Composition, cured product, and resin molded article

Abstract

The object of the present invention is to provide a low-temperature curable composition capable of forming a cured product with excellent solvent resistance. [Solution] A composition comprising a polymer (A) containing a constituent unit (a) having a group represented by the following formula (1), a base (B), and a polyfunctional thiol (C). TIFF2026114712000018.tif36149 (in formula (1), R 1 and R 2 These are each, independently, hydrocarbon groups having 1 to 20 carbon atoms. 3 and R 4 Each of these is independently either a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (* indicates a bonding site.)

Description

[Background technology]

[0001] The present invention relates to compositions, cured products, and resin molded articles, etc.

[0002] Blocked isocyanate compounds are compounds in which the reactivity of an isocyanate group in a compound having an isocyanate group is inactivated (blocked) by reacting the isocyanate group with a blocking agent. For example, when using a blocked isocyanate compound as a curing agent, blocking the isocyanate group eliminates the need to prepare, for example, a liquid 1 containing a main agent having an active hydrogen group and a liquid 2 containing a compound having an isocyanate group for reaction with the active hydrogen group. Instead, the main agent having an active hydrogen group and the blocked isocyanate compound can be pre-mixed into a single liquid. For this reason, blocked isocyanate compounds are widely used in adhesives, coatings, molding materials, resins, and the like.

[0003] Crosslinking during resin manufacturing is an important means of improving resin properties. On the other hand, in order to make substrates resinous and to save energy, it is necessary to lower the heating temperature during crosslinking, for example, to below 100°C. One method that enables crosslinking under low temperature conditions is to introduce double bonds into the (co)polymer that forms the main chain of the resin. The applicant has proposed such compositions in Patent Documents 1 and 2. Patent Document 1 describes a photocurable composition containing (a) a compound containing two or more allyl groups in the molecule, (b) a compound containing two or more mercapto groups in the molecule, (c) a compound containing an ethylenically unsaturated group and an isocyanate group, and (d) a photopolymerization initiator. Patent Document 2 describes a photopolymerization initiator composition with high sensitivity and excellent storage properties, a photosensitive composition containing the photopolymerization initiator composition, and a thiourethane compound suitable for the photopolymerization initiator composition. Patent Document 3 describes a compound having a double bond that can be crosslinked at low temperatures (below 100°C) using a blocked isocyanate compound in which a compound having an isocyanate group (a1) and a compound having a hydroxyl group (a2) are bonded via the isocyanate group and the hydroxyl group. Furthermore, in Patent Document 4, the applicant describes that a copolymer containing a structural unit (a) having a conjugated diene moiety in its side chain and a structural unit (b) having a group containing a malic acid ester, and not containing a carboxyl group, has low-temperature curability and can form a cured product with good solvent resistance. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-117832 [Patent Document 2] Patent No. 5254793 [Patent Document 3] International Publication No. 2022 / 145298 [Patent Document 4] Japanese Patent Publication No. 2023-74384 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] For curing, lower heating temperatures are generally preferable as they are more energy-efficient. In particular, for compositions used in components of image display elements, it is necessary to keep the heating temperature low to protect the elements. However, conventional compositions failed to produce cured products with sufficient solvent resistance when heated at low curing temperatures. Therefore, there is a need for a composition that can form cured products with excellent solvent resistance even at low curing temperatures.

[0006] This invention has been made in view of the above circumstances, and aims to provide a composition capable of forming a cured product with excellent solvent resistance, and a blocked isocyanate polymer contained in this composition. [Means for solving the problem]

[0007] In order to solve the above problems, the present inventors conducted diligent research and found that a composition containing a base and a polyfunctional thiol, along with a predetermined polymer containing a structure such as malic acid ester, can solve the above problems, thus completing the present invention. [1] A composition comprising a polymer (A) containing a constituent unit (a) having a group represented by the following formula (1), a base (B), and a polyfunctional thiol (C).

[0008] [ka] (In formula (1), R 1 and R 2 These are each, independently, hydrocarbon groups having 1 to 20 carbon atoms. 3 and R 4 Each of these is independently either a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (* indicates a bonding site.) [2] The R 1 and R 2 However, each is independently a hydrocarbon group with 1 to 3 carbon atoms, R 3 and R 4 A composition in which each is independently a hydrogen atom or a methyl group.[1] [3] A composition of [1] or [2] in which the content of the constituent unit (a) is 1 to 99 mol% with respect to 100 mol% of all constituent units. [4] A composition of any of the following [1] to [3] in which the base (B) is one or more selected from 1,8-diazabicyclo[5.4.0]-7-undecene or a salt thereof, 1,5-diazabicyclo[4.3.0]-5-nonene or a salt thereof, 1,5,7-triazabicyclo[4.4.0]deca-5-ene or a salt thereof, and triethylmethylammonium 2-ethylhexanoate. [5] The composition according to any one of [1] to [4], wherein the polyfunctional thiol (C) is a compound having three or more thiol groups in the molecule. [6] In the structural unit (a), R 1 and R 2 are ethyl groups, and R 3 and R 4 are hydrogen atoms, the composition according to any one of [1] to [5]. [7] A cured product having a structure represented by formula (7) or (8).

[0009]

Chemical formula

Advantages of the Invention

[0010] According to the present invention, a composition that can be crosslinked at a low temperature (100 ° C or lower) can be provided. The cured product and resin molded body using the composition exhibit high solvent resistance.

Embodiments for Carrying out the Invention

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid. For example, a (meth) acrylic acid ester compound means an acrylic acid ester compound or a methacrylic acid ester compound.

[0012] <Composition> A composition in one embodiment of the present invention comprises a polymer (A), a base (C), and a polyfunctional thiol (C).

[0013] [Potassium (A)] The polymer (A) of this embodiment contains a constituent unit (a) having a group represented by the following formula (1) (hereinafter also simply referred to as "constituent unit (a)"). The main chain of constituent unit (a) is usually a hydrocarbon chain having 2 or more carbon atoms, and is formed, for example, by polymerization of ethylenically unsaturated groups. The group may be directly bonded to the main chain, or it may be bonded via an alkylene group, an ether bond, a carbonyl group, a carbonyloxy structure (including oxycarbonyl), etc.

[0014] Constituent unit (a) The constituent units (a) contained in polymer (A) are constituent units derived from monomers (ma) having the group shown in the following formula (1) (hereinafter also simply referred to as "monomer (ma)"). Constituent units (a) may consist of only one type or two or more types. A monomer (ma) is a monomer having an ethylenically unsaturated bond and a group represented by the following formula (1).

[0015] [ka] (In formula (1), R 1 and R 2 These are each, independently, hydrocarbon groups having 1 to 20 carbon atoms. 3 and R 4 Each of these is independently either a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (* indicates a bonding site.)

[0016] In formula (1), R 1 and R 2 Each of these is independently 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. 1 and R 2It is preferably an alkyl group, preferably a methyl group or an ethyl group, and particularly preferably an ethyl group. 1 and R 2 These may be the same or different, but it is preferable that they be the same because the monomer (MA) can be easily produced.

[0017] In formula (1), R 3 and R 4 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. 3 and R 4 These may be the same or different, but it is preferable that they be the same because the monomer (MA) can be easily produced.

[0018] Examples of monomers (ma) include compounds obtained by urethane reaction between an isocyanate group in an isocyanate compound having an ethylenically unsaturated group such as a vinyl group or a (meth)acryloyloxy group in the molecule and a hydroxyl group in a hydroxyl group-containing compound represented by the following formula (2).

[0019] [ka] (In formula (2), R 1 , R 2 , R 3 and R 4 R in equation (1) 1 , R 2 , R 3 and R 4 It is the same as this.

[0020] Examples of hydroxyl group-containing compounds represented by formula (2) that can be used as raw materials for monomers (MA) include malic acid esters, tartaric acid esters, and citrate esters, with malic acid esters being preferred due to their availability. The number of carbon atoms in the two ester moieties contained in the hydroxyl group-containing compound shown in formula (2) (-COOR 1 and -COOR 2 In R 1 and R 2 The number of carbon atoms is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 2.

[0021] The hydroxyl group-containing compound represented by formula (2) is preferably one or more selected from 2-[(diethyl malate)carbonylamino]ethyl (meth)acrylate and 2-[2-[(diethyl malate)carbonylamino]ethoxy]ethyl (meth)acrylate, and is particularly preferred to be 2-[(diethyl malate)carbonylamino]ethyl acrylate. The hydroxyl group-containing compound represented by formula (2) is particularly preferably diethyl malate, as it is more readily converted to a dienophile moiety that is susceptible to the Diels-Alder reaction, as will be described later.

[0022] Conventional known methods can be used to carry out the urethane reaction between the isocyanate compound having the ethylenically unsaturated group described above and the hydroxyl group-containing compound represented by formula (2). The above urethane formation reaction can be carried out with or without the presence of a solvent. When the above urethane formation reaction is carried out using a solvent, any solvent that is inert to isocyanate groups may be used, and any known solvent can be used.

[0023] The above urethane formation reaction is generally preferably carried out at a temperature of -10°C to 90°C, more preferably at a temperature of 5°C to 70°C, and even more preferably at a temperature of 10°C to 40°C. When carrying out the above urethane reaction, urethane catalysts such as dibutyltin dilaurate, polymerization inhibitors such as phenothiazine, p-methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (hereinafter also referred to as "BHT") may be used as needed.

[0024] Examples of isocyanate compounds used as raw materials for monomers (MA) include the compound represented by the following formula (3).

[0025] [ka] (In formula (3), R 5 R represents a hydrogen atom or a methyl group. 6 -CO-, -COOR 7 - or -COO-R 8 O-CONH-R 9 - and R 7 R is an alkylene group with 1 to 6 carbon atoms, 8 R is an alkylene group with 2 to 6 carbon atoms, 9 (This is an alkylene group having 2 to 12 carbon atoms, which may have substituents, or an arylene group having 6 to 12 carbon atoms, which may have substituents. The substituents are alkyl groups having 1 to 20 carbon atoms, halogen atoms, hydroxyl groups, etc.)

[0026] R 6 Since the compounds used as raw materials for the isocyanate compounds represented by formula (3) are readily available, -C(=O)OR 7 - Preferably, R 7 It is more preferable that the group is an alkylene group having 1 to 4 carbon atoms.

[0027] Examples of isocyanate compounds represented by formula (3) above include 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, and methacryloyl isocyanate.

[0028] Furthermore, as the isocyanate compound used as a raw material for the monomer (MA), a reaction product obtained by reacting 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound in equimolar amounts (2-hydroxyalkyl (meth)acrylate:diisocyanate compound = 1 mole:1 mole) may be used. The alkyl group of the 2-hydroxyalkyl(meth)acrylate is a compound that readily reacts with diisocyanate compounds, and is therefore preferably an ethyl group or an n-propyl group, and more preferably an ethyl group.

[0029] Examples of the 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, and lysine diisocyanate.

[0030] Other isocyanate compounds used as raw materials for monomers (MA) include 1,1-bis(methacryloyloxymethyl)methyl isocyanate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 1,1-bis(acryloyloxymethyl)methyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0031] The isocyanate compound used as a raw material for 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, more preferably 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, and even more preferably 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate.

[0032] Because polymer (A) contains constituent unit (a), when a composition containing copolymer (A) and base (B) is heat-cured, the group represented by formula (1) of constituent unit (a) is converted to a group having a dienophile moiety by the action of the basic catalyst (B). As a result, the composition containing copolymer (A) and basic catalyst (B) hardens sufficiently even at a sufficiently low heating temperature for curing, and a cured product with excellent solvent resistance is obtained.

[0033] Other constituent units (b) Polymer (A) may optionally contain other constituent units (b) besides constituent unit (a). Constituent unit (b) may consist of only one type or two or more types. Constituent unit (b) is a constituent unit derived from a monomer (mb) other than the monomer (ma) mentioned above (hereinafter also simply referred to as "monomer (mb)"), and is a constituent unit that does not have a conjugated diene moiety or a carboxyl group. Note that the conjugated diene moiety does not contain an ethylenically unsaturated group.

[0034] The monomer (mb) is not particularly limited as long as it does not have a conjugated diene moiety or a carboxyl group and has an ethylenically unsaturated group. Examples of monomers (mb) include (meth)acrylic acid esters, (meth)acrylamides, vinyl compounds, styrenes, unsaturated dicarboxylic acid diesters, unsaturated polybasic acid anhydrides, unsaturated carboxylic acids, and salts thereof.

[0035] • Methyl methacrylate (MMA) (manufactured by Mitsubishi Chemical Corporation) Butyl acrylate (BuA) (manufactured by Nippon Shokubai Co., Ltd.) • 2-Hydroxyethyl methacrylate (HEMA) (manufactured by Kanto Chemical Co., Ltd.) • Glycidyl methacrylate (GMA) (manufactured by Kanto Chemical Co., Ltd.) • Methacrylic acid (MAA) (manufactured by Kuraray Co., Ltd.) • Sodium styrene sulfonate (NASS) (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, and 2-ethylhexyl (meth)acrylate. )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, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, naphthalene N(meth)acrylate, anthracene(meth)acrylate, glycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, (3-ethyloxetane-3-yl)methyl(meth)acrylate, 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, N,Examples include N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, and hexamethylpiperidyl (meth)acrylate.

[0036] Specific examples of (meth)acrylamides include (meth)acrylamide, (meth)acrylamide N,N-dimethylamide, (meth)acrylamide N,N-diethylamide, (meth)acrylamide N,N-dipropylamide, (meth)acrylamide N,N-diisopropylamide, (meth)acrylamide anthracenylamide, N-isopropyl(meth)acrylamide, (meth)acrylmorpholin, and diacetone(meth)acrylamide.

[0037] Specific examples of vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, and 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 Deca-8-en, tricyclo[5.2.1.0 2,6 Deca-3-en, tricyclo[4.4.0.1 2,5 ]Undeca-3-ene, tricyclo[6.2.1.0 1,8 ]Undeca-9-en, tricyclo[6.2.1.0 1,8 ]Undeca-4-ene, 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-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,12 ] Dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ] Dodeca-3-ene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]Pentadeca-4-ene, pentacyclo[7.4.0.1 2,5 .1 9,12 .0 8,13 Examples include pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, vinyltoluene, norbornene, etc.

[0038] Specific examples of styrenes include styrene, α-, o-, m-, p-alkyl, nitro, cyano, and amide derivatives of styrene. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate. Specific examples of unsaturated polybasic anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Specific examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, 2-pentenoic acid, and cinnamic acid; and unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid. Among these, (meth)acrylic acid is preferred.

[0039] Composition and molecular weight The polymer (A) may not contain other constitutional units (b), but when it contains other constitutional units (b), the content ratios of the constitutional unit (a) and the constitutional unit (b) in the polymer (A) can be appropriately determined according to the use of the polymer (A). The content ratio of the constitutional unit (a) in the polymer (A) is preferably more than 1 and less than 99 mol% when the total is 100 mol%, more preferably 1 to 50 mol%, and even more preferably 2 to 20 mol%. By containing in such a ratio, it becomes easier to balance the storage stability, curability, solvent resistance, etc. of the composition containing the polymer (A).

[0040] The weight average molecular weight of the polymer (A) is preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 30,000 or less from the viewpoint of suppressing the increase in the viscosity of the polymer. The weight average molecular weight of the block isocyanate polymer (H) is preferably 1,000 or more. The weight average molecular weight can be measured by gel permeation chromatography (GPC method).

[0041] 〔Base (B)〕 The base (B) is such that in the group represented by the formula (1) in the polymer (A), the carbon atom to which the substituent R 3 is bonded and the carbon atom to which R 4 is bonded can be double-bonded, and it is not particularly limited as long as it can do so. The base (B) is preferably an amine and may be an ammonium salt.

[0042] The base (B) is more preferably represented by the following formula (4). R 7 N=CR 8 -NR 9 R 10 ···(4) In the formula, R 7 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by -NR 11 2. R 8 , R 9 , R 10 and R 11 are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and two R11 may be the same as or different from each other. R 7 , R 8 , R 9 , R 10 , and any two or more of the two Rs 11 may combine to form a cyclic structure.

[0043] When the base (B) contains a cyclic structure in which any two or more groups are bonded, the one represented by the formula (4-2) is preferred. R 7a N=CR 8a -NR 9a R 10a ···(4-2) In the formula, R 7a , R 8a , R 9a and R 10a are hydrocarbon groups, R 7a and R 10a are combined with each other, and R 8a and R 9a are combined with each other to form a cyclic structure, and the sum of the carbon numbers of R 7a and R 10a is 3 to 20, preferably 5 to 10, and the sum of the carbon numbers of R 8a and R 9a [[ID=5l]]is 3 to 20, preferably 5 to 10.

[0044] Of the base (B) represented by formula (4), at least one selected from 1,8-diazabicyclo[5.4.0]-7-undecene or its salt, 1,5-diazabicyclo[4.3.0]-5-nonene or its salt, 1,1,3,3-tetramethylguanidine or its salt, 1,5,7-triazabicyclo[4.4.0]deca-5-ene or its salt, and triethylmethylammonium 2-ethylhexanoate is preferred. Among these, 1,8-diazabicyclo[5.4.0]-7-undecene or its salt, 1,5-diazabicyclo[4.3.0]-5-nonene or its salt, 1,5,7-triazabicyclo[4.4.0]deca-5-ene or its salt, and triethylmethylammonium 2-ethylhexanoate is preferred, and 1,8-diazabicyclo[5.4.0]-7-undecene is more preferred.

[0045] The base (B) preferably has a pKa of 12.5 or higher at 25°C. Note that base (B) with a pKa of 12.5 or higher at 25°C includes bases with a pKa of 12.5 or higher in aqueous solution, and bases that are too acidic to be measured in aqueous solution and whose pKa is calculated from measurement results in an organic solvent.

[0046] The amount of base (B) is preferably 0.001 parts by mass or more and 10 parts by mass ppm or less per 100 parts by mass of polymer (A), more preferably 0.01 parts by mass or more and 1.0 part by mass or less, and even more preferably 0.015 parts by mass or more and 0.5 parts by mass or less. If the amount of base (A) is 0.001 parts by mass or more per 100 parts by mass of polymer (A), a sufficient reaction rate can be obtained when introducing an ethylenic double bond to the group represented by formula (1) in polymer (A), which is preferable. If the amount of base (B) is 10 parts by mass or less relative to polymer (A), the amount of base will not be in excess, which is preferable.

[0047] The polymer (A) and base (B) in the composition may be pre-reacted. The reaction product of polymer (A) having the group represented by formula (1) and base (B) is a blocked isocyanate polymer (E) having an ethylenic double bond (d2). The reaction between polymer (A) and base (B) is not particularly limited, but it is preferable to carry it out in the presence of a solvent. When carried out in the presence of a solvent, examples of solvents include alcohol-based solvents such as cellosolve, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, methanol, ethanol, propanol, isopropanol, butanol, benzyl alcohol, and hexylene glycol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monobutyl ether acetate; ether-based solvents such as ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, and diethylene glycol dimethyl ether; aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene; and amide-based solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, with propylene glycol monomethyl ether acetate being preferred. These may be used individually or in combination of two or more.

[0048] The amount of solvent is preferably 0.1 to 100 times the mass of the resulting ethylenically double-bonded blocked isocyanate polymer (E), more preferably 1 to 50 times the mass, and even more preferably 5 to 30 times the mass. Within this range, the exothermic reaction is suppressed, which is preferable.

[0049] The reaction temperature is preferably 0 to 150°C, more preferably 50 to 120°C, and even more preferably 80 to 110°C.

[0050] The reaction time is preferably 0.1 to 10 hours, more preferably 0.3 to 5 hours, and even more preferably 0.5 to 3 hours.

[0051] The gas in the reaction vessel is not particularly limited, but can be air, dry air, nitrogen gas, helium gas, etc., with dry air or nitrogen gas being preferred. The pressure in the reaction vessel is not particularly limited, but atmospheric pressure is preferred. When a composition containing polymer (A) and base (B) is heat-cured, the constituent unit (a) is converted from a group represented by the following formula (1) to a group having a dienophile moiety.

[0052] Block isocyanate polymer (E) having an ethylenically double bond (d2) is subjected to a base (B) to remove substituent R from polymer (A). 3 The carbon atom to which R is bonded 4 It is obtained by forming a double bond with the carbon atom to which it is bonded. The ethylenic double bond (d2) is obtained when the blocked isocyanate polymer (A) undergoes a dealcoholization reaction to become, for example, a compound represented by the following formula (6-1), and then decarboxylation occurs through a reaction with a base (B), R 3 and R 4 It is thought that these are formed between the carbon-carbon atoms to which they are bonded, thereby yielding the blocked isocyanate polymer (E). R in formula (6-1) 2 , R 3 and R 4 These are equivalent to the signs in equation (1).

[0053] [ka]

[0054] Furthermore, the ethylenic double bond (d2) becomes, for example, a compound represented by the following formula (6-2), and then decarboxylates upon reaction with a base (B), R 3 and R 4 It is thought that these are formed between the carbon-carbon atoms to which they are bonded, thereby yielding the blocked isocyanate polymer (E). R in formula (6-2) 1 , R 3 and R 4 These are equivalent to the signs in equation (1).

[0055] [ka]

[0056] [Polyfunctional thiol (C)] Polyfunctional thiols (C) are thiol compounds having two or more mercapto groups. Due to their polyfunctional nature, the crosslinking density increases when curing compared to monofunctional compounds. A polyfunctional thiol (C) is a group that has two or more groups represented by the following general formula (5) within its molecule.

[0057] [ka] In the above general formula (5), R 5 and R 6 Each of these independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aromatic group with 6 to 10 carbon atoms, and s represents an integer from 0 to 2. *2 indicates the bond to the linking group. From the viewpoint of improving the strength of the film (cured product) obtained by the curing reaction, the polyfunctional thiol (C) is preferably one having 2 to 4 groups represented by general formula (1), and more preferably one having 4 groups.

[0058] In the above general formula (1), R 1 and R 6 Each of these is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. Among them, R 5 and R 6 Each of these groups is independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 to 2 carbon atoms. Specifically, examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group, etc., with methyl group or ethyl group being preferred among them.

[0059] From the standpoint of photocurability and storage stability, R 5 and R 6 It is preferable that one or both of them are an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms (i.e., a secondary or tertiary thiol). In particular, R 5 and R 6It is more preferable that one of the members is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms, and the other is a hydrogen atom (i.e., a secondary thiol). That is, the thiol compound (a) is preferably a secondary or tertiary thiol, and more preferably a secondary thiol. The polyfunctional thiol (C) is composed of the group represented by the general formula (5) above -(CH2) s - is bonded to the linking group (X) via -CO-O- (CO on the SH side). If s is 0, it is directly bonded to the linking group (X) via -CO-O- (CO on the SH side). The linking group (X) is not particularly limited as long as it can bond to two or more groups represented by the above general formula (5), and examples include linear or branched hydrocarbon groups, fatty rings, aromatic rings, heterocyclic rings, and other cyclic structures.

[0060] Specific examples of polyfunctional thiols (C) include 1,4-bis(3-mercaptobutyryloxy)butane (product name: Karenz MT (trademark) BD1, manufactured by Resonaq Corporation), di(1-mercaptoethyl phthalate), di(2-mercaptopropyl phthalate), di(3-mercaptobutyl phthalate), di(3-mercaptoisobutyl phthalate), ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonaq Corporation). Karenz MT (registered trademark) PE1), pentaerythritol tetrakisthiopropionate, dipentaerythritol hexakis(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetrakis(2-mercaptopropionate), dipentaerythritol hexakis(2-mercaptopropionate), ethylene glycol 3-mercaptoisobutyrate, 3-mercaptoisobutyrate, 3-mercaptoisobutyrate, 4-mercaptoisobutyrate, 3-mercaptoisobutyrate, 4-mercaptoisobutyrate, 3-mercaptoisobutyrate, 4-mercaptoisobutyrate, 3-mercaptoisobutyrate, 4-mercaptoerythritol tetrakis (3-mercaptoisobutyrate), 4-mercaptoacetate, 5-mercaptoerythritol hexakis (3-mercaptoisobutyrate), 3-mercaptoisobutyrate, 4-mercaptoisobutyrate, 5-mercaptoisobutyrate, 6-mercaptoisobutyrate, 3-mercaptoisobutyrate, 4-mercaptoisobutyrate, 5-mercaptoisobutyrate, 6-mercaptoisobutyrate, 7-mercaptoisobutyrate, 8-mercaptoisobutyrate, 9-mercaptoisobutyrate, 1Diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane tris(2-mercaptoisobutyrate), pentaerythritol tetrakis(2-mercaptoisobutyrate), dipentaerythritol hexakis(2-mercaptoisobutyrate), ethylene glycol bis(4-mercaptovalerate), propylene glycol bis(4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane tris(4-mercaptovalerate), pentaerythritol tetrakis(4-mercaptovalerate), dipentaerythritol hexakis(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3 -Mercaptovalerate), Octanediol bis(3-mercaptovalerate), Trimethylolpropanetris(3-mercaptovalerate), Pentaerythritol tetrakis(3-mercaptovalerate), Dipentaerythritol hexakis(3-mercaptovalerate), Hydrogenated bisphenol A bis(3-mercaptobutyrate), Bisphenol A dihydroxyethyl ether-3-mercaptobutyrate, 4,4'-(9-fluorenylidene)bis(2-phenoxyethyl(3-mercaptobutyrate)), Ethylene Glycol Rubis (3-mercapto-3-phenylpropionate), propylene glycol bis(3-mercapto-3-phenylpropionate), diethylene glycol bis(3-mercapto-3-phenylpropionate), butanediol bis(3-mercapto-3-phenylpropionate), octanediol bis(3-mercapto-3-phenylpropionate), trimethylolpropane tris(3-mercapto-3-phenylpropionate), tris-2-(3-mercapto-3-phenylpropionate)ethyl isocyanurate,Examples include pentaerythritol tetrakis(3-mercapto-3-phenylpropionate), dipentaerythritol hexakis(3-mercapto-3-phenylpropionate), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT (trademark) NR1, manufactured by Resonaq Corporation).

[0061] In the composition of this embodiment, when the total amount of polymer (A) and polyfunctional thiol (C) is 100 parts by mass, the amount of (C) is preferably about 20 to 80 parts by mass, and more preferably about 30 to 70 parts by mass. Furthermore, when a polymer (A) is reacted with a base (B), the reaction depends on the concentration of the functional groups in the reactants and the polyfunctional thiol (C).

[0062] When the number of double bonds in the reactant is set to 100, the preferred amount of polyfunctional thiol (C) is such that the number of mercapto groups is 30 to 200, more preferably 50 to 150, and most preferably 100. Here, the number of mercapto groups in polyfunctional thiol (C) when the number of double bonds in the reactant is set to 100 can be determined by the following formula. Here, the double bond equivalent of the reactant is a value obtained by dividing the molecular weight of polymer (A) by the number of double bonds per molecule, with 1 g / eq being used, and the mercapto group equivalent of polyfunctional thiol (C) is a value obtained by dividing the molecular weight of polyfunctional thiol (C) by the number of mercapto groups per molecule, with 1 g / eq being used. Double bond equivalent of the polymer: A g / eq Polymer content: X g Mercapto group equivalent of polyfunctional thiol (C): B g / eq Amount of polyfunctional thiol (C) component: Y g Functional group ratio = 100 × (A × Y) / (B × X)

[0063] [Other ingredients] The composition of this embodiment may optionally include a solvent, a reactive diluent, a photopolymerization initiator, and the like.

[0064] solvent The solvent reacts with the polymer (A) and, in the group represented by formula (1), R 3 The carbon atoms to which it is bonded, and R 4It is sufficient that it is inert to reactions that form double bonds with the bonded carbon atom, and is not particularly limited. Specifically, (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 hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate; hydroxyl group-containing solvents such as diethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. Poly)alkylene glycol monoalkyl ether acetates; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, Examples include esters such as 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, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and hydroxyl group-free solvents such as carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.These solvents may be used individually or in combination of two or more.

[0065] Among these solvents, ethers are preferred from the viewpoint of ease of availability, cost, solubility and dispersibility of raw materials when preparing the composition, and storage stability of the composition. More 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.

[0066] The solvent content in the composition is preferably 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of polymer (A) (or the total of polymer (A) and the reactive diluent if a reactive diluent described later is included). When the solvent content is within the above range, a composition with an appropriate viscosity for the application can be obtained, and the solvent in the coating film can be easily removed when it is applied.

[0067] Reactive diluent The reactive diluent is a monomer comprising a compound having at least one ethylenically unsaturated bond as a polymerizable functional group within its molecule. The reactive diluent is included as needed. The reactive diluent may be a monofunctional monomer or a polyfunctional monomer having multiple polymerizable functional groups. By including the reactive diluent, the composition of this embodiment can have an appropriate viscosity depending on the application. Furthermore, because the composition of this embodiment contains the reactive diluent, it has good photocurability and can form a cured product with good strength and adhesion to the substrate.

[0068] Monofunctional monomers used as reactive diluents 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, and 2-phenoxy-2-hydroxypropyl Examples include (meth)acrylates such as pyr(meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, 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 individually or in combination of two or more.

[0069] Polyfunctional monomers used as reactive diluents include 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, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth) Examples include acrylates, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl 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 with 2-hydroxyethyl (meth)acrylate, tri(meth)acrylate of tris(hydroxyethyl) isocyanurate, and other (meth)acrylates; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols with N-methylol(meth)acrylamide. These polyfunctional monomers may be used individually or in combination of two or more.

[0070] Among these monomers, polyfunctional (meth)acrylates are preferred as reactive diluents because they result in compositions with good photocurability. More specifically, it is preferable to use polyfunctional (meth)acrylates with three or more functions, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0071] If the composition contains a reactive diluent, its content is preferably 10 to 90 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total of polymer (A) and reactive diluent. When the reactive diluent content is within this range, the effect is significant, resulting in a composition with good low-temperature curability.

[0072] Photopolymerization initiator The photopolymerization initiator is not particularly limited, but examples include benzoins such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,-1-(O-acetyloxime), benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; 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, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1. Examples of photopolymerization initiators include acetophenones; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as xanthones, thioxanthones, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals 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 may be used alone or in combination of two or more.

[0073] The content of the photopolymerization initiator in the composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of polymer (A) (or the total of polymer (A) and the reactive diluent if a reactive diluent is included). If the content of the photopolymerization initiator is within this range, the composition has good curability.

[0074] In addition, the invention may contain, if necessary, one or more known additives such as polymerization inhibitors. The amount of these additives included is not particularly limited, as long as it does not hinder the effects of the present invention. The additives contained in the composition may be those added when preparing the composition, those added when producing polymer (A), or residual materials used when synthesizing the raw material monomers used when producing polymer (A).

[0075] Furthermore, other components may include, as needed, colorants such as pigments and dyes, thermoplastic resins, Adhesion enhancers such as silane coupling agents and titanium coupling agents, Antioxidants such as hindered amines, hydroquinones, and hindered phenols, UV absorbers such as benzophenones, benzotriazoles, salicylates, and metal complex salts. Stabilizers such as metal soaps, inorganic and organic salts of heavy metals (e.g., zinc, tin, lead, cadmium, etc.), and organotin compounds. pH adjusters such as acetic acid, acrylic acid, palmitic acid, oleic acid, mercaptocarboxylic acid and other aliphatic carboxylic acids, phenol, naphthol, benzoic acid, salicylic acid and other aromatic organic acids, Phthalates, phosphates, fatty acids, epoxidized soybean oil, castor oil, liquid paraffin alkyl polycyclic aromatic hydrocarbons and other plasticizers, Waxes such as paraffin wax, microcrystalline wax, polymerized wax, beeswax, whale wax, and low molecular weight polyolefins, Non-reactive diluents such as benzyl alcohol, tar, and pichumen. Fillers such as calcium carbonate, kaolin, talc, mica, bentonite, clay, sericite, glass fiber, carbon fiber, aramid fiber, nylon fiber, acrylic fiber, glass powder, glass balloons, shirasu balloons, coal powder, acrylic resin powder, phenolic resin powder, metal powder, ceramic powder, zeolite, slate powder, etc. Solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, etc., (M) foaming agents, Dehydrating agents such as silane coupling agents, monoisocyanate compounds, and carbodiimide compounds. It may contain antistatic agents, antibacterial agents, antifungal agents, viscosity modifiers, fragrances, deodorizers, flame retardants, leveling agents, sensitizers, and dispersants. These can be used individually or in combination of two or more in any proportion.

[0076] <Method for producing the composition> The composition of this embodiment can be produced by mixing a polymer (A), a base (B), and a polyfunctional thiol (C) using a known mixing apparatus. At this time, along with the polymer (A), base (B), and polyfunctional thiol (C), one or more selected from a solvent, a reactive diluent, a photopolymerization initiator, and the above-mentioned additives may be mixed as needed. Furthermore, the composition of this embodiment may be prepared by mixing a polymer (A) and a base (B), reacting them, and then adding a polyfunctional thiol (C) to the reactant. It may also be prepared by adding one or more of the following as needed: a solvent, a reactive diluent, a photopolymerization initiator, and the additives mentioned above, and then mixing the mixture.

[0077] <Cured product> A cured product, which is one embodiment of the present invention, is obtained by heat curing the above composition. It is presumed that upon heating, the ethylenic double bonds in the polymer (A), particularly in the reaction product of polymer (A) and base (B), react with the polyfunctional thiol to form a crosslinked structure. The structure of the reactants is not particularly limited, but in the present invention, it is preferable that they have a structure represented by the following formula (7) or (8).

[0078] [ka] (In formula (7) or (8), *1 is the binding site to the main chain. 5 and R 6 Each of these independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aromatic group with 6 to 10 carbon atoms, and s represents an integer from 0 to 2. 7 R is in equation (1) 1 and R 2 It is similar to the above. (*2 indicates the bond to the linking group.)

[0079] The heating temperature is preferably 50 to 100°C, and more preferably 70 to 90°C. Compositions having the above specific composition can form crosslinked structures even at such low temperatures within the temperature range.

[0080] The cured product can be used in various resin molded products. For example, it can be suitably used in automotive paints, industrial paints, marine paints, film coatings, adhesives, photoresists, etc. Furthermore, a film-like molded body can be obtained by coating the composition onto a substrate and then heat-curing it, which can be used as a protective film for color filters, etc. It is also possible to shape it using known thermosetting molding methods. [Examples]

[0081] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way to these examples.

[0082] [Manufacturing Example 1] (Synthesis of polymer (A)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube contained 336 g of propylene glycol monomethyl ether acetate as a solvent, and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 90°C.

[0083] Next, a mixed solution was prepared by mixing 30.1 g (3.8 mol%) of 2-[(diethyl malate)carbonylamino]ethyl acrylate (manufactured by Resonac Co., Ltd., AOI-MDE) as monomer (ma), 123.9 g (52.5 mol%) of methyl methacrylate (MMA) (manufactured by Mitsubishi Chemical Corporation) and 146.2 g (43.6 mol%) of butyl acrylate (BuA) (manufactured by Nippon Shokubai Co., Ltd.) as monomer (mb), and 36.1 g of dimethyl 2,2'-azobis(2-methylpropionate) as a polymerization initiator.

[0084] The entire volume of the prepared mixed solution was added dropwise over 2 hours using a dropping funnel to a solvent (propylene glycol monomethyl ether acetate, 0.85 mol) in a flask at atmospheric pressure under a nitrogen gas atmosphere. After the addition was complete, the solution in the flask was polymerized at 90°C for 3 hours while stirring to produce copolymer (A). To the reaction solution containing copolymer (A) thus obtained, propylene glycol monomethyl ether acetate was added as a solvent so that the non-solvent components accounted for 48% by mass, to obtain the polymer (A) solution of Production Example 1 (solid content concentration 48% by mass).

[0085] [Manufacturing Examples 2-8] Polymer (A) solutions of Production Examples 2 to 8 were obtained in the same manner as in Production Example 1, except that the monomers listed in Table 1 were used in the proportions shown in Table 1.

[0086] [Table 1]

[0087] [Manufacturing Example 9] (Synthesis of double bond-containing polymer (A')) 50 g of polymer (A) synthesized in Production Example 7 was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 60°C. Next, a mixed solution was prepared by mixing 1.4 g (0.009 mol) of 2-methacryloyloxyethyl isocyanate (Kalenz MOI) (manufactured by Resonaq Corporation) and 0.01 g of dibutyltin dilaurate (DBTDL) (manufactured by Nitto Kasei Co., Ltd.) as post-addition monomers (mc). The entire volume of the prepared mixed solution was added dropwise over 0.5 hours using a dropping funnel to copolymer (A) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 60°C for 3 hours to obtain a double bond-containing polymer (A') solution.

[0088] [Manufacturing Example 10] The double bond-containing polymer (A') solution of Production Example 10 was obtained in the same manner as in Production Example 9, except that the monomers listed in Table 2 were used in the proportions shown in Table 2.

[0089] [Manufacturing Example 11] (Synthesis of double bond-containing polymer (A')) 50 g of polymer (A) synthesized in Production Example 8 was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and stirred while purging with nitrogen gas, and the temperature was raised to 100°C. Next, a mixed solution was prepared by mixing 0.7 g (0.009 mol) of methacrylic acid (MAA) (manufactured by Kuraray Co., Ltd.) and 0.01 g of 4-dimethylaminopyridine (DMAP) (manufactured by Tokyo Chemical Industry Co., Ltd.) as post-addition monomers (mc). The entire volume of the prepared mixed solution was added dropwise over 0.5 hours using a dropping funnel to polymer (A) in a flask under atmospheric pressure and nitrogen gas. After the addition was complete, the solution in the flask was stirred and polymerized at 100°C for 6 hours to obtain a double-bond-containing polymer (A') solution.

[0090] [Manufacturing Example 12] The double bond-containing polymer (A') solution of Production Example 12 was obtained in the same manner as in Production Example 11, except that the monomers listed in Table 2 were used in the proportions shown in Table 2.

[0091] [Table 2]

[0092] In the manufacturing example, the monomers listed in Tables 1 and 2 were as follows: "Monomer (ma) having the group shown in formula (1)" • 2-[(Diethyl Malate) Carbonylamino] Ethyl Acrylate (manufactured by Resonaq Corporation, Karenz® AOI-MDE) • 2-[(Diethyl Malate) Carbonylamino] Ethyl Methacrylate (Manufactured by Resonaq Corporation, MOI-MDE) ·2-[2-[(Diethyl Malate)carbonylamino]ethoxy]ethyl methacrylate (manufactured by Resonaq Corporation, Karenz® MOI-EG-MDE)

[0093] "Other monomers (mb)" • Methyl methacrylate (MMA) (manufactured by Mitsubishi Chemical Corporation) Butyl acrylate (BuA) (manufactured by Nippon Shokubai Co., Ltd.) • 2-Hydroxyethyl methacrylate (HEMA) (manufactured by Kanto Chemical Co., Ltd.) • Glycidyl methacrylate (GMA) (manufactured by Kanto Chemical Co., Ltd.) • Methacrylic acid (MAA) (manufactured by Kuraray Co., Ltd.) • Sodium styrene sulfonate (NASS) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0094] "Post-added monomer (mc)" • Acrylates 2-methacryloyloxyethyl isocyanate (manufactured by Resonaq Corporation, Karenz MOI® registered trademark) • 2-Acryloyloxyethyl isocyanate (manufactured by Resonac Co., Ltd., Karenz AOI® registered trademark) • Methacrylic acid (MAA) (manufactured by Kuraray Co., Ltd.) • Acrylic acid (Aa) (manufactured by Kanto Chemical Co., Ltd.)

[0095] "catalyst" • Dibutyltin dilaurate (DBTDL) (manufactured by Nitto Kasei Co., Ltd.) • 4-Dimethylaminopyridine (DMAP) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0096] Tables 1 and 2 show the weight-average molecular weight (Mw) of polymer (A) or (A') in the polymer solutions of Production Examples 1 to 12. The weight-average molecular weight (Mw) of polymer (A) or (A') was calculated by the method shown below.

[0097] [Weight average molecular weight (Mw)] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the copolymer in the copolymer emulsion were measured by GPC (gel permeation chromatography) after dissolving approximately 0.1 g of emulsion by adding 1.5 mL of THF and shaking it by hand, and then calculating the values ​​in terms of polystyrene. For the GPC measurement, a GPC system from Shimadzu Corporation was used as the GPC measuring instrument, and a differential refractive index detector RID-10A was used as the detector. In addition, three Shodex® LF-804 columns and one KF-801 column from Showa Denko K.K. were used as the columns. The GPC measurement was performed under the conditions of a column temperature of 40°C and a flow rate of 1.0 mL / min.

[0098] [Examples 1-16, Comparative Examples 1-9] In a 200 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, polymer (A) or (A') from the polymer solutions of Production Examples 1-12 was mixed with base (B) and base (B) to obtain the compositions shown in Tables 3-5. The internal temperature was raised to 80°C, and foaming was observed after 5 minutes. The temperature was then maintained at 80°C for 30 minutes to obtain a blocked isocyanate polymer having an ethylenic double bond (d2). Subsequently, polyfunctional thiol (C) was mixed to obtain the compositions shown in Tables 3-5 to prepare the compositions.

[0099] [Evaluation of solvent resistance] The compositions of Examples 1-16 and Comparative Examples 1-9 were each applied to a glass substrate (alkali-free glass substrate) measuring 5 cm in length and 2 cm in width using a barcoder (#34) to a thickness of 78 μm, forming a coated film. Then, the solvent in the coated film was evaporated and the film was baked by heating at temperatures of 40°C, 80°C, 100°C, 120°C, or 140°C for 30 minutes to form a cured film. At 25°C, the solvent in the coated film was evaporated overnight.

[0100] The mass of each cured film obtained was measured. Next, each glass substrate with the cured film was immersed in 100g of acetone at 25°C for 24 hours. After that, the glass substrates were removed from the acetone and dried at 110°C for 1 hour. The mass of the cured film remaining on the dried glass substrate was measured, and the residual film percentage was calculated using the following formula to evaluate the solvent resistance of the cured film. In other words, the closer the residual film percentage is to 100%, the better the solvent resistance of the cured film. For evaluation, a residual film percentage of 20% or more was considered acceptable. The results are shown in Tables 3 to 5. Residual film percentage = (Mass of cured film after acetone immersion / Mass of cured film before acetone immersion) × 100 (%)

[0101] The following ingredients were used, as listed in Tables 3 to 5. "Base (B)" 1,8-Diazabicyclo[5.4.0]-7-Undecene (DBU) (manufactured by Tokyo Chemical Industry Co., Ltd.) • DBU formate (manufactured by Sunapro Co., Ltd., U-CAT SA603) • DBU phenolic salt (manufactured by Sunapro Co., Ltd., U-CAT SA1) • Triethylmethylammonium 2-ethylhexanoate (manufactured by Sunapro Co., Ltd., U-CAT 18X) 1,5-Diazabicyclo[4.3.0]-5-nonene (manufactured by Sunapro Co., Ltd., DBN) • 1,5,7-Triazabicyclo[4.4.0]deca-5-ene (TBD) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0102] "Polyfunctional thiol (C)" Pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonac Co., Ltd., Karenz MT PE-1) • 1,3,5-Tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinan-2,4,6-trione (manufactured by Resonaq Corporation, Karenz MT NR1) • Trimethylolpropane Tris(3-mercaptobutyrate) (manufactured by Resonac Corporation, Karens MT TPMB) • Pentaerythritol tetrakis (mercaptoacetate) (manufactured by Tokyo Chemical Industry Co., Ltd., product code P0888) • Tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd., product code T3484) • Dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd., product code D5212)

[0103] [Table 3-1]

[0104] [Table 3-2]

[0105] [Table 4]

[0106] [Table 5]

[0107] The compositions of the embodiments of the present invention exhibit high solvent resistance in the cured product at curing temperatures of 100°C or higher.

Claims

1. A composition comprising a polymer (A) containing a structural unit (a) having a group represented by the following formula (1), a base (B), and a polyfunctional thiol (C). 【Chemistry 1】 (In formula (1), R 1 and R 2 Each of these is independently a hydrocarbon group having 1 to 20 carbon atoms. 3 and R 4 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (* indicates a bonding site.)

2. The aforementioned R 1 and R 2 However, each is independently a hydrocarbon group having 1 to 3 carbon atoms, R 3 and R 4 The composition according to claim 1, wherein each is independently a hydrogen atom or a methyl group.

3. The composition according to claim 1, wherein the content of the constituent unit (a) is 1 to 99 mol% with respect to 100 mol% of all constituent units.

4. The composition according to claim 1, wherein the base (B) is one or more selected from 1,8-diazabicyclo[5.4.0]-7-undecene or a salt thereof, 1,5-diazabicyclo[4.3.0]-5-nonene or a salt thereof, 1,5,7-triazabicyclo[4.4.0]deca-5-ene or a salt thereof, and triethylmethylammonium 2-ethylhexanoate.

5. The composition according to claim 1, wherein the polyfunctional thiol (C) is a compound having three or more thiol groups in its molecule.

6. In the constitutional unit (a), R 1 and R 2 are ethyl groups, and R 3 and R 4 are hydrogen atoms. The composition according to claim 1.

7. A cured product having a structure represented by formula (7) or (8). 【Chemistry 2】 (In formula (7) or (8), *1 is the binding site to the main chain. R 5 and R 6 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms, and s represents an integer from 0 to 2. 7 R is in equation (1) 1 and R 2 It is similar to the above. (*2 indicates the bonding site to the linking group.)

8. A resin molded article using the cured product described in claim 7.

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