Resin precursor, resin, resin composition, and resin cured film

Abstract

A resin having a constituent unit (a) having a block isocyanate group, a constituent unit (b) having one or more groups selected from formula (2-2) and formula (3-2), and a constituent unit (c) having a hydroxyl group (wherein R1 to R4 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms).

Description

Technology Field

[0001] The present invention relates to a resin precursor, a resin derived from said resin precursor, a method for manufacturing a resin using said resin precursor, a resin composition containing said resin, a resin cured film, a color filter, and an image display element.

[0002] The present application claims priority based on Japanese Patent Application No. 2021-169527 filed on October 15, 2021, and incorporates the contents thereof herein. Background Technology

[0003] Image display devices include organic electroluminescence (EL) display devices (particularly, the WRGB method combining a white-emitting organic EL and a color filter), liquid crystal display devices, integrated circuit devices, and solid-state image devices. These image display devices are generally provided with films and fine patterns such as color filters, photospacers, protrusions for liquid crystal alignment, microlenses, and insulating films for touch panels. As for the color filter, a black matrix and pixels formed by a colored pattern formed on a substrate, and a protective film formed thereon are typically used.

[0004] In recent years, with the increasing flexibility and wearability of displays, there has been a transition from glass to organic materials such as resins as substrate materials. Organic materials have lower heat resistance compared to glass. For this reason, in the case of a member formed by heat-curing a resin composition on a substrate, it is desired to lower the temperature at which the resin composition is heat-cured according to the heat resistance of the substrate containing the organic material.

[0005] For example, color filters were conventionally formed by heat-curing a resin composition on a substrate at a temperature of 210 to 230°C. However, when forming a color filter on a flexible substrate containing resin, the heat resistance of the substrate is reduced, so it is required to form it by heat-curing the resin composition at a temperature of 80 to 150°C.

[0006] In particular, for color filters used in organic EL display devices, there is a tendency to increase the content of the colorant included in the resin composition in order to improve color reproduction. Generally, resin compositions containing a large amount of colorant are difficult to photocur. For this reason, in resin compositions used in color filters of organic EL display devices, it is even more important to cure them by crosslinking with heat. In this regard, there is an increasing need to improve the thermal curability, especially at low temperatures, in resin compositions used in color filters of organic EL display devices.

[0007] Conventionally, resin compositions used as materials for color filters include those described in Patent Document 1 and Patent Document 2.

[0008] Patent Document 1 describes (a) an absorption coefficient of 1.0 × 10⁻⁶ at 365 nm in methanol. 3 (b) a polymerization initiator with a mL / gcm or higher, and an absorption coefficient of 1.0×10 at 365 nm in methanol. 2 It is ≤ mL / gcm and the absorption coefficient at 254 nm is 1.0×10 3 A photosensitive coloring composition is disclosed that contains a polymerization initiator of mL / gcm or more, (c) a compound having an unsaturated double bond, (d) an alkali-soluble resin, and (e) a colorant.

[0009] Patent document 2 discloses a photosensitive composition for a color filter comprising a compound (A) containing a furyl group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and a coloring agent. Prior art literature

[0010] Japanese Patent Publication No. 2015-041058 Japanese Patent Publication No. 2017-194662 The problem to be solved

[0011] In the resin composition used for the component of an image display element, it is required to lower the heating temperature for curing.

[0012] However, conventional resin compositions did not yield a cured product with sufficient solvent resistance when the heating temperature for curing was lowered. For this reason, there is a demand for a resin composition with good low-temperature curing properties that can form a cured product with excellent solvent resistance even at a low heating temperature for curing.

[0013] The present invention is made in consideration of the above circumstances and aims to provide a resin composition capable of forming a cured product having excellent low-temperature curing properties and good solvent resistance, a resin contained in the resin composition, a resin precursor imparting the resin, and a method for manufacturing a resin using the resin precursor.

[0014] In addition, the purpose is to provide a resin cured film with good solvent resistance comprising a cured product of a resin composition having excellent low-temperature curing properties, a color filter, and an image display element equipped with said color filter. means of solving the problem

[0015] The present invention provides a resin of the following first embodiment.

[0016] [1] A constituent unit (a) having a block isocyanate, and,

[0017] A constituent unit (b) having one or more types of groups selected from the following formulas (2-2) and (3-2), and

[0018] Constituent unit having a hydroxyl group (c)

[0019] A resin characterized by having

[0020]

[0021] (In Equation (2-2), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0022]

[0023] (In Equation (3-2), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0024] The resin of the first embodiment of the present invention preferably has the features described in [2] to [8] below. It is also preferable to arbitrarily combine two or more of the features described in [2] to [8] below.

[0025] [2] The constituent unit (a) having the above block isocyanate group is a resin described in [1], in which the dissociation rate of the block isocyanate group is 5 to 99% when heated at 100°C for 30 minutes.

[0026] [3] The constituent unit (a) having the block isocyanate group is a constituent unit derived from a monomer having an ethylenically unsaturated bond and a block isocyanate group, and

[0027] The monomer having the above-mentioned ethylenically unsaturated bond and a blocked isocyanato group is a compound in which the isocyanato group of an isocyanate compound having the above-mentioned ethylenically unsaturated bond and an isocyanato group is blocked by a blocking agent, and

[0028] The resin described in [1] or [2], wherein the blocking agent is one or more selected from γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methylethyl ketoxime and 3,5-dimethylpyrazole.

[0029] [4] The above-mentioned constituent unit (a) having a block isocyanate group is a constituent unit of (meth)acrylate containing a block isocyanate group, and

[0030] A resin described in any one of [1] to [3], wherein the above-mentioned block isocyanato group-containing (meth)acrylate is a compound in which the isocyanato group-containing (meth)acrylate is blocked by one or more blocking agents selected from 3,5-dimethylpyrazole and methylethyl ketoxime.

[0031] [5] A resin described in any of [1] to [4] in which the above-mentioned constituent unit (b) is a constituent unit derived from a monomer having a (meth)acryloyloxy group and a group represented by the following formula (1).

[0032]

[0033] (In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0034] [6] R of the above-mentioned constituent unit (b) 1 and R 2 Each of these is independently a hydrocarbon group having 1 to 3 carbon atoms, and R 3 and R 4 a. A resin described in any of [1] to [5], each independently a hydrogen atom or a methyl group.

[0035] [7] The above-mentioned hydroxyl group-containing constituent unit (c) is a resin described in any of [1] to [6] which is a constituent unit derived from a hydroxyl group-containing (meth)acrylate.

[0036] [8] A resin described in any one of [1] to [7] in which a portion of the constituent unit (c) having the above hydroxyl group comprises a carboxyl group derived from a polybasic acid (e).

[0037] A second aspect of the present invention provides the following resin precursor.

[0038] [9] Constituent unit (a) having block isocyanate, and,

[0039] A constituent unit (pb) having a group represented by the following formula (1), and

[0040] Constituent unit having a hydroxyl group (c)

[0041] A resin precursor characterized by containing

[0042]

[0043] (In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0044] A third aspect of the present invention provides the following resin manufacturing method.

[0045]

[10] A method for producing a resin described in any one of [1] to [8], characterized by carrying out a dealcoholization and decarboxylation reaction of a resin precursor (PA) described in [9] in a solvent (PC) using a basic catalyst (PB).

[0046] A fourth aspect of the present invention provides the following resin composition.

[11] A resin (A) described in any one of [1] to [8], and

[0047] Solvent (C) and,

[0048] Reactive diluent (D) and,

[0049] Photopolymerization initiator (E)

[0050] A resin composition containing

[0051]

[12] A resin composition described in

[11] containing a coloring agent (F).

[0052]

[13] For every 100 parts by mass of the total of the resin (A) and the reactive diluent (D), the resin (A) is contained in an amount of 10 to 90 parts by mass,

[0053] Containing 30 to 1000 parts by mass of the above solvent (C),

[0054] Containing 10 to 90 parts by mass of the above-mentioned reactive diluent (D),

[0055] Containing 0.1 to 30 parts by mass of the above photopolymerization initiator (E),

[0056] Containing 3 to 80 parts by mass of the above coloring agent (F),

[0057]

[12] Resin composition described in

[12] .

[0058] A fifth aspect of the present invention provides the following resin cured film.

[0059]

[14] A resin cured film comprising a cured product of a resin composition described in any of

[11] to

[13] .

[0060] A sixth aspect of the present invention provides the following color filter.

[0061]

[15] A color filter having a colored pattern containing a cured resin composition as described in

[13] .

[0062] A seventh aspect of the present invention provides the following image display element.

[0063]

[16] An image display element having a color filter as described in

[15] . Effects of the invention

[0064] According to the present invention, a resin composition capable of forming a cured product having excellent low-temperature curability and good solvent resistance, a resin contained as a material in the resin composition, a resin precursor for imparting the resin, and a method for manufacturing a resin using the resin precursor can be provided. Furthermore, according to the present invention, a resin cured film having good solvent resistance comprising a cured product of the resin composition having excellent low-temperature curability, a color filter, and an image display element having the color filter can be provided. Brief explanation of the drawing

[0065] Figure 1 is a graph showing the IR spectrum of the resin precursor composition of Example 1 (before conversion reaction) and the IR spectrum of the reaction solution after conversion reaction (after conversion reaction). Specific details for implementing the invention

[0066] Hereinafter, preferred examples of the resin precursor, the resin derived from the resin precursor, the method for manufacturing the resin using the resin precursor, the resin composition, the resin cured film, the color filter, and the image display element of the present invention will be described in detail. Furthermore, the present invention is not limited only to the embodiments described below. Within the scope of not departing from the spirit of the present invention, additions, omissions, substitutions, or changes to the number, amount, ratio, type, location, material, composition, etc., are possible.

[0067] In this specification, “(meth)acrylic acid” means at least one selected from methacrylic acid and acrylic acid. “(meth)acrylate” means at least one selected from methacrylate and acrylate.

[0068] Additionally, in this specification, "*" in the structural formulas indicates a connection point between the above-mentioned structural formula and other structural parts.

[0069] <Resin Precursor (PA)>

[0070] The resin precursor (PA) of the present embodiment is a copolymer containing a constituent unit (a) having a block isocyanate group (hereinafter also simply referred to as “constituent unit (a)”), a constituent unit (pb) having a group represented by the following formula (1) (hereinafter also simply referred to as “constituent unit (pb)”), and a constituent unit (c) having a hydroxyl group (hereinafter also simply referred to as “constituent unit (c)”). The resin precursor (PA) of the present embodiment may, if necessary, contain other constituent units (d) (hereinafter also simply referred to as “constituent unit (d)”) other than constituent units (a) to (c).

[0071]

[0072] (In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0073] The resin precursor (PA) of the present embodiment is used as a material for the resin (A) described below. In the present embodiment, the resin precursor (PA) of the present embodiment is subjected to a dealolysis reaction and a decarboxylation reaction in a solvent (PC) using a basic catalyst (PB). By doing so, the group represented by Formula (1) having the constituent unit (pb) is converted into a group represented by Formula (2-2) and / or Formula (3-2) included in the constituent unit (b) of the resin (A) described below, and the resin (A) is produced.

[0074] [Constituent unit having block isocyanate pottery (a)]

[0075] A constituent unit (a) having a block isocyanate group included in the resin precursor (PA) has a block isocyanate group and does not have a hydroxyl group or a group represented by the above formula (1). The constituent unit (a) may be of only one type or two or more types. The constituent unit (a) is a constituent unit derived from a block isocyanate group-containing monomer (ma) (hereinafter also simply referred to as "monomer (ma)").

[0076] In this embodiment, the monomer (ma) that serves as the constituent unit (a) does not have a hydroxyl group and a group represented by the formula (1) above, but has an ethylenically unsaturated bond and a blocked isocyanato group. As the monomer (ma), for example, a compound in which the isocyanato group of an isocyanate compound having an ethylenically unsaturated bond and an isocyanato group is blocked by a blocking agent may be used. Examples of ethylenically unsaturated groups included in the monomer (ma) include a vinyl group, a (meth)acryloyloxy group, etc.

[0077] When preparing the monomer (ma), the blocking reaction between the isocyanate compound and the blocking agent can be carried out regardless of the presence or absence of a solvent. When the above blocking reaction is carried out using a solvent, the solvent used must be inert to the isocyanate group, and known solvents may be used. During the blocking reaction, organometallic salts such as tin, zinc, and lead, or tertiary amines may be used as catalysts. The blocking reaction can generally be carried out at -20 to 150°C, and it is preferable to carry out it at 0 to 100°C.

[0078] As for the above isocyanate compound used as a raw material for monomer (ma), for example, a compound represented by the following formula (4) can be used.

[0079]

[0080] (In Equation (4), R 5represents a hydrogen atom or a methyl group; R 6 -CO-, -COOR 7 - (here, R 7 (is an alkylene group having 1 to 6 carbon atoms) or -COO-R 8 O-CONH-R 9 - (here, R 8 is an alkylene group having 2 to 6 carbon atoms, and R 9 ...is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms that may have substituents.)

[0081] In the isocyanate compound represented by formula (4), R 5 is a hydrogen atom or a methyl group. R in Equation (4) 6 -CO-, -COOR 7 -(Here, R 7 (is an alkylene group having 1 to 6 carbon atoms) or -COO-R 8 O-CONH-R 9 -(Here, R 8 is an alkylene group having 2 to 6 carbon atoms, and R 9 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms that may have substituents.) R 6 From the good reactivity of the isocyanate after deblocking or the ease of preparing the isocyanate compound, -COOR 7 It is desirable that..., R 7 It is more preferable that this be an alkylene group having 1 to 4 carbon atoms.

[0082] Examples of isocyanate compounds represented by the above formula (4) include, specifically, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, etc.

[0083] In addition, as an isocyanate compound used as a raw material for monomer (ma), a reaction product obtained by reacting 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound in an equimolar ratio (2-hydroxyalkyl (meth)acrylate:diisocyanate compound = 1 mol:1 mol) may be used.

[0084] The alkyl group of the above 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group, due to the good reactivity of the isocyanate after deblocking, the ease of preparing the isocyanate compound, and the simplicity of the reaction.

[0085] Examples of the above diisocyanate compounds include hexamethylene diisocyanate, 2,4-(or 2,6-)tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, etc.

[0086] Other isocyanate compounds mentioned above used as raw materials for monomer (ma) include 1,1-bis(methacryloyloxymethyl)methylisocyanate, 1,1-bis(methacryloyloxymethyl)ethylisocyanate, 1,1-bis(acryloyloxymethyl)methylisocyanate, and 1,1-bis(acryloyloxymethyl)ethylisocyanate.

[0087] A constituent unit (a) having a block isocyanato group is preferably a constituent unit derived from a block isocyanato group-containing (meth)acrylate, in terms of the low-temperature curability of a resin composition containing a resin (A) that can be prepared using a resin precursor (PA). When the monomer (ma) is a block isocyanato group-containing (meth)acrylate, the isocyanate compound used as a raw material is an isocyanato group-containing (meth)acrylate.

[0088] The isocyanato group-containing (meth)acrylate used as a raw material for the monomer (ma) is preferably 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate, and more preferably 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate.

[0089] When the monomer (ma) is a (meth)acrylate containing a blocked isocyanato group, the blocking agent for blocking the isocyanato group of the isocyanate compound used as a raw material is, for example, a lactam-based agent such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; an alcohol-based agent such as methanol, ethanol, propanol, 1-methoxy-2-propanol, butanol, ethylene glycol, methylcellosolve, butylcellosolve, methylcarbitol, benzyl alcohol, phenylcellosolve, furfuryl alcohol, cyclohexanol, etc. Phenols such as phenol, 2,6-dimethylphenol, cresol, 3,5-xylenol, ethylphenol, butylphenols such as o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styreneated phenol, 2-methyl hydroxybenzoate, 4-methyl hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; active methylenes such as dimethyl malonicate, diethyl malonicate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.; mercaptans such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; amines such as diisopropylamine, diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; acidamides such as acetanilide, acetanisidide, acetamide, benzamide, etc.; Examples include acid imide types such as succinate imide, maleate imide; imidazole types such as imidazole, 2-methylimidazole, 2-ethylimidazole; pyrazole types such as pyrazole, 3,5-dimethylpyrazole; urea types such as urea, thiourea, ethyleneurea; carbamate types such as N-phenylcarbamate phenyl, 2-oxazolidone; imine types such as ethyleneimine, polyethyleneimine; oxime types such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime; bisulfite types such as sodium bisulfite, potassium bisulfite, etc., and since the low-temperature curing properties of a resin composition containing a resin (A) prepared using a resin precursor (PA) are improved, 3,5-dimethylpyrazole and methyl ethyl ketoxime are preferred. These block systems may be used individually or in combination of two or more types.

[0090] In the constituent unit (a) having a block isocyanate group, the highly reactive isocyanate group is protected by a blocking agent. When a resin composition containing a resin (A) prepared using a resin precursor (PA) containing the constituent unit (a) is heated, the block isocyanate group of the constituent unit (a) dissociates and the isocyanate group is regenerated. Therefore, in the present embodiment, when the resin composition described below is heated and cured, the isocyanate group of the constituent unit (a) is regenerated. The regenerated isocyanate group reacts with the reactive functional group contained in the resin (A) prepared using the resin precursor (PA) to form a cured product with a high crosslinking density. The reactive functional group contained in the resin (A) is the hydroxyl group contained in the constituent unit (c) having a hydroxyl group in the resin precursor (PA), and the acid group, amino group, etc. contained in other constituent units (d) included as needed.

[0091] The constituent unit (a) having a block isocyanate group preferably has a dissociation rate of the block isocyanate group of 5 to 99% when heated at 100°C for 30 minutes, more preferably 10 to 90%, and most preferably 15 to 80%. The dissociation rate may be, for example, 8 to 70%, 15 to 60%, 30 to 50%, etc. If the dissociation rate of the block isocyanate group of the constituent unit (a) is 99% or less, the isocyanate group of the constituent unit (a) can be suppressed from regenerating and causing unintended cross-linking reactions during the synthesis of the resin (A) produced using the resin precursor (PA) and during the storage of the resin composition containing the resin (A), thereby ensuring the stability of the resin (A). In addition, if the dissociation rate of the block isocyanate group of the constituent unit (a) is 5% or higher, good curability is obtained even if the heating temperature for curing the resin composition containing the resin (A) prepared using the resin precursor (PA) is sufficiently low, and a cured product having excellent solvent resistance is obtained.

[0092] Examples of blocking agents used as raw materials for monomers (ma) that form constituent units (a) having a dissociation rate of 5 to 99% of block isocyanato groups when heated at 100°C for 30 minutes include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methylethyl ketoxime, and 3,5-dimethylpyrazole. Among these blocking agents, 3,5-dimethylpyrazole and methylethyl ketoxime are more preferred from the perspective of low-temperature curability of a resin composition containing a resin (A) prepared using a resin precursor (PA).

[0093] The dissociation rate of the block isocyanate pottery when a constituent unit (a) having a block isocyanate pottery is heated at 100°C for 30 minutes is the same as the dissociation rate of the block isocyanate pottery when a block isocyanate pottery-containing monomer (ma) is heated at 100°C for 30 minutes, and can be calculated by the method shown below.

[0094] That is, an n-octanol solution is prepared with a monomer (ma) concentration of 20 mass%. To the obtained n-octanol solution, 1 mass% of dibutyltin laurate (catalyst) and 3 mass% of phenothiazine (polymerization inhibitor) are added, and the solution is heated at 100°C for 30 minutes. The n-octanol solution after heating is analyzed by high-performance liquid chromatography (HPLC), and the mass of the monomer (ma) in the n-octanol solution is determined. Using the results, the mass reduction ratio of the block isocyanate group-containing monomer (ma) caused by heating at 100°C for 30 minutes is calculated and used as the dissociation rate.

[0095] It is preferable that the dissociation temperature at which the dissociation rate of the block isocyanate group of the constituent unit (a) having a block isocyanate group is 80% or more in 30 minutes is 80°C or higher. If the above dissociation temperature of the block isocyanate group of the constituent unit (a) is 80°C or higher, during the synthesis of the resin (A) prepared using the resin precursor (PA) and during the storage of the resin composition containing the resin (A), the isocyanate group of the constituent unit (a) can be regenerated and unintended cross-linking reactions can be suppressed, and the stability of the resin (A) can be secured. If the above dissociation temperature of the block isocyanate group of the constituent unit (a) is 160°C or lower, good curability is obtained even if the heating temperature for curing the resin composition containing the resin (A) prepared using the resin precursor (PA) is sufficiently low, and a cured product having excellent solvent resistance is obtained.

[0096] The dissociation temperature at which the dissociation rate of the block isocyanate of the constituent unit (a) having block isocyanate is 80% or more in 30 minutes can be calculated by the method shown below.

[0097] That is, an n-octanol solution is prepared with a monomer (ma) concentration of 20 mass%. To the obtained n-octanol solution, 1 mass% of dibutyltin laurate (catalyst) and 3 mass% of phenothiazine (polymerization inhibitor) are added, and the solution is heated for 30 minutes under multiple conditions of different temperatures. After heating, the n-octanol solution is analyzed by high-speed liquid chromatography (HPLC) for each temperature condition, and the mass of the monomer (ma) in the n-octanol solution is determined. Using the results, the lowest temperature at which the mass loss rate of the block isocyanate group-containing monomer (ma) by heating for 30 minutes is 80% or more in 30 minutes is determined and set as the dissociation temperature.

[0098] Where the constituent unit (a) having a block isocyanate group is a constituent unit derived from a (meth)acrylate containing a block isocyanate group, specifically, a constituent unit derived from MOI-BP (registered trademark) represented by the following formula (6) (a compound in which methachlorooxyethyl isocyanate is blocked with 3,5-dimethylpyrazole, manufactured by Showa Denko Co., Ltd., dissociation temperature at which the dissociation rate of the block isocyanate group is 80% or more in 30 minutes: 110°C, dissociation rate when heated at 100°C for 30 minutes: 70%) and / or MOI-BM (registered trademark) represented by the following formula (7) (a compound in which methachlorooxyethyl isocyanate is blocked with methyl ethyl ketoxime, manufactured by Showa Denko Co., Ltd., dissociation temperature at which the dissociation rate of the block isocyanate group is 80% or more in 30 minutes: 130°C, for 30 minutes at 100°C It is desirable that the constituent unit be derived from the dissociation rate when heated: 18%).

[0099]

[0100] The content ratio of constituent unit (a) in the resin precursor (PA) can be appropriately determined according to the use of the resin precursor (PA). The content ratio of constituent unit (a) is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 10 to 25 mol%. The above ratio may be 8 to 35 mol% or 15 to 20 mol%, etc. If the content ratio of constituent unit (a) is 1 mol% or more, the resin composition containing the resin (A) prepared using the resin precursor (PA) can be sufficiently cured even at a sufficiently low heating temperature, and a cured product having excellent solvent resistance is obtained. This is because, by heating to cure the resin composition, the blocking agent of the block isocyanate group of constituent unit (a) dissociates, and a sufficient number of isocyanate groups are regenerated. The regenerated isocyanate group has high reactivity with hydroxyl groups and rapidly reacts with the hydroxyl group included in the constituent unit (c) to form crosslinks. As a result, a resin composition is obtained in which a cured product with better low-temperature curing properties and excellent solvent resistance is obtained.

[0101] If the content ratio of constituent unit (a) is 40 mol% or less, the content ratio of constituent unit (pb) and constituent unit (c) in the resin precursor (PA) can be sufficiently secured, and a resin composition with better low-temperature curing properties is obtained. In addition, if the content ratio of constituent unit (a) is 40 mol% or less, during the synthesis of the resin (A) manufactured using this and during the storage of the resin composition containing the resin (A), the isocyanate group having constituent unit (a) can be regenerated, and the occurrence of an unintended cross-linking reaction can be suppressed, and the stability of the resin (A) can be secured.

[0102] [Constituent unit (pb)]

[0103] The constituent unit (pb) included in the resin precursor (PA) is a constituent unit derived from a monomer (m-pb) having a group represented by the following formula (1) (hereinafter also simply referred to as "monomer (m-pb)"). The constituent unit (pb) may be of one type or two or more types.

[0104] Monomer (m-pb) is a monomer that does not have hydroxyl groups, isocyanate groups, or block isocyanate groups, but has ethylenically unsaturated bonds and groups represented by the following formula (1).

[0105]

[0106] (In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0107] In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms in terms of ease of reaction with respect to a constituent unit (b) having one or more groups selected from Formula (2-2) and Formula (3-2). R 1 and R 2 It is preferably an alkyl group, preferably a methyl or ethyl group, and particularly preferably an ethyl group. R 1 and R 2 It may be the same or different, and since the monomer (m-pb) can be easily manufactured, it is preferable that it be the same.

[0108] In Equation (1), R 3 and R 4R is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a group having 1 to 5 carbon atoms, and is more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, in terms of ease of reaction with respect to a constituent unit (b) having one or more groups selected from Formula (2-2) and Formula (3-2) below. 3 and R 4 It may be the same or different, and since the monomer (m-pb) can be easily manufactured, it is preferable that it be the same.

[0109] As monomers (m-pb), examples include isocyanato groups in isocyanate compounds having ethylenically unsaturated groups such as vinyl groups and (meth)acryloyloxy groups in the molecule, and compounds in which hydroxyl groups in hydroxyl group-containing compounds represented by the following formula (8) are urethane-reacted.

[0110]

[0111] (Equation (8), R 1 , R 2 , R 3 and R 4 is R in Equation (1) 1 , R 2 , R 3 and R 4 It is the same as.)

[0112] As a method for urethane-reacting the above-mentioned isocyanate compound having an ethylene unsaturated group and the hydroxyl group-containing compound represented by formula (8), a conventionally known method may be used.

[0113] The above urethane reaction can be carried out regardless of the presence or absence of a solvent. When the above urethane reaction is carried out using a solvent, the solvent used must be inert to isocyanate groups, and known solvents may be used.

[0114] The above urethane reaction is generally preferably carried out at a temperature of -10°C or higher and 90°C or lower, more preferably at a temperature of 5°C or higher and 70°C or lower, and even more preferably at a temperature of 10°C or higher and 40°C or lower.

[0115] When carrying out the above urethane reaction, a urethane catalyst such as dibutyltin dilaurate; a polymerization inhibitor such as phenothiazine, p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (hereinafter also referred to as "BHT"); etc. may be used as needed.

[0116] As an isocyanate compound used as a raw material for the monomer (m-pb), any compound that can be used as an isocyanate compound for the aforementioned block isocyanate group-containing monomer (ma) and preferred examples thereof may be used.

[0117] Examples of hydroxyl group-containing compounds represented by formula (8) used as raw materials for monomer (m-pb) include malic acid esters, 2-methyl malic acid esters, 3-methyl malic acid esters, 2,3-dimethyl malic acid esters, tartaric acid esters, and citric acid esters, and malic acid esters are preferred from the perspective of ease of reaction to convert into a constituent unit (b) having one or more groups selected from formulas (2-2) and (3-2) below, and ease of obtaining.

[0118] The number of carbon atoms in two ester sites included in the hydroxyl group-containing compound represented by formula (8) (-COOR 1 and -COOR 2 R in 1 and R 2 The number of carbon atoms (of) is 1 to 20, but is preferably 1 to 5 each, and more preferably 1 to 3. The hydroxyl group-containing compound represented by formula (8) is particularly preferably diethyl malate for ease of availability.

[0119] As for the monomer (m-pb), specifically, it is preferable to be one or more selected from 2-[(diethyl malate)carbonylamino]ethyl acrylate, 2-[(diethyl malate)carbonylamino]methyl acrylate, 2-[(diethyl malate)carbonylamino]propyl acrylate, and 2-[(diethyl malate)carbonylamino]butyl acrylate, and from the perspective of ease of manufacturing, it is particularly preferable to be 2-[(diethyl malate)carbonylamino]ethyl acrylate.

[0120] A resin composition is obtained by including a resin precursor (PA) containing a constituent unit (pb), thereby having a resin (A) having a constituent unit (b) derived from the constituent unit (pb). The constituent unit (b) introduces an ethylenically unsaturated group into the resin (A). Because of this, a resin composition containing a resin (A) having constituent unit (b) has good photocurability and low-temperature curability, and a cured product having excellent solvent resistance is obtained.

[0121] The content ratio of the constituent unit (pb) in the resin precursor (PA) can be appropriately determined according to the use of the resin precursor (PA). The content ratio of the constituent unit (pb) in the resin precursor (PA) is preferably 1 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 20 to 35 mol%. The above ratio may be 5 to 45 mol% or 15 to 30 mol%, etc. If the content ratio of the constituent unit (pb) is 1 mol% or more, the resin (A) derived from the resin precursor (PA) sufficiently contains the constituent unit (b) derived from the constituent unit (pb) in the resin precursor (PA). As a result, the resin composition containing the resin (A) has sufficiently introduced ethylenically unsaturated groups into the resin (A), and a cured product having good photocurability and low-temperature curability and excellent solvent resistance is obtained. If the content ratio of the constituent unit (pb) is 50 mol% or less, the content ratio of the constituent unit (a) and constituent unit (c) in the resin precursor (PA) can be sufficiently secured, and a resin composition with better low-temperature curing properties is obtained.

[0122] [Constituent unit (c)]

[0123] The constituent unit (c) having a hydroxyl group included in the resin precursor (PA) is a constituent unit derived from a hydroxyl group-containing monomer (mc) (hereinafter also simply referred to as "monomer (mc)"). The constituent unit (c) may be one type or two or more types.

[0124] The monomer (mc) does not have a block isocyanate group and a group represented by the above formula (1), but has an ethylenically unsaturated group and a hydroxyl group, and is not particularly limited.

[0125] Examples of monomers (mc) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

[0126] Among these monomers (mc), 2-hydroxyethyl (meth)acrylate is preferred from the perspective of ease of availability. These monomers (mc) may be used alone or in combination of two or more types.

[0127] Since the resin precursor (PA) contains constituent unit (c), when a resin composition containing resin (A) prepared using the resin precursor (PA) is heated and cured, the blocked isocyanate group of constituent unit (a) is deblocked (dissociated) and the regenerated isocyanate group reacts with the hydroxyl group of constituent unit (c). As a result, good curability is obtained even when the heating temperature for curing the resin composition is sufficiently low, and a cured product having excellent solvent resistance is obtained.

[0128] The content ratio of constituent unit (c) in the resin precursor (PA) can be appropriately determined according to the use of the resin precursor (PA). The content ratio of constituent unit (c) in the resin precursor (PA) is preferably 1 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 30 to 60 mol%. If necessary, the above ratio may be 5 to 50 mol% or 20 to 40 mol%, etc. If the content ratio of constituent unit (c) is 1 mol% or more, a sufficient number of hydroxyl groups can be secured to react with isocyanate groups regenerated by heating to cure a resin composition containing a resin prepared using the resin precursor (PA). For this reason, a resin composition is obtained in which a cured product with better low-temperature curing properties and excellent solvent resistance is obtained. If the content ratio of constituent unit (c) is 80 mol% or less, the content ratio of constituent unit (pb) and constituent unit (c) in the resin precursor (PA) can be sufficiently secured, and the resin composition containing the resin prepared using the resin precursor (PA) has a balance of photocurability and low-temperature curability.

[0129] [Other constituent units (d)]

[0130] The resin precursor (PA) may, if necessary, contain other constituent units (d) other than constituent units (a) to (c). Constituent unit (d) may be one type or two or more types. Constituent unit (d) is a constituent unit derived from other monomers (md) (hereinafter simply referred to as “monomer (md)”) other than the aforementioned monomers (ma) (ma-pb) (mc).

[0131] Monomer (md) is a monomer having an ethylenically unsaturated group, without having a hydroxyl group, an isocyanate group, a block isocyanate group, or a group represented by the above formula (1), and is not particularly limited. Examples of monomers (md) include dienes such as butadiene, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, styrenes, unsaturated dicarboxylic acid diesters, etc.

[0132] Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate. Ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, dicyclopentenyl (meth)acrylate, Examples include dicyclofentanyl (meth)acrylate, isobornyl (meth)acrylate, adamanthyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetane-3-yl)methyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, hexamethylpiperidyl (meth)acrylate, etc.

[0133] Specific examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenilamide, N-isopropyl(meth)acrylamide, (meth)acrylmorpholine, diacetone(meth)acrylamide, etc.

[0134] Specific examples of vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-en), 5-methylbicyclo[2.2.1]hept-2-en, 5-ethylbicyclo[2.2.1]hept-2-en, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6 ]Deck-8-en, Tricycle[5.2.1.0 2,6 ]Deck-3-en, Tricyclo[4.4.0.1 2,5 ]Undeca-3-en, tricyclo[6.2.1.0 1,8 ]Undeca-9-en, Tricyclo[6.2.1.0 1,8 ]Undeca-4-en, tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodeca-3-ene, 8-ethylidene tetracyclo[4.4.0.1 2,5 .1 7,12 ]dodeca-3-ene, 8-ethylidene tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]Dodeca-3-en, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13]Pentadech-4-en, Pentacyclo[7.4.0.1 2,5 .1 9,12 .0 8,13 Examples include ]pentadec-3-en, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth)acrylate anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, vinyltoluene, norbornene.

[0135] Specific examples of styrenes include styrene, α-, o-, m-, p-alkyl, nitro, cyano, and amide derivatives of styrene.

[0136] Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.

[0137] Specific examples of unsaturated polybasic acid anhydrides include itaconic anhydride and citraconic anhydride.

[0138] These monomers (md) may be used alone or in combination of two or more.

[0139] Among these monomers (md), (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates having an alkyl group having 1 to 10 carbon atoms are more preferred from the viewpoint of ease of availability and the ability to express the role of constituent units (a) to (c) without hindering it, and in particular, in order to efficiently express the role of constituent units (a) to (c), methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Alkyl (meth)acrylates having straight-chain alkyl groups that do not have a cyclic backbone having 1 to 10 carbon atoms, such as lauryl (meth)acrylate and dodecyl (meth)acrylate, are more preferable.

[0140] When the resin precursor (PA) contains a constituent unit (d), the content ratio in the resin precursor (PA) can be appropriately determined according to the application of the resin precursor (PA). The content ratio of the constituent unit (d) in the resin precursor (PA) is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, and even more preferably 5 to 20 mol%. The above ratio may be 2 to 18 mol% or 8 to 15 mol%, etc. If the content ratio of the constituent unit (d) is 1 mol% or more, the effect of including the constituent unit (d) becomes significant. If the content ratio of the constituent unit (d) is 30 mol% or less, the content ratios of constituent unit (a), constituent unit (pb), and constituent unit (c) in the resin precursor (PA) can be sufficiently secured. For this reason, a resin composition containing a resin prepared using the resin precursor (PA) can be obtained as a cured product having good low-temperature curing properties and excellent solvent resistance.

[0141] The weight-average molecular weight of the resin precursor (PA) in terms of polystyrene is not particularly limited, but is preferably 1,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 10,000. If the weight-average molecular weight of the resin precursor (PA) is 1,000 or more, a resin composition containing a resin prepared using the resin precursor (PA) yields a cured product having better solvent resistance. If the weight-average molecular weight of the resin precursor (PA) is 40,000 or less, a suitable viscosity can be imparted to the resin composition containing the resin prepared using the resin precursor (PA), and it becomes easier to obtain a resin composition that is easy to handle.

[0142] The resin precursor (PA) of the present embodiment contains a constituent unit (a) having a block isocyanate group and contains a block isocyanate group in the molecule. The content of the block isocyanate group in the resin precursor (PA) can be appropriately selected, but is typically selected in the range where the block isocyanate group equivalent is 400 to 6,000 g / mol, preferably 500 to 5,000 g / mol, and more preferably 700 to 3,000 g / mol. If the block isocyanate group equivalent in the resin precursor (PA) is 400 g / mol or more, the resin composition containing the resin prepared using the resin precursor (PA) can be sufficiently cured even if the heating temperature for curing is sufficiently low, thereby obtaining a cured product with better solvent resistance. If the block isocyanate group equivalent in the resin precursor (PA) is 6,000 g / mol or less, the isocyanate group of the constituent unit (a) can be regenerated and an unintended cross-linking reaction can occur during the synthesis of the resin produced using this and during the storage of the resin composition containing the resin, thereby ensuring stability.

[0143] The block isocyanate equivalent in the resin precursor (PA) is the mass of the resin precursor (PA) per mole of block isocyanate contained in the resin precursor (PA), and is obtained by dividing the mass of the resin precursor (PA) by the number of moles of block isocyanate contained in the resin precursor (PA) (g / mol). In the present invention, the block isocyanate equivalent in the resin precursor (PA) is a theoretical value calculated from the input amount of the block isocyanate-containing monomer (ma) used as a raw material for the resin precursor (PA).

[0144] The resin precursor (PA) of the present embodiment contains a constituent unit (c) having a hydroxyl group and contains a hydroxyl group in the molecule. The content of the hydroxyl group in the resin precursor (PA) can be appropriately selected, but is typically selected in the range where the hydroxyl group equivalent is 200 to 5000 g / mol, preferably 300 to 3000 g / mol, and more preferably 400 to 2000 g / mol. It is preferable that the hydroxyl group equivalent in the resin precursor (PA) be 200 g / mol or more, as this does not impair the compatibility of other components of the resin precursor composition. If the hydroxyl group equivalent in the resin precursor (PA) is 5000 g / mol or less, the resin composition containing the resin prepared using the resin precursor (PA) can sufficiently secure the number of hydroxyl groups that react with the isocyanate groups regenerated by heating to cure it. For this reason, a resin composition is obtained in which a cured product with better low-temperature curing properties and excellent solvent resistance is obtained.

[0145] The hydroxyl group equivalent in the resin precursor (PA) is the mass of the resin precursor (PA) per mole of hydroxyl groups contained in the resin precursor (PA), and is obtained by dividing the mass of the resin precursor (PA) by the number of moles of hydroxyl groups contained in the resin precursor (PA) (g / mol). In the present invention, the hydroxyl group equivalent in the resin precursor (PA) is a theoretical value calculated from the input amount of a constituent unit (c) having hydroxyl groups used as a raw material for the resin precursor (PA).

[0146] <Method for manufacturing resin precursor (PA)>

[0147] A resin precursor (PA) can be prepared by copolymerizing monomers (ma), (m-pb), and (mc) corresponding to each of the constituent units (a), (pb), and (c) included in the resin precursor (PA). The proportions of constituent units (a), (pb), and (c) included in the resin precursor (PA) are equivalent to the proportions of each monomer (ma), (m-pb), and (mc) in the total sum of all monomers used as raw materials for the resin precursor (PA) (hereinafter referred to as "raw material monomers").

[0148] Accordingly, the ratio of each monomer (ma), (m-pb), and (mc) among the raw monomers used as raw materials for the resin precursor (PA) is preferably 1 to 40 mol% for (ma), 1 to 50 mol% for (m-pb), and 1 to 80 mol% for (mc); more preferably 5 to 30 mol% for (ma), 10 to 40 mol% for (m-pb), and 10 to 70 mol% for (mc); and even more preferably 10 to 25 mol% for (ma), 20 to 35 mol% for (m-pb), and 30 to 60 mol% for (mc).

[0149] When manufacturing a resin precursor (PA) that includes a constituent unit (d), additional monomer (md) may be used in addition to monomers (ma), (m-pb), and (mc) as raw material monomers for the resin precursor (PA). In that case, the proportion of monomer (md) among the raw material monomers used as raw materials for the resin precursor (PA) is preferably 1 to 30 mol%, more preferably 3 to 25 mol%, and even more preferably 5 to 20 mol%.

[0150] The copolymerization reaction of raw monomers (monomers (ma), (m-pb), (mc), and monomer (md) used as needed) used when manufacturing a resin precursor (PA) can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. Specifically, for example, a method can be used in which a raw monomer, a polymerization initiator, and a polymerization solvent are mixed to form a raw monomer solution, and the polymerization reaction is carried out for 1 to 20 hours at a temperature of 50 to 100°C under a nitrogen gas atmosphere.

[0151] As a polymerization solvent used when manufacturing a resin precursor (PA), one or more types that can be used as a solvent (PC) included in the resin precursor composition described below may be used.

[0152] The temperature at which the raw material monomer is copolymerized is preferably lower than the dissociation temperature at which the dissociation rate of the block isocyanate group of the block isocyanate group-containing monomer (ma) is 80% or more in 30 minutes. This is because, in the raw material monomer solution during the copolymerization reaction, the dissociation of the block isocyanate group of the monomer (ma) to generate isocyanate groups and their reaction with the hydroxyl group of the hydroxyl group-containing monomer (mc) to gelation can be suppressed. The temperature at which the raw material monomer is copolymerized is more preferably 20 to 50°C lower than the dissociation temperature at which the dissociation rate of the block isocyanate group of the monomer (ma) is 80% or more in 30 minutes.

[0153] Specifically, the temperature at which the raw monomer is copolymerized can be 50 to 100°C, preferably 60 to 90°C, and more preferably 65 to 85°C.

[0154] Examples of polymerization initiators used when copolymerizing raw monomers include 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more types. The amount of polymerization initiator used may be 0.5 to 20 parts by mass per 100 parts by mass of raw monomer (total amount of monomer input), and preferably 1.0 to 10 parts by mass.

[0155] When manufacturing a resin precursor (PA), additives such as polymerization inhibitors, chain transfer agents, photosensitizers, fillers, and plasticizers may be used as needed, to the extent that the effects of the present invention are not impaired.

[0156] <Resin Precursor Composition>

[0157] The resin precursor composition of the present embodiment contains the resin precursor (PA) of the present embodiment, a basic catalyst (PB), and a solvent (PC). By containing the basic catalyst (PB), the resin precursor composition can convert the constituent unit (pb) included in the resin precursor (PA) into the constituent unit (b) described below, thereby enabling the production of the resin (A) of the present embodiment.

[0158] [Basic Catalyst (PB)]

[0159] The basic catalyst (PB) is a group represented by Formula (1) having a constituent unit (pb) included in the resin precursor (PA), R 3 The carbon atom bonded to this and R 4 It is sufficient if it can form a double bond between the carbon atoms bonded together, and is not particularly limited.

[0160] As for the basic catalyst (PB), it is preferable to use one having a pKa (acidity constant) of 12.5 or higher at 25°C. Basic catalysts (PB) having a pKa of 12.5 or higher at 25°C include those having a pKa of 12.5 or higher in an aqueous solution, and those whose acidity is too strong to be measured in an aqueous solution, but whose pKa in an aqueous solution calculated from the measurement result in an organic solvent is 12.5 or higher.

[0161] The basic catalyst (PB) is preferably a compound represented by the following formula (5).

[0162] R 11 N=CR 12 -NR 13 R 14 … (5)

[0163] (In Equation (5), R 11 A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or -N(R 15 R in the expression expressed as )2 15is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 2 R 15 (They may be identical or different.) R 12 , R 13 and R 9 is, respectively, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 11 , R 12 , R 13 , R 14 and 2 R 15 Among them, any two or more ki may combine to form a ring structure.)

[0164] The basic catalyst (PB) may be a compound represented by formula (5-2).

[0165] R 16 N=CR 17 -NR 18 R 19 … (5-2)

[0166] (In Equation (5-2), R 16 , R 17 , R 18 and R 19 is a hydrocarbon group. R 16 and R 19 They combine to form a ring structure. R 16 and R 19 The sum of the number of carbon atoms is 3 to 20. R 17 and R 18 They combine to form a ring structure. R 17 and R 18 The sum of the number of carbon atoms is 3 to 20.

[0167] In the compound represented by formula (5-2), R forming a cyclic structure 16 and R 19 The sum of the number of carbon atoms is 3 to 20, and preferably 3 to 10 from the perspective of ease of availability.

[0168] In the compound represented by formula (5-2), R forming a cyclic structure17 and R 18 The sum of the number of carbon atoms is 3 to 20, and preferably 3 to 10 from the perspective of ease of availability.

[0169] As for the basic catalyst (PB), specifically, it is preferable to use one or more selected from 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU) (pKa 12.5), 1,5-diazabicyclo[4.3.0]-5-nonene (pKa 12.7), and 1,1,3,3-tetramethylguanidine (pKa 13.6), and in particular, it is preferable to use 1,8-diazabicyclo[5.4.0]-undecene-7 from the perspective of the strength of catalytic activity, compatibility with solvents, and ease of availability.

[0170] The content of the basic catalyst (PB) is preferably 0.01 to 10 parts by mass per 100 parts by mass of the resin precursor (PA), more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass. The above content may be 0.2 to 2 parts by mass or 0.5 to 1 part by mass, etc. If the content of the basic catalyst (PB) is 0.01 parts by mass or more, it is preferable that the reaction rate of converting the constituent unit (pb) included in the resin precursor (PA) into the constituent unit (b) is sufficiently fast. If the content of the basic catalyst (PB) is 10 parts by mass or less, the influence of the basic catalyst (PB) can be suppressed when curing the resin composition prepared using the resin precursor composition.

[0171] [Solvent (PC)]

[0172] As a solvent (PC), for example, (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, 3-methoxy-1-butanol; hydroxyl group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutyrate; Hydroxyl group-containing solvents such as diethylene glycol, (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Esters such as 3-methyl methoxypropionate, 3-methyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxo-butyrate, etc.; aromatic hydrocarbons such as toluene and xylene; Examples include hydroxyl group-free solvents such as carboxylic acid amides, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more types.

[0173] Among these solvents (PC), it is preferable to use ethers for ease of availability, cost, and stability during resist production, and specifically, it is more preferable to use one or more 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.

[0174] The content of the solvent (PC) is preferably 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, based on 100 parts by mass of the total of components other than the solvent (PC) included in the resin precursor composition. Depending on the needs, the above content may be 70 to 500 parts by mass or 100 to 300 parts by mass, etc. It is preferable that the content of the solvent (PC) be 30 parts by mass or more because a stable polymerization reaction can be performed. It is preferable that the content of the solvent (PC) be 1,000 parts by mass or less because the viscosity of the resin precursor composition can be appropriately adjusted.

[0175] Method for preparing a resin precursor composition

[0176] The resin precursor composition of the present embodiment can be prepared by a method of mixing a resin precursor (PA), a basic catalyst (PB), and a solvent (PC) using a known mixing apparatus.

[0177] When preparing the resin precursor composition of the present embodiment, the reaction solution obtained by copolymerizing raw material monomers to produce a resin precursor (PA) may be used as is as a raw material. In this case, the resin precursor composition of the present embodiment may contain additives such as a polymerization initiator used when preparing the resin precursor (PA), a solvent used as necessary, and a polymerization inhibitor. Additionally, as a raw material for preparing the resin precursor composition, the resin precursor (PA) isolated from the reaction solution obtained by copolymerizing raw material monomers to produce the resin precursor (PA) may be used.

[0178] When preparing the resin precursor composition of the present embodiment, the resin precursor (PA) and / or basic catalyst (PB) used as raw materials may be in the form of a mixture with a solvent. In this case, the solvent included in the mixture with the resin precursor (PA) and / or basic catalyst (PB) may be used as the solvent (PC) included in the resin precursor composition.

[0179] The resin precursor composition of the present embodiment may contain, in addition to the resin precursor (PA), basic catalyst (PB), and solvent (PC), one or more known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors as needed. The content of these additives may be within a range that does not impede the effects of the present invention and is not particularly limited. The additives included in the resin precursor composition may be those added when adjusting the resin precursor composition, those added when manufacturing the resin precursor (PA), or those remaining from the synthesis of the raw monomer used when manufacturing the resin precursor (PA).

[0180] Suzy (A)

[0181] The resin (A) of the present embodiment is a copolymer containing a constituent unit (a) having a block isocyanate group, a constituent unit (b) having one or more groups selected from the following formula (2-2) and the following formula (3-2) (hereinafter simply referred to as “constituent unit (b)”), and a constituent unit (c) having a hydroxyl group.

[0182]

[0183] (In Equation (2-2), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0184]

[0185] (In Equation (3-2), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0186] The constituent unit (a) having a block isocyanate group in the resin (A) is identical to the constituent unit (a) having a block isocyanate group in the resin precursor (PA). The constituent unit (c) having a hydroxyl group in the resin (A) is identical to the constituent unit (c) having a hydroxyl group in the resin precursor (PA). Therefore, as monomers that derive constituent units (a) and (c) in the resin (A), respectively, compounds identical to the monomers (monomers (ma), (mc)) that derive constituent units (a) and (c) in the resin precursor (PA), respectively, may be cited.

[0187] The resin (A) of the present embodiment may, if necessary, contain other constituent units (d) other than constituent units (a) to (c).

[0188] Other constituent units (d) that may be included in the resin (A) are the same as other constituent units (d) that may be included in the resin precursor (PA). Therefore, as a monomer that derives the constituent unit (d) in the resin (A), a compound that is the same as the monomer (md) that derives the constituent unit (d) in the resin precursor (PA) can be cited.

[0189] In the resin (A) of the present embodiment, a portion of the constituent unit (c) having a hydroxyl group may include a carboxyl group derived from a polybasic acid (e).

[0190] The proportions of constituent units (a), (b), and (c) in resin (A) are the same as the proportions of constituent units (a), (pb), and (c) in resin precursor (PA), respectively.

[0191] When the resin (A) contains a constituent unit (d), the ratio of constituent units (a) to (d) in the resin (A) is the same as the ratio of constituent units (a), (pb), (c), and (d) in the resin precursor (PA), respectively.

[0192] [Constituent unit (b)]

[0193] The constituent unit (b) is a constituent unit having one or more groups selected from the above formulas (2-2) and (3-2), and is derived from the constituent unit (pb) contained in the aforementioned resin precursor (PA). Accordingly, it is preferable that the constituent unit (b) is a constituent unit derived from a monomer (m-pb) having a (meth)acryloyloxy group and a group represented by formula (1).

[0194] The resin (A) of the present embodiment has an ethylenically unsaturated group introduced by containing a constituent unit (b). Since the resin composition containing the resin (A) contains the constituent unit (b), when photocured, the reactive diluent (D) described later polymerizes together with the ethylenically unsaturated group contained in the constituent unit (b), and exhibits good photocurability.

[0195] In the apparatus represented by Equation (2-2) which may be included in the constituent unit (b), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R in the group represented by formula (1). 1 Likewise, it is preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. R in the group represented by Formula (2-2). 1 R in the device represented by Equation (1) 1 Likewise, it is preferable that it be an alkyl group, preferably a methyl or ethyl group, and particularly preferable that it be an ethyl group.

[0196] In Equation (2-2), R 3 and R 4 is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R in the group represented by formula (1). 3 and R 4 Likewise, preferably it is a hydrogen atom or has 1 to 5 carbon atoms, more preferably it is a hydrogen atom or a methyl group, and particularly preferably it is a hydrogen atom. R in Formula (2-2) 3 and R 4 is R in the device represented by Equation (1). 3 and R 4 Likewise, it may be the same or different.

[0197] In the apparatus represented by Equation (3-2) which may be included in the constituent unit (b), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R in the group represented by formula (1). 2 Likewise, it is preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. R in the group represented by Formula (2-3). 2R in the device represented by Equation (1) 2 Likewise, it is preferable that it be an alkyl group, preferably a methyl or ethyl group, and particularly preferable that it be an ethyl group.

[0198] In Equation (3-2), R 3 and R 4 is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R in the group represented by formula (1). 3 and R 4 Likewise, preferably it is a hydrogen atom or has 1 to 5 carbon atoms, more preferably it is a hydrogen atom or a methyl group, and particularly preferably it is a hydrogen atom. R in Formula (3-2) 3 and R 4 is R in the device represented by Equation (1). 3 and R 4 Likewise, it may be the same or different.

[0199] [Polybasic acid (e)]

[0200] In the resin (A) of the present embodiment, a portion of the constituent unit (c) having a hydroxyl group may include a carboxyl group derived from a polybasic acid (e). When a portion of the constituent unit (c) includes a carboxyl group derived from a polybasic acid (e), alkali developability can be imparted to the resin composition containing the resin (A). Furthermore, the resin composition containing such resin (A) obtains better curability and a cured product having superior solvent resistance.

[0201] Polybasic acid (e) is a compound having multiple carboxyl groups within one molecule. As for the polybasic acid (e), it is preferable that it be a compound in which at least two carboxyl groups undergo dehydration condensation to form an acid anhydride. Among such polybasic acid (e), a dibasic acid is preferred, and using a dibasic acid anhydride is more preferable. When a dibasic acid anhydride is used as the polybasic acid (e), the synthesis of resin (A) is easy, and the adjustment of the acid value of resin (A) is also easy.

[0202] Examples of polybasic acids (e) include, specifically, maleic anhydride, phthalic anhydride, succinic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, trimellitic anhydride, etc. Among these polybasic acids (e), succinic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, and maleic anhydride are preferred in terms of ease of availability, and succinic anhydride is more preferred in that it has the simplest structure and efficiently exhibits the effects of polybasic acid (e). Polybasic acid (e) may be used alone or in combination of two or more types.

[0203] When a portion of the constituent unit (c) having a hydroxyl group includes a carboxyl group derived from a polybasic acid (e), the content of the constituent unit (c) containing the carboxyl group derived from the polybasic acid (e) is preferably 1 to 30 moles with respect to 100 moles of the total of constituent units (a) to (d) included in the resin (A), more preferably 5 to 25 moles, and even more preferably 10 to 23 moles. If the content of the constituent unit (c) containing the carboxyl group derived from the polybasic acid (e) is 1 mole or more, sufficient alkali development properties can be imparted to the resin composition containing the resin (A). Furthermore, the resin composition containing the resin (A) obtains better curability and a cured product having excellent solvent resistance is obtained. If the content of the constituent unit (c) containing a carboxyl group derived from the polybasic acid (e) is 30 moles or less, the solubility of the resin composition containing the resin (A) in the alkaline developer can be suppressed.

[0204] When a portion of the constituent unit (c) having a hydroxyl group includes a carboxyl group derived from a polybasic acid (e), the content of the constituent unit (c) containing the carboxyl group derived from the polybasic acid (e) is preferably 10 to 80 moles per 100 moles of constituent unit (c) contained in the resin (A), more preferably 20 to 70 moles, and even more preferably 30 to 60 moles. If the content of the constituent unit (c) containing the carboxyl group derived from the polybasic acid (e) is 10 moles or more, the resin (A) has a sufficient amount of carboxyl groups. If the content of the constituent unit (c) containing the carboxyl group derived from the polybasic acid (e) is 80 moles or less, the resin (A) contains a sufficient amount of hydroxyl groups of the constituent unit (c). Accordingly, a resin composition containing resin (A) is obtained such that, by heating to cure the resin composition, the hydroxyl group of the constituent unit (c) and the block isocyanate group of the constituent unit (a) dissociate and the regenerated isocyanate group undergo a cross-linking reaction, thereby obtaining good low-temperature curability.

[0205] The weight average molecular weight of the resin (A) in terms of polystyrene is not particularly limited, but is preferably 1,500 to 50,000, more preferably 3,500 to 40,000, and even more preferably 5,000 to 20,000. If the weight average molecular weight of the resin (A) is 1,500 or more, the resin composition containing the resin (A) can form a cured product having better solvent resistance. If the weight average molecular weight of the resin (A) is 50,000 or less, a suitable viscosity can be imparted to the resin composition containing the resin (A), and it becomes easier to obtain a resin composition that is easy to handle. In addition, if the weight average molecular weight of the resin (A) is 50,000 or less, the development time can be appropriately controlled when the resin composition containing the resin (A) is a photosensitive material.

[0206] The resin (A) of the present embodiment contains a constituent unit (a) having a block isocyanate group and contains a block isocyanate group in the molecule. The content of the block isocyanate group in the resin (A) may be appropriately selected, but, as with the block isocyanate group equivalent in the resin precursor (PA), it is typically selected in the range where the block isocyanate group equivalent is 400 to 6,000 g / mol, preferably 500 to 5,000 g / mol, and more preferably 700 to 3,000 g / mol.

[0207] The block isocyanate equivalent in resin (A) is the mass of resin (A) per mole of block isocyanate contained in resin (A), and is obtained by dividing the mass of resin (A) by the number of moles of block isocyanate contained in resin (A) (g / mol). In the present invention, the block isocyanate equivalent in resin (A) is a theoretical value calculated from the amount of block isocyanate-containing monomer (ma) used as a raw material for the resin precursor (PA).

[0208] The resin (A) of the present embodiment contains a constituent unit (b) having one or more groups selected from formula (2-2) and formula (3-2), and contains an ethylenically unsaturated group in the molecule. The content of the ethylenically unsaturated group in the resin (A) may be appropriately selected, but is typically selected in the range where the ethylenically unsaturated group equivalent is 200 to 5,000 g / mol, preferably 500 to 3,000 g / mol, and more preferably 500 to 1,500 g / mol. If the ethylenically unsaturated group equivalent in the resin (A) is 200 g / mol or more, the stability of the resin (A) can be sufficiently maintained. If the content of ethylenically unsaturated groups in the resin (A) is 5,000 g / mol or less, when the resin composition containing the resin (A) is a photosensitive material, it is desirable because the reactive diluent (D) described later polymerizes together with the ethylenically unsaturated groups included in the constituent unit (b) by photocuring, and exhibits good photocurability.

[0209] The equivalent of an ethylene unsaturated group in resin (A) is the mass of resin (A) per mole of an ethylene unsaturated group contained in resin (A), and is obtained by dividing the mass of resin (A) by the number of moles of an ethylene unsaturated group contained in resin (A) (g / mol). In the present invention, the equivalent of an ethylene unsaturated group in resin (A) is a theoretical value calculated from the input amounts of a monomer (m-pb) having a group represented by Formula (1) and a polybasic acid (e). When maleic anhydride is used as the polybasic acid (e), the equivalent of an ethylene unsaturated group in resin (A) is obtained by dividing the mass of resin (A) by the number of moles of a monomer (m-pb) having a group represented by Formula (1) and the polybasic acid (e).

[0210] When a portion of the constituent unit (c) having a hydroxyl group in the resin (A) includes a carboxyl group derived from a polybasic acid (e), the acid value (solid dispersion acid value) of the resin (A) is preferably in the range of 20 to 300 KOH mg / g, and more preferably in the range of 30 to 200 KOH mg / g. If the acid value of the resin (A) is 20 KOH mg / g or higher, the alkali developability of the resin composition containing the resin (A) becomes better. In addition, a cured product having better solvent resistance is obtained from the resin composition containing the resin (A). On the other hand, if the acid value of the resin (A) is 300 KOH mg / g or lower, when the resin composition containing the resin (A) is a photosensitive material, the exposed portion (photocured portion) becomes difficult to dissolve with respect to the alkali developer, and a good pattern shape can be formed.

[0211] The acid value of the resin (A) in this embodiment is measured by the method described in JIS K69015.3.

[0212] The hydroxyl group equivalent in the resin (A) may be appropriately selected, but is typically selected within a range of 300 to 6000 g / mol, preferably 400 to 4000 g / mol, and more preferably 500 to 2500 g / mol. It is preferable that the hydroxyl group equivalent in the resin (A) be 300 g / mol or more, as this does not impair the compatibility of other components of the resin composition. If the hydroxyl group equivalent in the resin (A) is 6000 g / mol or less, a sufficient number of hydroxyl groups can be secured to react with isocyanato groups regenerated by heating to cure the resin composition containing the resin (A). For this reason, the resin composition is obtained in which a cured product with better low-temperature curing properties and excellent solvent resistance is obtained.

[0213] The hydroxyl group equivalent in resin (A) is the mass of resin (A) per mole of hydroxyl group contained in resin (A), and is obtained by dividing the mass of resin (A) by the number of moles of hydroxyl group contained in resin (A) (g / mol). In the present invention, the hydroxyl group equivalent in resin (A) is a theoretical value calculated from the input amount of constituent unit (c) having a hydroxyl group.

[0214] <Method for manufacturing resin (A)>

[0215] The resin (A) of the present embodiment is derived from the aforementioned resin precursor (PA). Specifically, a resin precursor composition containing the resin precursor (PA), a basic catalyst (PB), and a solvent (PC) is maintained at a temperature of, for example, 0 to 150°C for 0.1 to 10 hours. By doing so, the resin precursor (PA) is subjected to a dealolysis reaction and a decarboxylation reaction to convert the constituent unit (pb) contained in the resin precursor (PA) into a constituent unit (b), and a reaction solution containing the resin (A) and the solvent (PC) is produced.

[0216] The conversion reaction for converting constituent unit (pb) into constituent unit (b) is preferably carried out under a temperature condition below which the dissociation rate of the block isocyanate group in constituent unit (a) having a block isocyanate group is 70% or more in 30 minutes. This is because, in the resin precursor composition during the conversion reaction, the dissociation of the block isocyanate group in constituent unit (a) to generate isocyanate groups and their reaction with the hydroxyl group in constituent unit (c) having a hydroxyl group to cause gelation can be suppressed. The temperature condition for carrying out the conversion reaction is more preferably 20 to 50°C lower than the temperature at which the dissociation rate of the block isocyanate group in constituent unit (a) is 70% or more in 30 minutes.

[0217] Specifically, the temperature of the conversion reaction that converts the constituent unit (pb) into the constituent unit (b) can be 0 to 150°C, preferably 50 to 120°C, and more preferably 60 to 100°C. These temperatures are also preferred as the temperature for forming the reaction solution.

[0218] The holding time for maintaining the resin precursor composition under the above temperature conditions to carry out the above conversion reaction can be 0.1 to 10 hours, preferably 0.3 to 5 hours, and more preferably 0.5 to 3 hours. The holding time can be appropriately determined according to the content of the constituent unit (pb) included in the resin precursor (PA) in the resin precursor composition, the content of the basic catalyst (PB), temperature conditions, etc.

[0219] The atmosphere within the reaction vessel in which the above conversion reaction is carried out may be an atmosphere including, for example, air, dry air, nitrogen gas, helium gas, etc., and it is preferable that it be a dry air or nitrogen gas atmosphere.

[0220] The pressure in the reaction vessel carrying out the above conversion reaction is not particularly limited, but it is preferably atmospheric pressure.

[0221] (Reaction Pathway)

[0222] In the method for manufacturing resin (A) of the present embodiment, the constituent unit (pb) included in the resin precursor (PA) is presumed to be converted into constituent unit (b) by the reaction pathway shown below.

[0223] That is, in a constituent unit (pb) having a group represented by formula (1) included in a resin precursor (PA), the -NH- portion in the urethane bond and the ester portion (-COOR 1 or -COOR 2 ) undergoes a de-alcoholization reaction.

[0224] Accordingly, a unit having a complex number represented by the following equation (2-1) and / or the following equation (3-1) is formed. The unit having a complex number represented by equation (2-1) is R in the unit represented by equation (1). 2 The ester portion containing is dealolated (-R 2 It is formed by the reaction of OH). The group having a complex ring represented by Equation (3-1) is R in the group represented by Equation (1). 1 The ester portion containing is dealolated (-R 1 It is formed by the reaction of OH.

[0225]

[0226] (In Equation (2-1), R 1 , R 3 and R 4 is R in Equation (1) 1 , R 3 and R 4 It is the same as.)

[0227]

[0228] (In Equation (3-1), R 2 , R 3 and R 4 is R in Equation (1) 2 , R 3 and R 4 It is the same as.)

[0229] Next, in the device having a complex ring represented by the above equation (2-1), decarbonation (-CO2) occurs in the complex ring portion. As a result, the device having a complex ring represented by the equation (2-1) is converted into a device represented by the following equation (2-2).

[0230]

[0231] (In Equation (2-2), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0232] In addition, in the process having a complex cycle represented by the above equation (3-1), decarbonation (-CO2) occurs in the complex cycle portion. As a result, the process having a complex cycle represented by the above equation (3-1) is converted into a process represented by the following equation (3-2).

[0233]

[0234] (In Equation (3-2), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0235] In the density functional method, when wB97XD was used as the functional and 6-31+g(d) as the basis function, the transition state calculations in the production pathways of each product were performed. As a result, the conversion reaction that converts the aforementioned constituent unit (pb) into constituent unit (b) showed that the reaction pathways of Equation (1), Equation (3-1), and Equation (3-2) had lower activation barriers compared to the conversion routes of Equation (1), Equation (2-1), and Equation (2-2). Therefore, it is presumed that the former is the main conversion route. Accordingly, in the resin (A), constituent units having the group represented by Equation (3-2) and constituent units having the group represented by Equation (2-2) are mixed, and it is also presumed that constituent units having the group represented by Equation (3-2) exist in greater numbers than constituent units having the group represented by Equation (2-2).

[0236] (Addition reaction of polybasic acid (e))

[0237] In the case of manufacturing a resin (A) of the present embodiment in which a portion of the constituent unit (c) having a hydroxyl group includes a carboxyl group derived from a polybasic acid (e), it can be manufactured by the method described below. First, a conversion reaction is performed to convert a constituent unit (pb) included in a resin precursor (PA) into a constituent unit (b) by the above method, thereby forming a reaction solution containing resin (A) and a solvent (PC). Then, a polybasic acid (e) is added to the reaction solution, and an addition reaction is performed between the resin (A) and the polybasic acid (e). By doing so, a portion of the constituent unit (c) having a hydroxyl group included in the resin (A) is made to include a carboxyl group derived from the polybasic acid (e), and a reaction solution is formed containing the resin (A) to which the polybasic acid (e) has been added.

[0238] When carrying out an addition reaction between a resin (A) and a polybasic acid (e), metal catalysts such as lithium naphthenate, chromium naphthenate, zirconium naphthenate, or cobalt naphthenate, phosphorus catalysts such as triphenylphosphine or trimethylphosphine, or amine catalysts such as triethylamine may be used as needed. The amount of catalyst used can be appropriately determined according to conditions such as the temperature and / or time of the addition reaction, the type of resin (A) and polybasic acid (e), and is not particularly limited.

[0239] The reaction between the resin (A) and the polybasic acid (e) can be carried out, for example, at a temperature of 50 to 120°C, preferably at a temperature of 60 to 100°C, and more preferably at a temperature of 65 to 90°C.

[0240] The temperature at which the addition reaction between the resin (A) and the polybasic acid (e) is carried out is preferably less than the temperature at which the dissociation rate of the block isocyanate group in the constituent unit (a) having the block isocyanate group included in the resin (A) is 70% or more in 30 minutes. This is because by carrying out the addition reaction between the resin (A) and the polybasic acid (e), the dissociation of the block isocyanate group in the constituent unit (a) to generate isocyanate groups, and the reaction with the hydroxyl group in the constituent unit (c) having the hydroxyl group to gelation can be suppressed. It is more preferable to carry out the addition reaction between the resin (A) and the polybasic acid (e) at a temperature 20 to 50°C lower than the temperature at which the dissociation rate of the block isocyanate group in the constituent unit (a) is 70% or more in 30 minutes.

[0241] The holding time (reaction time) for maintaining the above temperature to carry out the addition reaction between the resin (A) and the polybasic acid (e) can be, for example, 10 to 300 minutes, preferably 15 to 120 minutes, and preferably continued until the polybasic acid (e) is consumed. The consumption of the polybasic acid (e) can be confirmed, for example, by the IR spectrum measured using infrared absorption (IR) spectroscopy.

[0242] <Resin Composition>

[0243] Next, the resin composition of the present embodiment will be described in detail.

[0244] The resin composition of the present embodiment contains the resin (A) of the present embodiment, a solvent (C), a reactive diluent (D), and a photopolymerization initiator (E). The resin composition of the present embodiment may also contain a coloring agent (F) if necessary.

[0245] The content of resin (A) in the resin composition is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total of resin (A) and reactive diluent (D), more preferably 30 to 85 parts by mass, and even more preferably 60 to 80 parts by mass. If the content of resin (A) is 10 parts by mass or more, the resin composition can form a cured product having superior low-temperature curing properties and good solvent resistance. If the content of resin (A) is 90 parts by mass or less, the content of reactive diluent (D) can be sufficiently secured, so a cured product with good strength and adhesion to the substrate can be formed.

[0246] [Solvent (C)]

[0247] As for the solvent (C), the same solvent (PC) used in the resin precursor composition may be used. The solvent (C) in the resin composition and the solvent (PC) in the resin precursor composition used when manufacturing the resin composition may be the same or different.

[0248] The content of solvent (C) in the resin composition is preferably 30 to 1,000 parts by mass with respect to 100 parts by mass of the total of resin (A) and reactive diluent (D), and more preferably 50 to 800 parts by mass. If necessary, the above content may be 80 to 500 parts by mass or 100 to 300 parts by mass, etc. If the content of solvent (C) is 30 parts by mass or more, it can be made to have an appropriate viscosity according to the application. If the content of solvent (C) is 1,000 parts by mass or less, the solvent (C) can be easily removed when removing the solvent (C) from the coating film formed by applying the resin composition onto a substrate.

[0249] [Reactive Diluent (D)]

[0250] The reactive diluent (D) is a monomer comprising a compound having at least one ethylenically unsaturated bond as a polymerizable functional group within the molecule. The reactive diluent (D) may be a monofunctional monomer or a polyfunctional monomer having multiple polymerizable functional groups. By containing the reactive diluent (D), the resin composition of the present embodiment can be made to have an appropriate viscosity for the application. Furthermore, because the resin composition of the present embodiment contains the reactive diluent (D), it is possible to form a cured product having good photocurability and good strength and adhesion to the substrate.

[0251] Monofunctional monomers used as reactive diluents (D) include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth)acrylate, Examples include (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. These monofunctional monomers may be used alone or in combination of two or more.

[0252] As polyfunctional monomers used as reactive diluents (D), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, (Meth)acrylates such as 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), reaction products of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; Examples include aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; dicarboxylic acid esters such as divinyl adipoyl; trialyl cyanurate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohol and N-methylol(meth)acrylamide. These polyfunctional monomers may be used alone or in combination of two or more.

[0253] Among these monomers, it is preferable to use a polyfunctional (meth)acrylate as a reactive diluent (D) because it results in a resin composition with good photocuring properties, and specifically, it is more preferable to use a polyfunctional (meth)acrylate with three or more functions, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0254] The content of the reactive diluent (D) in the resin composition is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the total of the resin (A) and the reactive diluent (D), more preferably 15 to 70 parts by mass, and even more preferably 20 to 40 parts by mass. If the content of the reactive diluent (D) is 10 parts by mass or more, the effect of containing the reactive diluent (D) becomes significant. If the content of the reactive diluent (D) is 90 parts by mass or less, the content of the resin (A) can be sufficiently secured, so the resin composition becomes one with even better low-temperature curing properties.

[0255] [Photopolymerization initiator (E)]

[0256] As a photopolymerization initiator (E), examples include, but are not particularly limited, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-, -1-(O-acetyloxime); benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; Examples include anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxantones such as xanthone, thioxantone, 2,4-dimethylthioxantone, 2,4-diisopropylthioxantone, and 2-chlorothioxantone; ketal types such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxides. These photopolymerization initiators (E) may be used alone or in combination of two or more types.

[0257] The content of the photopolymerization initiator (E) in the resin composition is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total of the resin (A) and the reactive diluent (D), more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass. If the content of the photopolymerization initiator (E) is 0.1 parts by mass or more, the resin composition has good photocuring properties. If the content of the photopolymerization initiator (E) is 30 parts by mass or less, it is possible to prevent adverse effects on the physical properties of the cured product of the resin composition caused by an excessive amount of the photopolymerization initiator (E).

[0258] [Colorant (F)]

[0259] The resin composition of the present embodiment may contain a coloring agent (F). A resin composition containing a coloring agent (F) can be used as a material for a color filter.

[0260] The coloring agent (F) is not particularly limited as long as it is dissolved or dispersed in the solvent (C), and examples include dyes, pigments, etc.

[0261] As for the dye, it is preferable to use an acid dye having an acidic group such as a carboxylic acid and / or sulfonic acid, a salt of an acid dye with a nitrogen compound, or a sulfonamide of an acid dye, in terms of solubility in a solvent (C) and an alkaline developer, interaction with other components in the resin composition, and heat resistance.

[0262] Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44, 70; acid chrome violet K; fusynic acid; 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; Examples include 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 derivatives thereof. Among these, azo, xanthen, anthraquinone, or phthalocyanine acid dyes are preferred.

[0263] Examples of pigments include yellow pigments such as CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments such as CI Pigment Green 7, 36, 58, 59; brown pigments such as CI Pigment Brown 23, 25; Examples of black pigments include CI pigment black 1, 7, carbon black, titanium black, iron oxide, etc.

[0264] The coloring agent (F) can be appropriately determined according to the color of the intended coloring pattern (black matrix and pixel), etc., when the resin composition of the present embodiment can be used as a material for the coloring pattern of the color filter. The coloring agent (F) may be used as a single type or as a combination of two or more types. When two or more types are used as coloring agents (F), the above dye and the above pigment may be used in combination.

[0265] When using a pigment as the coloring agent (F), a known dispersant may be incorporated into the resin composition to improve the dispersibility of the coloring agent (F). As the dispersant, it is preferable to use a polymeric dispersant that has excellent dispersion stability over time. Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As such polymeric dispersants, commercially available products under trade names such as EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by B.C.), Dispalon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) may be used. The content of the dispersant can be appropriately set according to the type and amount of the pigment, etc. used as the coloring agent (F).

[0266] The content of the coloring agent (F) in the resin composition is preferably 3 to 80 parts by mass with respect to 100 parts by mass of the total of the resin (A) and the reactive diluent (D), more preferably 5 to 70 parts by mass, and even more preferably 10 to 60 parts by mass. If the content of the coloring agent (F) is 3 parts by mass or more, the effect of containing the coloring agent (F) becomes significant, and the resin composition becomes suitable as a material for the coloring pattern of a color filter. If the content of the coloring agent (F) is 80 parts by mass or less, the coloring agent (F) in the resin composition does not cause any impediment to the curability of the resin composition, and the resin composition has good low-temperature curability.

[0267] The resin composition of the present embodiment may, in addition to the resin (A), solvent (C), reactive diluent (D), photopolymerization initiator (E), and colorant (F) contained as needed, incorporate known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors as needed. The amount of these additives incorporated may be within a range that does not impede the effects of the present invention and is not particularly limited.

[0268] Method for manufacturing a resin composition

[0269] The resin composition of the present embodiment can be prepared by a method of mixing a resin (A), a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and a coloring agent (F) included as needed, using a known mixing device.

[0270] When preparing the resin composition of the present embodiment, as a raw material, a reaction solution containing a resin (A) obtained by converting a constituent unit (pb) in the resin precursor composition into a constituent unit (b) and a solvent (PC) may be used as is, or a reaction solution containing a resin (A) to which a polybasic acid (e) has been added may be used as is. In this case, the solvent (PC) included in the reaction solution may be used as part or all of the solvent (C) included in the resin composition.

[0271] When preparing the resin composition of the present embodiment, the resin (A) isolated by a known method from a reaction solution containing the above resin (A) and a solvent (PC) or a reaction solution containing the resin (A) to which a polybasic acid (e) has been added may be used as a raw material.

[0272] The resin composition of the present embodiment contains a resin (A) having a constituent unit (b) having one or more groups selected from formula (2-2) and formula (3-2), a reactive diluent (D), and a photopolymerization initiator (E). By photocuring, the reactive diluent (D) polymerizes together with the ethylenically unsaturated group included in the constituent unit (b) of the resin (A), and exhibits good photocurability.

[0273] In addition, the resin composition of the present embodiment has good low-temperature curing properties because it contains a resin (A) having a constituent unit (a) having a block isocyanate group and a constituent unit (c) having a hydroxyl group.

[0274] In this regard, when forming a cured product using the resin composition of the present embodiment, the heating temperature for curing can be lowered compared to when using a conventional resin composition. Accordingly, when the resin composition of the present embodiment performs a baking treatment after, for example, exposing a coating film formed on a substrate to light, the crosslinking reaction proceeds sufficiently even if the baking treatment temperature is lowered, thereby obtaining a cured product with excellent solvent resistance.

[0275] Therefore, when forming a cured product using the resin composition of the present embodiment, the energy required for heating to cure is reduced. Furthermore, by using the resin composition of the present embodiment, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without causing damage to the substrate. Additionally, when the resin composition includes a coloring agent (F), it becomes possible to use a coloring agent (F) with low heat resistance. As a result, a cured product can be formed in which the inherent characteristics of the coloring agent (F) are exhibited.

[0276] In addition, since the resin composition of the present embodiment yields a cured product with excellent solvent resistance even when the baking temperature is low, it is possible to increase the content of the coloring agent (F) in the resin composition. A resin composition with a high content of the coloring agent (F) can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproducibility.

[0277] In addition, when the resin (A) included in the resin composition of the present embodiment has a carboxyl group derived from a polybasic acid (e) in part of the constituent unit (c) having a hydroxyl group, it has better low-temperature curing properties and, furthermore, good storage stability and alkali developability. Since such a resin composition has excellent alkali developability, for example, by applying it onto a substrate to form a coating film, exposing it through a photomask corresponding to a predetermined pattern shape, developing the unexposed portion with an alkaline aqueous solution, and then baking it at a sufficiently low temperature, a cured product with excellent solvent resistance having a predetermined pattern shape can be formed.

[0278] In addition, when the resin composition of the present embodiment contains a coloring agent (F), it can be suitably used as a material for a color filter.

[0279] In this regard, the resin composition of the present embodiment is very useful as a material for forming components of an image display element, such as, for example, pixels of a color filter, a black matrix, a color filter protective film, a photospacer, a liquid crystal alignment protrusion, a microlens, and an insulating film for a touch panel.

[0280] <Resin hardening film>

[0281] Next, the resin cured film of the present embodiment will be described in detail.

[0282] The resin cured film of the present embodiment comprises a cured product of the resin composition of the present embodiment.

[0283] The resin composition of the present embodiment can be manufactured by a method of, for example, applying the resin composition onto a substrate, volatilizing and removing the solvent (C) to form a coating film, exposing the coating film to light to photocuring, and then performing a baking treatment.

[0284] In the case of forming a resin cured film having a predetermined pattern shape as of the present embodiment, the method described below may be used, for example. That is, a resin composition is applied onto a substrate, and a solvent (C) is removed by volatilizing it to form a coating film. Then, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed portion is photocured. Then, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, a resin cured film having a predetermined pattern shape can be formed by performing a baking treatment on the developed coating film.

[0285] In manufacturing the resin cured film of the present embodiment, known methods may be used for the method of applying the resin composition, the method of exposing the coated film, and the method of developing.

[0286] The conditions for the baking treatment performed when manufacturing the resin cured film of the present embodiment can be appropriately determined according to the composition of the resin composition, the film thickness of the coating film, the material of the substrate, etc. The baking treatment can be performed, for example, at a temperature of 70°C to 250°C. If the baking treatment temperature is 70°C or higher, the block isocyanate groups possessed by the constituent unit (a) having a block isocyanate group included in the resin (A) in the resin composition are sufficiently dissociated. As a result, isocyanate groups are generated and cross-link with the hydroxyl groups possessed by the constituent unit (c) having a hydroxyl group. As a result, good curability is obtained, and a cured product having excellent solvent resistance is obtained. The baking treatment temperature is preferably 75°C or higher, and more preferably 80°C or higher. If the baking treatment temperature is 250°C or lower, it is desirable because it is a condition that can withstand materials with low heat resistance and can suppress discoloration of the resin composition. The resin composition of the present embodiment has good low-temperature curability. For this reason, the temperature of the baking treatment can be set to 160°C or lower depending on the heat resistance of the substrate forming the resin cured film, for example, when a resin substrate is used as the substrate, it can be set to 150°C or lower, 120°C or lower, or 100°C or lower.

[0287] The baking treatment performed when manufacturing the resin cured film of the present embodiment can be performed for, for example, from 10 minutes to 4 hours, preferably from 20 minutes to 2 hours, and can be appropriately determined according to the composition of the resin composition, the temperature of the baking treatment, the film thickness of the coating film, etc.

[0288] The resin cured film of the present embodiment comprises a cured product of the resin composition of the present embodiment. Therefore, the resin cured film of the present embodiment can be manufactured using a baking treatment method at a low temperature, and furthermore, has excellent solvent resistance.

[0289] Color Filter

[0290] Next, the color filter of the present embodiment will be described in detail.

[0291] The color filter of the present embodiment comprises a member containing a cured product of the resin composition of the present embodiment. The color filter of the present embodiment preferably has a color pattern comprising a cured product of a resin composition containing, for every 100 parts by mass of the total of resin (A) and reactive diluent (D), 10 to 90 parts by mass of resin (A), 30 to 1000 parts by mass of solvent (C), 10 to 90 parts by mass of reactive diluent (D), 0.1 to 30 parts by mass of photopolymerization initiator (E), and 3 to 80 parts by mass of colorant (F).

[0292] The color filter of the present embodiment may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix.

[0293] In the color filter of the present embodiment, the pixels and the black matrix are colored patterns comprising a cured product of the resin composition. In the color filter of the present embodiment, components other than the materials of the pixels and the black matrix may be known.

[0294] The substrate used in the color filter of the present embodiment is not particularly limited, and may include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed circuit board, an array substrate, etc., depending on the application.

[0295] Method for manufacturing color filters

[0296] Next, a method for manufacturing a color filter according to the present embodiment is described. First, a coloring pattern is formed on a substrate. Specifically, a coloring pattern that becomes each RGB pixel and a coloring pattern that becomes a black matrix formed at the boundary of each pixel are sequentially formed on the substrate by the method shown below.

[0297] A colored pattern can be formed by photolithography. Specifically, the resin composition described above is applied onto a substrate to form a coating film. Then, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed portion is photocured. Subsequently, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, a colored pattern having a predetermined pattern shape can be formed by performing a baking treatment on the developed coating film.

[0298] The method of applying the resin composition is not particularly limited, but known methods such as screen printing, roll coating, curtain coating, spray coating, and spin coating may be used.

[0299] In addition, after applying a resin composition onto a substrate, if necessary, the solvent (C) contained in the coating film may be removed by volatilizing it by heating the substrate using a heating means such as a circulating oven, an infrared heater, or a hot plate. The conditions for heating the substrate to remove the solvent (C) are not particularly limited and can be appropriately set according to the material of the substrate, the composition of the resin composition, the thickness of the coating film, etc. Heating of the substrate may be performed, for example, at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0300] Next, an active energy line, such as ultraviolet light or excimer laser light, is irradiated onto the coating film formed in this manner through a negative-type photomask, partially exposed, and the exposed portion is photocured. The amount of active energy line irradiated onto the coating film can be appropriately selected according to the composition of the resin composition, and for example, can be 30 to 2000 mJ / cm². The light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc., can be used.

[0301] As for the alkaline aqueous solution used for developing the coating film, aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide may be used, although not specifically limited; aqueous solutions of amine-based compounds such as ethylamine, diethylamine, and dimethyl ethanolamine; aqueous solutions of tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and p-phenylenediamine-based compounds such as their sulfates, hydrochlorides, or p-toluenesulfonates. Additionally, defoaming agents and / or surfactants may be added to these aqueous solutions as needed.

[0302] After developing the coating film using the above alkaline aqueous solution, it is preferable to wash and dry the coating film.

[0303] The conditions for the baking treatment performed when manufacturing the color filter of the present embodiment can be appropriately determined according to the composition of the resin composition, the film thickness of the coating film, the material of the substrate, etc. The temperature of the baking treatment can be, for example, 70°C to 210°C. If the baking temperature is 70°C or higher, good curability is obtained, and a cured product having excellent solvent resistance is obtained. The temperature of the baking treatment is preferably 75°C or higher, and more preferably 80°C or higher. If the temperature of the baking treatment is 210°C or lower, it is preferable because a material with low heat resistance, such as a substrate with low heat resistance, can be used as the material for the color filter.

[0304] When forming a coloring pattern of a color filter using a conventional resin composition, if the baking temperature is 200°C or lower, the solvent resistance of the coloring pattern is insufficient. In contrast, since the resin composition of the present embodiment has good low-temperature curing properties, the baking temperature can be lowered compared to when using a conventional resin composition while ensuring the solvent resistance of the coloring pattern. Specifically, the baking temperature can be 160°C or lower depending on the heat resistance of the substrate forming the resin cured film; for example, when a resin substrate is used as the substrate to form a coloring pattern, it can be 150°C or lower, 120°C or lower, or 100°C or lower.

[0305] The baking treatment performed when manufacturing the color filter of the present embodiment can be performed for, for example, from 10 minutes to 4 hours, preferably from 20 minutes to 2 hours, and can be appropriately determined according to the composition of the resin composition, the temperature of the baking treatment, the thickness of the coating film, etc.

[0306] The resin composition of the present embodiment has good photocurability and low-temperature curability. Therefore, when forming a colored pattern using the resin composition of the present embodiment, if the baking temperature is made equivalent to that of forming a colored pattern using a conventional resin composition, the baking time can be shortened and a color filter can be formed efficiently.

[0307] Using the above-described method for manufacturing a coloring pattern, a coloring pattern that becomes each RGB pixel and a coloring pattern that becomes a black matrix formed at the boundary of each pixel are formed, and then a protective film is formed on the coloring pattern (each RGB pixel and the black matrix).

[0308] The method of manufacturing the protective film is not particularly limited and may be formed using the resin composition of the present embodiment, or may be formed using known materials and known methods.

[0309] By the above process, a color filter of the present embodiment is obtained.

[0310] The color filter of the present embodiment has a coloring pattern comprising a cured product of the resin composition described above. Accordingly, the coloring pattern in the color filter of the present embodiment can be formed by a method of performing a baking treatment at a low temperature. Therefore, the energy required for the baking treatment can be reduced.

[0311] In addition, in the color filter of the present embodiment, it is possible to use a colorant (F) with low heat resistance as the colorant included in the resin composition used as the material. Because of this, a wide range of options for the usable colorant (F) can be provided. Therefore, for example, it is possible to form a color filter that includes a colorant (F) with low heat resistance and has a color pattern in which the inherent characteristics of the colorant (F) with low heat resistance are exhibited.

[0312] Furthermore, the coloring pattern in the color filter of the present embodiment can be formed on a substrate with low heat resistance, such as a resin substrate, without causing damage to the substrate. Therefore, a wide range of usable substrate options is available. Specifically, since the color filter can be formed on a substrate with low heat resistance, such as a resin substrate, it can contribute to the flexibility of the display. In addition, the coloring pattern in the color filter of the present embodiment has excellent solvent resistance, resulting in minimal color change.

[0313] In the present embodiment, a case in which a colored pattern is manufactured by using a resin composition containing a photopolymerization initiator (E) and a method of photocuring the resin composition has been described as an example; however, instead of the photopolymerization initiator (E) included in the resin composition of the present embodiment, a resin composition containing a curing accelerator and a known epoxy resin may be used, and a method of applying it to a substrate by an inkjet method and then heating may be used to form a colored pattern containing a cured product of a resin composition containing resin (A).

[0314] Image display element

[0315] The image display element of the present embodiment is provided with a color filter of the present embodiment. The image display element of the present embodiment may employ known components other than the color filter of the present embodiment. Examples of the image display element of the present embodiment include a liquid crystal display element, an organic EL display element, a solid-state imaging element such as a CCD element or a CMOS element.

[0316] In the image display element of the present embodiment, components other than the color filter of the present embodiment can be manufactured by 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. Subsequently, electrodes, etc. are formed on another substrate and placed opposite the substrate having the color filter and joined together. After that, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0317] The image display element of the present embodiment is equipped with a color filter having excellent solvent resistance of the present embodiment, so that color change is minimal.

[0318] Examples

[0319] The present invention will be explained in detail below through examples and comparative examples. Furthermore, the examples described below are intended to facilitate a better understanding of the content of the present invention. The present invention is not limited to these examples.

[0320] [Example 1]

[0321] (Synthesis of resin precursor (PA))

[0322] 182 g of propylene glycol monomethyl ether (manufactured by Lyon Del Co.) was added as a solvent (PC) to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, stirred while purging with nitrogen gas, and heated to 78°C.

[0323] Next, 29.5 g (20 mol%) of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (manufactured by Showa Denko Co., Ltd., MOI-BP (registered trademark), dissociation temperature at which the dissociation rate of the blocked isocyanate group reaches 80% or more in 30 minutes: 110°C, dissociation rate when heated at 100°C for 30 minutes: 70%) as monomer (ma), 46.4 g (30 mol%) of 2-[(diethyl malate)carbonylamino]ethyl acrylate (manufactured by Showa Denko Co., Ltd., AOI-MDE (registered trademark)) as monomer (m-pb), 24.3 g (40 mol%) of hydroxyethyl methacrylate (HEMA) (manufactured by Nippon Shokubai Co., Ltd.) as monomer (mc), and monomer A mixed solution was prepared by mixing 8.6 g (10 mol%) of 2-ethylhexyl acrylate (2EHA) (manufactured by Doa Kose Co., Ltd.) as (md) and 17.4 g (16 parts per 100 parts by mass of the total monomer components) of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Junyaku Kogyo Co., Ltd.) as a polymerization initiator.

[0324] The entire amount of the prepared mixed solution was added dropwise over 1 hour using a dropping funnel to the solvent (PC) in a flask under atmospheric pressure in a nitrogen gas atmosphere. After the addition was finished, the solution in the flask was polymerized at 78°C for 2 hours while stirring to obtain a solution containing a resin precursor (PA) and the solvent (PC).

[0325] (Preparation of resin precursor composition)

[0326] A resin precursor composition was obtained by adding 0.2 g of 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU) (manufactured by San-Apro Co., Ltd.) as a basic catalyst (PB) (0.21 parts by mass per 100 parts by mass of the monomer components of the resin precursor (PA)) to a solution containing a resin precursor (PA) and a solvent (PC) in a flask under atmospheric pressure in a nitrogen gas atmosphere.

[0327] (Synthesis of resin (A))

[0328] In a flask under atmospheric pressure with a nitrogen gas atmosphere, the resin precursor composition was maintained at 78°C for 30 minutes while stirring, and the constituent unit (pb) having a group represented by Formula (1) included in the resin precursor (PA) was converted into a constituent unit (b) having one or more groups selected from Formulas (2-2) and (3-2). By doing so, a reaction solution containing resin (A) and solvent (PC) was produced. The obtained reaction solution containing resin (A) and solvent (PC) was analyzed using the infrared absorption (IR) spectroscopy method shown below.

[0329] [Infrared Absorption (IR) Spectroscopy]

[0330] For the analysis by IR spectroscopy, Thermo Fisher Scientific's NICOLETis10 was used as the analytical instrument, and SMART iTR was used as the accessory. In the ATR method, the C=C peak wavelength was 690 cm⁻¹. -1 By doing so, measurements were taken.

[0331] Figure 1 is a graph showing the IR spectrum of the resin precursor composition of Example 1 (before conversion reaction) and the IR spectrum of the reaction solution after the conversion reaction (after conversion reaction). As shown in Figure 1, in the IR spectrum after the conversion reaction, the wavelength is 690 cm⁻¹ -1 An infrared absorption peak that was not visible in the IR spectrum prior to the conversion reaction appears. In this respect, it was confirmed that an ethylenically unsaturated group (double bond) originating from the constituent unit (b) contained in the resin (A) is generated by the conversion reaction.

[0332] To the reaction solution containing the resin (A) and solvent (PC) obtained in this way, propylene glycol monomethyl ether acetate (manufactured by Dow Chemical Co.) was added as a solvent (C) so that the component other than the solvent was 35 mass%, and the resin (A) solution of Example 1 was obtained.

[0333] [Example 2]

[0334] A resin precursor composition was obtained in the same manner as in Example 1.

[0335] (Synthesis of resin (A))

[0336] In the same manner as in Example 1, a reaction solution containing resin (A) and solvent (PC) was obtained. The reaction solution containing the obtained resin (A) and solvent (PC) was analyzed in the same manner as in Example 1, and by the IR spectrum obtained, it was confirmed that an ethylenically unsaturated group (double bond) originating from the constituent unit (b) contained in the resin (A) is present.

[0337] (Addition reaction of polybasic acid (e))

[0338] Next, in a flask under atmospheric pressure with a nitrogen gas atmosphere, 9.4 g of succinic anhydride (SA) (manufactured by Shin Nippon Rika Co., Ltd.) as a polybasic acid (e) (20 mol per 100 mol of the total monomer used in the synthesis of the resin precursor (PA)) and 0.5 g of lithium naphthenate (manufactured by Toei Chemical Co., Ltd.) as a catalyst (0.4 parts by mass per 100 parts by mass of the monomer and succinic anhydride used in the synthesis of the resin precursor (PA)) were added to a reaction solution containing resin (A) to which the polybasic acid (e) was added, and an addition reaction was carried out by maintaining at 78°C for 60 minutes, thereby obtaining a reaction solution containing resin (A) to which the polybasic acid (e) was added.

[0339] The reaction solution containing the resin (A) to which the obtained polybasic acid (e) was added was analyzed using infrared absorption (IR) spectroscopy. By the obtained IR spectrum, the infrared absorption peak originating from the acid anhydride structure of the polybasic acid (e) disappeared, confirming that an addition reaction had occurred.

[0340] Analysis by IR spectroscopy was performed using the same analytical apparatus and accessories as for the analysis of the reaction solution containing resin (A) and solvent (PC).

[0341] To the reaction solution containing the resin (A) to which the polybasic acid (e) obtained in this way has been added, propylene glycol monomethyl ether acetate was added as a solvent (C) so that the component other than the solvent was 35 mass%, and the resin (A) solution of Example 2 was obtained.

[0342] [Example 3]

[0343] A resin (A) solution of Example 3 was obtained in the same manner as Example 2, except that monomer (ma) was 10 mol%, monomer (m-pb) was 20 mol%, monomer (mc) was 30 mol%, monomer (md) was 30 mol%, basic catalyst (PB) was 0.14 parts by mass, and polybasic acid (e) was 10 mol%.

[0344] [Example 4]

[0345] A resin (A) solution of Example 4 was obtained in the same manner as Example 2, except that 20 mol% of 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate (manufactured by Showa Denko Co., Ltd., MOI-BM (registered trademark), dissociation temperature at which the dissociation rate of the block isocyanate group is 80% or more in 30 minutes: 130°C, dissociation rate when heated at 100°C for 30 minutes: 18%) was used instead of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (MOI-BP) (registered trademark) as the monomer (ma).

[0346] [Example 5]

[0347] A resin (A) solution of Example 5 was obtained in the same manner as Example 2, except that 40 mol% of 2,3-dihydroxypropyl methacrylate (DHPMA) (manufactured by Nichiyu Co., Ltd.) was used instead of hydroxyethyl methacrylate (HEMA) as the monomer (mc).

[0348] [Example 6]

[0349] A resin (A) solution of Example 6 was obtained in the same manner as in Example 2, except that 10 mol% of methyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd.) was used instead of 2-ethylhexyl acrylate (2EHA) as the monomer (md).

[0350] [Example 7]

[0351] A resin (A) solution of Example 7 was obtained in the same manner as Example 2, except that 20 mol% of 1,2,3,6-tetrahydrophthalic anhydride (THPA) (manufactured by Shin Nippon Ricah Co., Ltd.) was used instead of succinic anhydride (SA) as the polybasic acid (e).

[0352] [Example 8]

[0353] A resin (A) solution of Example 8 was obtained in the same manner as in Example 2, except that 0.21 parts by mass of 1,1,3,3-tetramethylguanidine (manufactured by Tokyo Kasei High School Co., Ltd.) was used as the basic catalyst (PB) instead of 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU).

[0354] [Example 9]

[0355] A resin (A) solution of Example 9 was obtained in the same manner as in Example 2, except that monomer (md) was not used, and monomer (ma) was 22 mol%, monomer (m-pb) was 33 mol%, and monomer (mc) was 45 mol%.

[0356] [Comparative Example 1]

[0357] A solution containing a resin precursor (PA) and a solvent (PC) was obtained in the same manner as in Example 1. Propylene glycol monomethyl ether acetate was added to the obtained solution containing the resin precursor (PA) and the solvent (PC) such that the component other than the solvent was 35 mass%, thereby obtaining the resin solution of Comparative Example 1.

[0358] [Comparative Example 2]

[0359] In the same manner as in Example 1, a solution containing a resin precursor (PA) and a solvent (PC) was obtained.

[0360] Next, in a flask under atmospheric pressure with a nitrogen gas atmosphere, 9.4 g of succinic anhydride (SA) (20 mol per 100 mol of the total monomer used in the synthesis of the resin precursor (PA)) and 0.5 g of lithium naphthenate (catalyst) (0.4 parts by mass per 100 parts by mass of the total monomer and succinic anhydride used in the synthesis of the resin precursor (PA)) were added as polybasic acid (e) and an addition reaction was carried out by maintaining at 78°C for 60 minutes, thereby obtaining a solution containing a resin to which polybasic acid (e) was added.

[0361] The solution containing the resin to which the obtained polybasic acid (e) was added was analyzed in the same manner as in Example 2. By the obtained IR spectrum, the infrared absorption peak originating from the acid anhydride structure of the polybasic acid (e) disappeared, confirming that an addition reaction had occurred.

[0362] To the solution containing the resin to which the polybasic acid (e) obtained in this way was added, propylene glycol monomethyl ether acetate was added so that the component other than the solvent was 35 mass%, thereby obtaining the resin solution of Comparative Example 2.

[0363] [Comparative Example 3]

[0364] A resin solution of Comparative Example 3 was obtained in the same manner as in Example 2, except that 30 mol% of 2-[(diethyl lactic acid)carbonylamino]ethyl acrylate (AOI-MDE), which is another monomer (md), was used instead of 2-[(diethyl lactic acid)carbonylamino]ethyl acrylate (AOI-MDE) as the monomer (m-pb).

[0365] [Comparative Example 4]

[0366] A resin solution of Comparative Example 4 was obtained in the same manner as in Example 2, except that hydroxyethyl methacrylate (HEMA) was not used as the hydroxyl group-containing monomer (mc) and the amount of other monomer (md) used was 50 mol%.

[0367] The block isocyanate group-containing monomer (ma), the monomer having a group represented by formula (1) (m-pb), the hydroxyl group-containing monomer (mc), other monomer (md), the basic catalyst (PB), the solvent (PC), and the polybasic acid (e) used in the preparation of the resin solutions of Examples 1 to 9 and Comparative Examples 1 to 4, and their amounts are shown in Table 1 or Table 2, respectively.

[0368]

[0369]

[0370] Table 3 shows the weight average molecular weight (Mw), block isocyanato group equivalent (g / mol), and hydroxyl group equivalent (g / mol) of the resin precursor (PA) used to prepare the resin (A) solutions of Examples 1 to 9 and the resin solutions of Comparative Examples 1 to 4.

[0371] In addition, the weight average molecular weight (Mw), solid dispersion acid value (mgKOH / g), block isocyanate group equivalent (g / mol), hydroxyl group equivalent (g / mol), and ethylenically unsaturated group equivalent (g / mol) of the resins included in the resin (A) solutions of Examples 1 to 9 and the resin solutions of Comparative Examples 1 to 4 are shown in Table 3.

[0372] The weight average molecular weight (Mw) of the resin precursor (PA), the resin (A) solution, and the weight average molecular weight (Mw) of the resin contained in the resin solution were calculated by the method shown below.

[0373] [Weight Average Molecular Weight (Mw)]

[0374] The weight-average molecular weight was measured using gel permeation chromatography (GPC) under the following conditions and calculated as a polystyrene equivalent.

[0375] For GPC measurements, a GPC system manufactured by Shimadzu Seisakusho Co., Ltd. was used as the GPC measuring device, and a differential refractive index detector RID-10A was used as the detector. In addition, three Shodex (registered trademark) LF804 columns and one KF-801 column manufactured by Showa Denko Co., Ltd. were used. GPC measurements were performed under conditions of a column temperature of 40°C and a flow rate of 1.5 mL / min.

[0376]

[0377] [Examples 11 to 20, Comparative Examples 11 to 18]

[0378] The resin (A) solution of Examples 1 to 9 shown in Table 4 or the resin solution obtained in Comparative Examples 1 to 4 shown in Table 5 (resin (A)), the solvent (C), the reactive diluent (D) dipentaerythritol pentaacrylate (Doh-Gose Co., Ltd.), the photopolymerization initiator (E) 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,-1-(O-acetyloxime) (Ciba Japan Co., Ltd.), and the phthalocyanine-based dye Valifast Blue 2620 (Orient Chemical Co., Ltd.) as the coloring agent (F) were mixed in the proportions shown in Table 4 or Table 5, respectively, to prepare the resin compositions of Examples 11 to 20 and Comparative Examples 11 to 18.

[0379]

[0380]

[0381] The amount of resin (A) shown in Tables 4 and 5 does not include the amount of solvent contained in the resin solutions obtained in Examples 1 to 9 and Comparative Examples 1 to 4. In addition, the amount of solvent (C) shown in Tables 4 and 5 is listed by summing the amount of solvent contained in the resin solutions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 and the amount of solvent added during the preparation of the resin composition.

[0382] The content of each component of the resin (A), solvent (C), reactive diluent (D), photopolymerization initiator (E), and colorant (F) shown in Tables 4 and 5 is the content (parts by mass) per 100 parts by mass of the total of the resin (A) and reactive diluent (D).

[0383] [Evaluation of Content]

[0384] The resin compositions of Examples 11 to 20 and Comparative Examples 11 to 18 were each applied by spin coating on a square glass substrate (alkali-free glass substrate) with a width of 5 cm and a length of 5 cm, such that the thickness after exposure was 2.5 μm, thereby forming a coating film. Subsequently, the solvent (C) in the coating film was removed by volatilizing it by heating at 100°C for 3 minutes.

[0385] Next, the coating film was exposed by irradiating it with ultraviolet light of a wavelength of 365 nm at an energy dose of 40 mJ / cm², and the exposed area was photocured. Afterwards, the coating film was cured by performing a baking treatment at 80°C for 30 minutes to form a cured film. The thickness of the fabricated cured film was measured using a step meter. The thickness at this time was denoted as X.

[0386] Afterward, the prepared cured film was immersed in 20g of propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 15 minutes. After immersion, the coating film was vacuum dried at 40°C for 30 minutes, and the thickness of the coating film was measured using a step gauge. The thickness at this time was denoted as Y.

[0387] Then, using the following formula, the ratio of the thickness Y of the cured film after immersion in PGMEA to the thickness X of the cured film before immersion in PGMEA was calculated as the residual film rate, and the solvent resistance of the cured film was evaluated. That is, the closer the residual film rate is to 100%, the better the solvent resistance of the cured film. For evaluation, a residual film rate of 80% or higher was set as the passing line. The results are shown in Tables 4 and 5.

[0388] Residual film rate = (Y / X) × 100 (%)

[0389] As shown in Table 4, the cured films of the resin compositions of Examples 11 to 20 had a residual film rate (%) of 85% or more after immersion in PGMEA, and had good solvent resistance even at a low temperature of 80°C for the baking treatment.

[0390] In contrast, as shown in Table 5, the cured films of the resin compositions of Comparative Examples 11 to 18 had a residual film rate (%) of 50% or less after immersion in PGMEA, and their solvent resistance was insufficient. Industrial applicability

[0391] According to the present invention, a resin composition is provided that imparts a resin cured film having excellent solvent resistance. Furthermore, according to the present invention, an image display element is provided that comprises a color filter having a coloring pattern formed from a resin cured film having excellent solvent resistance. The resin composition of the present invention can preferably be used as a material such as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, or a resist for a color filter.

Claims

Claim 1 A resin having a constituent unit (a) having a block isocyanate group, a constituent unit (b) having one or more groups selected from the following formulas (2-2) and (3-2), and a constituent unit (c) having a hydroxyl group, wherein the constituent unit (a) is a constituent unit derived from a (meth)acrylate containing a block isocyanate group, the constituent unit (b) is a constituent unit derived from a monomer having a (meth)acryloyloxy group and a group represented by the following formula (1), the constituent unit (c) is a constituent unit derived from a (meth)acrylate containing a hydroxyl group, and the constituent unit (a) is characterized by having a dissociation rate of the block isocyanate group of 5 to 99% when heated at 100°C for 30 minutes. (In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) (In Equation (2-2), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) (In Equation (3-2), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) Claim 2 A resin according to claim 1, wherein the constituent unit (a) having the block isocyanato group is a constituent unit derived from a monomer having an ethylenically unsaturated bond and a block isocyanato group, the monomer having the ethylenically unsaturated bond and a block isocyanato group is a compound in which the isocyanato group of an isocyanate compound having an ethylenically unsaturated bond and an isocyanato group is blocked by a blocking agent, and the blocking agent is one or more selected from γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methylethyl ketoxime, and 3,5-dimethylpyrazole. Claim 3 A resin according to claim 1 or 2, wherein the constituent unit (a) having the block isocyanato group is a constituent unit derived from a block isocyanato group-containing (meth)acrylate, and the block isocyanato group-containing (meth)acrylate is a compound in which the isocyanato group-containing (meth)acrylate is blocked by one or more blocking agents selected from 3,5-dimethylpyrazole and methyl ethyl ketoxime. Claim 4 In claim 1 or 2, the R having of the above-mentioned constituent unit (b) 1 and R 2 Each of these is independently a hydrocarbon group having 1 to 3 carbon atoms, and R 3 and R 4 a, resins, each independently a hydrogen atom or a methyl group. Claim 5 A resin according to claim 1 or 2, wherein a portion of the constituent unit (c) having the hydroxyl group comprises a carboxyl group derived from a polybasic acid (e). Claim 6 A resin precursor comprising a constituent unit (a) having a block isocyanate group, a constituent unit (pb) having a group represented by the following formula (1), and a constituent unit (c) having a hydroxyl group, wherein the constituent unit (a) is a constituent unit derived from a (meth)acrylate containing a block isocyanate group, the constituent unit (pb) is a constituent unit derived from a monomer having a (meth)acryloyloxy group and a group represented by the following formula (1), the constituent unit (c) is a constituent unit derived from a (meth)acrylate containing a hydroxyl group, and the constituent unit (a) is characterized by having a dissociation rate of the block isocyanate group of 5 to 99% when heated at 100°C for 30 minutes. (In Equation (1), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) Claim 7 A method for manufacturing the resin described in claim 1, characterized by carrying out a dealolysis and decarboxylation reaction of the resin precursor (PA) described in claim 6 in a solvent (PC) using a basic catalyst (PB). Claim 8 A resin composition comprising a resin (A) described in claim 1 or 2, a solvent (C), a reactive diluent (D), and a photopolymerization initiator (E). Claim 9 A resin composition according to claim 8, further containing a coloring agent (F). Claim 10 A resin composition according to claim 9, wherein, with respect to a total of 100 parts by mass of the resin (A) and the reactive diluent (D), the composition contains 10 to 90 parts by mass of the resin (A), 30 to 1000 parts by mass of the solvent (C), 10 to 90 parts by mass of the reactive diluent (D), 0.1 to 30 parts by mass of the photopolymerization initiator (E), and 3 to 80 parts by mass of the coloring agent (F). Claim 11 A resin cured film comprising a cured product of the resin composition described in paragraph 8. Claim 12 A color filter having a coloring pattern comprising a cured product of the resin composition described in paragraph 10. Claim 13 An image display element having a color filter as described in paragraph 12. Claim 14 delete Claim 15 delete Claim 16 delete

Images