern shape was good.

[0389] 2: No residue was observed in the unexposed areas, but powder was observed in the developer; the pattern shape was relatively good.

[0390] 3: Residue remains in the unexposed areas, resulting in missing patterns or shapes.

[0391] 4: The film peels off in the exposure section, leaving no pattern residue.

[0392] (Seamless fit)

[0393] A colored pattern was obtained by placing the coated glass substrate in a dryer at 100°C for 30 minutes after the developing process to thermally cure the coating (post-baking process). The colored pattern obtained by this operation was observed under a microscope, and the adhesion was evaluated by the minimum developable linewidth, i.e., the minimum developable size (μm). The results are shown in Table 2.

Claims

1. A resin composition comprising: a copolymer precursor PA; an ethylenically unsaturated compound e having a functional group reactive with an acid group; and a solvent C, the copolymer precursor PA comprising: a structural unit a-1 having a blocked isocyanate group; a structural unit a-2 having a hydroxyl group; and a structural unit a-3 having an acid group, the basic catalyst B being contained in an amount of 0.5 to 12 parts by mass per 100 parts by mass of the total of the copolymer precursor PA and the ethylenically unsaturated compound e.

2. A modified resin composition comprising: a copolymer A; a basic catalyst B; and a solvent C, the copolymer A being a copolymer obtained by addition of a part of the acid groups of a structural unit a-3 having an acid group of a copolymer precursor PA to a functional group reactive with an acid group of an ethylenically unsaturated compound e, the copolymer precursor PA comprising: a structural unit a-1 having a blocked isocyanate group; a structural unit a-2 having a hydroxyl group; and a structural unit a-3 having an acid group, the basic catalyst B being contained in an amount of 0.5 to 12 parts by mass per 100 parts by mass of the copolymer A.

3. The resin composition according to claim 1 or the modified resin composition according to claim 2, the basic catalyst B satisfying the following condition 1 and condition 2, condition 1: the coordination number of the basic catalyst B with respect to glycidyl methacrylate calculated using the radial distribution function of the trajectory obtained by performing molecular dynamics calculation under conditions of 78°C and 1 atmosphere using the force field set as GAFF2 and the electric charge set as RESP(B3LYP / 6-31G(d) / / HF / 6-31G(d)) is 0.16 or greater, condition 2: the value of the orbital energy calculated after the structural optimization of the basic catalyst B is performed in quantum chemical calculation using B3LYP as the functional and 6-31G(d) as the basis function is -0.250 or greater, the unit of the orbital energy being Hartree. Basic catalyst B; 4. The resin composition according to claim 1 or the modified resin composition according to claim 2, the basic catalyst B being at least one selected from the group consisting of pyridine and pyridine derivatives, and phosphine derivatives.

5. The resin composition according to claim 1 or the modified resin composition according to claim 2, the basic catalyst B being at least one selected from the group consisting of 4-dimethylaminopyridine, tricyclohexylphosphine, tris(2,6-dimethoxyphenyl)phosphine, and tri(p-tolyl)phosphine.

6. The resin composition according to claim 1, in the total structural units of the copolymer precursor PA, the content of the structural unit a-1 having a blocked isocyanate group being 5 to 40 mol%, the content of the structural unit a-2 having a hydroxyl group being 1 to 35 mol%, the content of the structural unit a-3 having an acid group being 5 to 70 mol%, the amount of the ethylenically unsaturated compound e being 1 to 60 mol per 100 mol of the structural units of the copolymer precursor PA, the amount of the ethylenically unsaturated compound e being 1 to 60 mol per 100 mol of the structural unit a-3 having an acid group of the copolymer precursor PA, and the amount of the solvent C being 1 to 100 parts by mass per 100 parts by mass of the copolymer precursor PA. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ The amount of the ethylenically unsaturated compound e is 5 to 90 moles.

7. The modified resin composition according to claim 2, wherein, in the entirety of the constitutional units of the copolymer precursor PA, the content of the constitutional unit a-1 having a blocked isocyanate group is 5 to 40 mole%, the content of the constitutional unit a-2 having a hydroxyl group is 1 to 35 mole%, the content of the constitutional unit a-3 having an acid group is 5 to 70 mole%, with respect to 100 moles of the constitutional units of the copolymer precursor PA, the addition amount of the ethylenically unsaturated compound e is 1 to 55 moles, with respect to 100 moles of the constitutional unit a-3 having an acid group of the copolymer precursor PA, the addition amount of the ethylenically unsaturated compound e is 1 to 85 moles.

8. A photosensitive resin composition comprising: the modified resin composition according to claim 2; a reactive diluent D; and a photopolymerization initiator E.

9. A photosensitive colored composition comprising: the modified resin composition according to claim 2; a reactive diluent D; a photopolymerization initiator E; and a colorant F.

10. A resin cured film which is a cured product of the photosensitive resin composition according to claim 8.

11. A resin cured film which is a cured product of the photosensitive colored composition according to claim 9.

12. A color filter having a colored pattern which is a cured product of the photosensitive colored composition according to claim 9.

13. An image display element provided with the color filter according to claim 12.

14. A method for producing a resin composition, comprising a process I of preparing a resin composition containing a copolymer precursor PA, an ethylenically unsaturated compound e having a functional group reactive with an acid group, a basic catalyst B, and a solvent C, the copolymer precursor PA contains: a constitutional unit a-1 having a blocked isocyanate group; a constitutional unit a-2 having a hydroxyl group; and a constitutional unit a-3 having an acid group, the content of the basic catalyst B is 0.5 to 12 parts by mass with respect to 100 parts by mass of the total of the copolymer precursor PA and the ethylenically unsaturated compound e.

15. A method for producing a modified resin composition, comprising a heating process II of maintaining the resin composition obtained by the production method according to claim 14 at 50 to 120°C for 30 to 500 minutes, in the heating process II, the ethylenically unsaturated compound e having a functional group reactive with an acid group adds to the acid group of the constitutional unit a-3 having an acid group possessed by the copolymer precursor PA, and the copolymer precursor PA is converted into a copolymer A.

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