JP6791319B1 - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent coating film strength and high extensibility in the fields of a film substrate, an adhesive, a coating agent, an elastomer, a medical material, an optical material and the like. The purpose is. The above-mentioned problem contains a urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth) acrylic unit (B) are linked by a chain transfer agent residue, and a cross-linking agent (D). The curable resin composition (F), wherein the (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer (E) having one or more cross-linking groups. It is solved by the curable resin composition (F). [Selection diagram] None

Description

The present invention has a curable resin composition containing a urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth) acrylic unit (B) are linked by a chain transfer agent residue, and a cross-linking agent (D). A curable resin composition of the product (F), wherein the (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer (E) having one or more cross-linking groups. Regarding thing (F).

Examples of the resin preferably used in industrial applications include acrylic resins that can be designed in a wide range suitable for the applications due to the wide selection of raw materials, and urethane resins that can impart wear resistance and flexibility. Further, when a crosslinkable functional group is introduced into these resins, the crosslink density of the cured product can be increased, so that the strength can be improved. Therefore, acrylic resins and urethane resins are being studied in a wide range of fields such as film substrates, adhesives, coating agents, and elastomers by utilizing the high degree of freedom in design and the characteristics of resins.

However, in general, acrylic resin alone can obtain a relatively high-strength coating film or molded product, but has a problem of inferior extensibility and stress relaxation property. On the other hand, urethane resin alone has excellent extensibility. It was difficult to achieve both strength and extensibility because the extensibility was lost when the design was made to impart strength.

In response to such problems, for example, in Patent Document 1, acrylic resin is polymerized in the presence of urethane resin to form a composite film composed of urethane resin and acrylic resin, thereby providing excellent breaking strength and high extensibility. Adhesive sheets that have been proposed, but in general, the compatibility between acrylic resin and urethane resin is poor and the applicable range is limited, so both strength and extensibility are not sufficient for applications that require higher strength. It was.

JP-A-2003-96140

An object of the present invention is to provide a curable resin composition having excellent coating film strength and high extensibility in the fields of film substrates, adhesives, coating agents, elastomers, medical materials, optical materials and the like. And.

The present invention has a curable resin composition containing a urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth) acrylic unit (B) are linked by a chain transfer agent residue, and a cross-linking agent (D). A curable resin composition of the product (F), wherein the (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer (E) having one or more cross-linking groups. Regarding thing (F).

Further, in the present invention, the ethylenically unsaturated monomer (E) having one or more of the cross-linking groups is an ethylenically unsaturated monomer (E-1) having a hydroxyl group, and the cross-linking agent (D) is used. The curable resin composition (F) according to claim 1, wherein the curable resin composition (F) contains polyisocyanate.

The present invention also comprises the curable resin composition (F) in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by residues of a chain transfer agent having an amino group. ).

Further, in the present invention, the content of the structural unit derived from the ethylenically unsaturated monomer (E) having one or more cross-linking groups is 1 to 60 parts by weight in 100 parts by weight of the (meth) acrylic unit (B). The curable resin composition (F) according to any one of claims 1 to 3, wherein the curable resin composition (F) is characterized by the above.

Further, the present invention is characterized in that the content of the (meth) acrylic unit (B) is 5 to 75 parts by weight in 100 parts by weight of the urethane / acrylic composite resin (C). The present invention relates to the curable resin composition (F) according to item 1.

The present invention also relates to a resin layer obtained by curing the curable resin composition (F).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a curable resin composition having excellent coating film strength and high extensibility, which can be expected to be used for film substrates, adhesives, coating agents, elastomers, medical materials, optical materials and the like. It was.

The curable resin composition (F) of the present invention contains a urethane-acrylic composite resin (C) and a cross-linking agent (D).

<Urethane / acrylic composite resin (C)>
The urethane-acrylic composite resin (C) of the present invention has a structure in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by a chain transfer agent residue, and the (meth) acrylic unit. (B) has a structural unit derived from the ethylenically unsaturated monomer (E) having one or more cross-linking groups.

The urethane / acrylic composite resin (C) can be produced by the following method. First, a chain transfer agent having an isocyanate group in a urethane prepolymer having isocyanate groups at both ends, which is obtained by reacting a polyol and an isocyanate group-containing compound, and a functional group and a mercapto group capable of reacting with the isocyanate group in the molecule. To synthesize a urethane unit (A) having a mercapto group, which is a chain transfer agent residue, at both ends. Then, using the terminal mercapto group in the obtained urethane unit (A), an ethylenically unsaturated monomer containing one or more crosslinked groups (E) is used as a polymerization initiator. In the presence, chain transfer polymerization is carried out to form a (meth) acrylic unit (B). In this way, the urethane-acrylic composite resin (C) in which the urethane unit (A) and the (meth) acrylic unit (B) are linked by a chain transfer agent residue can be obtained.

First, the urethane unit (A) of the urethane-acrylic composite resin (C) will be described in detail below.

<Polyprethane>
Typical examples of the polyols constituting the urethane unit (A) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, vegetable oil-based polyols, and other polyols. One of these may be used alone, or two or more thereof may be used in combination.

Examples of the polyether polyol include polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran and the like, specifically, polyethylene glycol, polypropylene glycol, poly (ethylene / propylene) glycol and polytetramethylene glycol. And so on. Further, examples thereof include hexanediol, methylhexanediol, heptanediol, octanediol, and polyether polyols obtained by condensing a mixture thereof.

Further, as the polyether polyol, a compound having at least two or more active hydrogen groups such as a low molecular weight polyol, an aliphatic amine compound, an aromatic amine compound, an alkanolamine, and a bisphenol is used as a starting material. Examples thereof include a polyol obtained by adding an alkylene oxide such as methylene oxide, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or polyoxytetramethylene oxide.

Among the compounds having two or more active hydrogen groups, examples of the low molecular weight polyol include a bifunctional low molecular weight polyol and a trifunctional or higher functional low molecular weight polyol.

The bifunctional low molecular weight polyol is not particularly limited, but for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4. -Butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, nonanediol, dipropylene glycol, diethylene glycol, triethylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 , 3-Propanediol, 2-Ethyl-1,3-Hexanediol, 2-Methyl-1,8-octanediol, Polyoxyethylene glycol (additional moles: 10 or less), Polyoxypropylene glycol (additional moles: 10 or less) ), Cyclohexanediol, Cyclohexanedimethanol, Tricyclodecanedimethanol, Cyclopentadienedimethanol, Dimerdiol, Bisphenol A, N, N-bis (2-hydroxypropyl) aniline, Dimethylolacetic acid, Dimethylolpropionic acid, Dimethylolbutane Acids, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, dihydroxybenzoic acid and the like can be mentioned.

The trifunctional or higher functional low molecular weight polyol is not particularly limited, but is limited to trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,2,3-butanetriol, 1,2,4-butanetriol. , 1,2,6-butanetriol, trimethylolpropane, trimethylolpentene, trimethylolhexene, trimethylolhepten, trimethylolocten, trimethylolnonen, trimethylolpropane, trimethylolpropane, trimethylolpropane, tri Methylolpropane, trimethylolpentadecene, trimethylolhexadecene, trimethylolheptadecene, trimethyloloctadecene, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl -Hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, trimethylolhexene, 1,2,3-octanetriol, 1,3 7-octanetriol, 3,7-dimethyl-1,2,3-octanetriol, 1,1,1-, 1,1,1-trimethylolpropane, 1,2,10-decantryol, 1,1, 1-trimethylolisoheptadecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonan, 1,1 , 1-trimethylol-tert-tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl -Hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane, 1,2,3 , 4-Butanetetraol, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, triglycerin, polyglycerin, trimethylolethane, dimethylolpropane, tris (2-hydroxyethyl) isocyanurate, benzene-1 , 3,5-Triol, benzene-1,2,3-triol, Stilben-3,4', 5-Triol, shoe claus, inositol, sorbitan, sorbitol, mannitol, saccharose, cellulose, xylitol Le etc. can be mentioned.

Among the compounds having two or more active hydrogen groups, examples of the aliphatic amine compounds include ethylenediamine, triethylenetetramine, diethylenetriamine, and triaminopropane. Examples of the aromatic amine compound include toluenediamine, diphenylmethane-4,4-diamine and the like. Examples of alkanolamines include ethanolamine and diethanolamine. Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol B, bisphenol C, bisphenol E, bisphenol F and the like.

Examples of the polyester polyol include a polyester polyol obtained by a condensation reaction of the above-mentioned low molecular weight polyol and a dibasic acid component.

Examples of the dibasic acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic anhydride, isophthalic acid, trimellitic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, etc. Included are aliphatic or aromatic dibasic acids, and their anhydrides.
Examples thereof include polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as ε-caprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone.

Examples of the polycarbonate polyol include those obtained by reacting the above-mentioned low molecular weight polyol with a carbonate compound such as a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate.
Further, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate and the like, examples of the alkylene carbonate include ethylene carbonate and the like, and examples of the diaryl carbonate include diphenyl carbonate and the like.

Examples of the polyolefin-based polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene.

Examples of the vegetable oil-based polyol include castor oil derived from plants, dimer acid, and polyols made from soybean oil.

Among these, a polyether polyol, a polyester polyol, and a polycarbonate polyol are preferable, and a polyether polyol is more preferable.

The molecular weight of these polyols is preferably a number average molecular weight of 500 or more and less than 5000, and more preferably 700 or more and less than 3,500.

Further, the above-mentioned low molecular weight polyol can be used in combination for the purpose of adjusting the urethane bond concentration and introducing various functional groups.

<Isocyanate group-containing compound>
Examples of the isocyanate group-containing compound constituting the urethane unit (A) include aromatic, aliphatic, and alicyclic isocyanate group-containing compounds. One of these may be used alone, or two or more thereof may be used in combination.

Examples of the aromatic isocyanate group-containing compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-diphenylmethane. Diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, trizine diisocyanate, xylylene diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 3,3'- Dimethyl-4,4'-biphenylenediocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, 3,3'-dichloro-4,4'-biphenylenediocyanate, 1,5-tetrahydronaphthalenedi isocyanate, etc. Be done.

Examples of the aliphatic isocyanate group-containing compound include trimethylene diisocyanis, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanis, 2,3-butylenedisocyanate, 1,3-butylenedisocyanate, and dodecamethylene. Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanis, lysine diisocyanis, lysine ester triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate tetramethylene diisocyanate, pentamethylene diisocyanate, Examples thereof include trimethylhexamethylene diisocyanate.

Examples of the alicyclic isocyanate group-containing compound include isophorone diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, and methyl-2. Examples thereof include 6-cyclohexanediisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, hydrogenated xylylene diisocyanate, dimerate diisocyanate, norbornene diisocyanate and the like.

The reaction between the polyol and the isocyanate group-containing compound may be carried out in a solvent or in a solvent-free manner, and is carried out using a known urethanization reaction. A catalyst may be used in combination for the purpose of adjusting the reactivity.

<Reaction solvent>
As the reaction solvent, any solvent can be used as long as it does not react with the isocyanate group. The reaction solvent is not limited to the following examples, for example, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, toluene, xylene, anisole, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol. Monobutyl ether acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m -Cresol, γ-butyrolactone, γ-valerolactone and the like can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.

<Catalyst>
As the catalyst, known metal-based catalysts and amine-based catalysts can be used. Metallic catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), lead 2-ethylhexoate, 2-ethylhexyl titanate, titanium ethyl acetate, 2-ethylhexoate. Examples thereof include iron, 2-ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin and the like. Examples of the amine-based catalyst include tertiary amines such as tetramethylbutanediamine. These catalysts are used in the range of 0.05 to 1 mol% with respect to the polyol.

<Chain transfer agent with mercapto group>
The chain transfer agent having a mercapto group is not particularly limited as long as it has a functional group capable of reacting with an isocyanate group and a mercapto group in the molecule, but preferably one amino group and one mercapto in the molecule. It is a compound containing a group. The mercapto group also has reactivity with the isocyanate group, but by having an amino group in the molecule that is more reactive than the mercapto group, the amino group quickly reacts with the isocyanate group in the urethane prepolymer to form a urea bond. Then, the mercapto group is efficiently introduced into the end of the urethane prepolymer. When a compound having a hydroxyl group is used instead of the amino group, the difference in reactivity between the hydroxyl group and the mercapto group is small, so that the side reaction between the mercapto group and the isocyanate group proceeds at a high rate, and it is accurate at the end of the urethane prepolymer. It is difficult to introduce a mercapto group into.

The compound containing one amino group and one mercapto group in the molecule is not limited to the following examples, for example, 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2. Amino alkanethiols such as −thiol, 4-amino-1-butanethiol;
Examples thereof include aminobenzenethiols such as 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Of these, 2-aminoethanethiol is particularly preferable.

<Number average molecular weight of urethane unit (A)>
The number average molecular weight of the urethane unit (A) is not particularly limited, but is preferably 3,000 to 200,000. When it is 3,000 or more, the extensibility of the obtained resin layer is excellent, and when it is 200,000 or less, the viscosity can be easily adjusted.

Next, the (meth) acrylic unit (B) of the urethane-acrylic composite resin (C) will be described in detail below. The (meth) acrylic unit (B) has a structural unit derived from an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (E) having one or more cross-linking groups.

<Ethylene unsaturated monomer (E) having one or more cross-linking groups>
As the ethylenically unsaturated monomer (E) having one or more cross-linking groups, for example, a compound having one polymerizable unsaturated double bond and one or more cross-linking groups in the molecule can be used. The crosslinkable group is not limited to the following examples, and examples thereof include a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group and a block thereof. Among them, an ethylenically unsaturated monomer (E-1) having a hydroxyl group is particularly preferable, and a resin layer having particularly excellent strength and extensibility can be obtained by reacting with a cross-linking agent (D) described later and curing. preferable.

<Ethylene unsaturated monomer having a hydroxyl group (E-1)>
The ethylenically unsaturated monomer (E-1) having a hydroxyl group is not limited to the following examples, and is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl. (Meta) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl- Examples thereof include 2-hydroxypropyl phthalate or a caprolactone adduct of these monomers (the number of moles added is 1 to 5), polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, glycerin mono (meth) acrylate and the like.

Examples of the (meth) acrylate having a carboxyl group include (meth) acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) (meth) acrylic acid, and 2-(. Meta) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, Examples thereof include ethylene oxide-modified succinic acid (meth) acrylate, ω-carboxypolycaprolactone (meth) acrylate, and p-vinylbenzoic acid.

Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycyl diether, 3,4-epoxide butyl (meth) acrylate, and 3-methyl. -3,4-epoxide butyl (meth) acrylate, 3-ethyl-3,4-epoxide butyl (meth) acrylate, 4-methyl-4,5-epoxide pentyl (meth) acrylate, 5-methyl-5,6- Epoxide hexyl (meth) acrylate, glycidyl α-ethylacrylate, allyl glycidyl ether, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, (3,4-epoxide cyclohexyl) methyl (meth) acrylate, N- (3, 5-Dimethyl-4-glycidyl) benzylacrylamide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl Benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-diglycidyl oxymethyl styrene, 2,4-diglycidyl oxymethyl styrene, 2,5-diglycidyl oxymethyl styrene, 2,6-di Glycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxy Examples thereof include methylstyrene and 2,4,6-triglycidyloxymethylstyrene.

Examples of the (meth) acrylate having an isocyanate group and its block body include (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloyloxyethoxyethyl isocyanate, and 1,1- (bis (meth). ) Acryloyloxymethyl) ethyl isocyanate, m- (meth) acryloylphenyl isocyanate, α, α-dimethyl-4-isopropenylbenzyl isocyanate and the like. One type may be used alone, or two or more types may be used in combination.

The ethylenically unsaturated monomer (E) having one or more cross-linking groups preferably contains 1 to 60 parts by weight, more preferably 5 to 50 parts by weight, out of 100 parts by weight of the (meth) acrylic unit (B). Is. When the ethylenically unsaturated monomer (E) having one or more cross-linking groups is 1 to 60 parts by weight, a resin layer having excellent strength and extensibility can be obtained, which is preferable.

The (meth) acrylic unit (B) may contain other ethylenically unsaturated monomers in addition to the ethylenically unsaturated monomer (E) having one or more cross-linking groups.

Other ethylenically unsaturated monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (Meta) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate , Decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Alkyl (meth) acrylates;
Cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Cyclic alkyl (meth) acrylates such as acrylates and isobornyl (meth) acrylates;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meta) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meta) acrylates having an aromatic ring of
Methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, Phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, Nonylphenoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxy (Meta) acrylates having an alkyl ether group such as ethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate;
3- (Acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane Have (meth) acrylates;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Examples thereof include vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether. One of these may be used alone, or two or more thereof may be used in combination.

The (meth) acrylic unit (B) preferably contains 5 to 75 parts by weight, more preferably 10 to 60 parts by weight, out of 100 parts by weight of the urethane / acrylic composite resin (C). By containing 5 to 75 parts by weight of the (meth) acrylic unit (B), a resin layer having excellent strength and extensibility can be obtained.

<Polymerization initiator>
As the polymerization initiator, known azo-based compounds and organic peroxides can be used, and the azo-based compound is not limited to the following examples, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate) , Dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] and the like, and examples of the organic peroxide are not limited to the following examples, but for example, benzoyl peroxide and t-butylperoxy. 2-ethylhexaate, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylper Examples thereof include oxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. One of these may be used alone, or two or more thereof may be used in combination.

The polymerization initiator is preferably used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic unit (B). A range of 0.001 to 15 parts by weight is preferable because chain transfer polymerization effectively proceeds.

<Number average molecular weight of (meth) acrylic unit (B)>
The number average molecular weight of the (meth) acrylic unit (B) is not particularly limited, but is preferably 2,000 to 200,000. When it is 2,000 or more, the breaking strength of the obtained resin layer is excellent, and when it is 200,000 or less, the viscosity can be easily adjusted.

<Number average molecular weight of urethane / acrylic composite resin (C)>
The number average molecular weight of the urethane-acrylic composite resin (C) is not particularly limited, but is preferably 5,000 to 300,000. When it is 5,000 or more, the breaking strength of the obtained resin layer is excellent, and when it is 300,000 or less, the viscosity can be easily adjusted.

<Crosslinking agent (D)>
The cross-linking agent (D) reacts with the cross-linking group in the urethane-acrylic composite resin (C) and is cured to obtain a resin layer having excellent strength and extensibility.
The cross-linking agent (D) includes a functional group contained in the urethane-acrylic composite resin (C) that can react with the cross-linking group in the ethylenically unsaturated monomer (E) having one or more cross-linking groups. The functional group is not particularly limited as long as it has, and examples of the functional group include, but are not limited to, an isocyanate group, an epoxy group, a carboxy group, an amino group, and a hydroxyl group.

The cross-linking agent containing an isocyanate group is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in the molecule, and for example, the above-mentioned isocyanate group-containing compounds and their biuret, nurate, adduct, and the like. In addition, a bifunctional or higher functional isocyanate compound such as a condensate can be used.

Examples of the biuret body include a hexamethylene diisocyanate biuret body (product name "Sumijour N-75", manufactured by Sumika Bayer Urethane Co., Ltd .; product name "Duranate 24A-100", manufactured by Asahi Kasei Chemicals Co., Ltd.).

Examples of the nurate form include a nurate form of hexamethylene diisocyanate (product name "Sumijour N-3300", manufactured by Sumika Bayer Urethane Co., Ltd.), a nurate form of isophorone diisocyanate (product name "Death Module Z-4370", Sumika). Bayer Urethane Co., Ltd.), tolylene diisocyanate nurate (product name "Coronate 2030", manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like.

As the adduct, a bifunctional or higher functional isocyanate compound obtained by reacting the above-mentioned isocyanate group-containing compound with the above-mentioned compound having two or more active hydrogen groups, and the above-mentioned isocyanate group-containing compound with the above-mentioned polyol can be used. For example, hexamethylene diisocyanate adduct compound of trimethylolpropane (product name "Takenate D-160N", manufactured by Mitsui Chemicals, Inc.), isophorone diisocyanate adduct compound of trimethylolpropane (product name "Takenate D-140N", Mitsui Chemicals Co., Ltd.) (Manufactured by the company) and the like.

Examples of other condensates include polyfunctionals of the above-mentioned isocyanate group-containing compounds, carbodiimide-modified products, biuret-modified products, and allophanate-modified products. For example, polymethylene polyphenyl polyisocyanate (product name "PAPI27", Dow Co., Ltd.) , Hexamethylene diisocyanate biuret (product name "Takenate D-165N", manufactured by Mitsui Chemicals, Inc.), carbodiimide-modified diphenylmethane diisocyanate (product name "Isonate143L", manufactured by Dow Co., Ltd.) and the like.

The cross-linking agent containing an epoxy group is not limited to the following examples, and for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether. , Trimethylol Propane triglycidyl ether, diglycidyl aniline, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane, and Examples thereof include N, N, N', N'-tetraglycidylaminophenylmethane and the like.

The cross-linking agent containing an amino group is not limited to the following examples, for example, ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, p-phenylenediamine and the like. Diamines;
2-Hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyropylethylenediamine Diamines having hydroxyl groups such as di-2-hydroxypyrropyltylenediamine, di-2-hydroxypropylethylenediamine;
Diethylenetriamine, iminobispropylamine, triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine, 6,6-iminodihexylamine, 3,7-diazanonan-1,9-diamine, N, N '-Bis (3-aminopropyl) ethylenediamine, trifunctional or higher functional amines such as JEFFAMINE D-230, D-400, D-2000, T-403, T-3000 (all manufactured by HUNTSMAN) Kind.

The cross-linking agent containing a carboxyl group is not limited to the following examples, and for example, succinic acid, adipic acid, sebacic acid, maleic acid, phthalic acid, naphthalenedicarboxylic acid, methylphthalic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, Examples thereof include methylnorbornenedicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid and the like.

The cross-linking agent containing a hydroxyl group is not limited to the following examples, and for example, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, methylpropanediol, pentanediol, methylpentanediol, and hexane. Diol, nonanediol, neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol , 2-Ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalic acid-neopentyl glycol ester, dimethylolpropanoic acid, dimethylolbutanoic acid, trimethylolethane, Examples thereof include trimethylolpropane, trimethylolbutane, glycerin, and pentaerythritol. One of these may be used alone, or two or more thereof may be used in combination.

The combination of the cross-linking group derived from the ethylenically unsaturated monomer (E) having one or more cross-linking groups in the (meth) acrylic unit (B) and the cross-linking agent (D) is not particularly limited, but is a cross-linking group. The ethylenically unsaturated monomer (E) having one or more of the above is an ethylenically unsaturated monomer (E-1) having a hydroxyl group, and the cross-linking agent (D) has two or more isocyanate groups in the molecule. A polyisocyanate having is preferable because a resin layer having particularly excellent strength and extensibility can be obtained.

The ratio of the number of moles of these functional groups in the cross-linking agent (D) to the number of moles of the cross-linking groups in the urethane-acrylic composite resin (C) (in the functional group / urethane-acrylic composite resin (C) in the cross-linking agent (D)). The cross-linking group) is preferably 0.2 to 5.0, and more preferably 0.5 to 3.0. When it is 0.2 to 5.0, the strength and extensibility are excellent.

<Resin layer>
The cured product (resin layer) formed from the curable resin composition (F) of the present invention is known on a substrate by adjusting the curable resin composition to a viscosity suitable for the coating method with the above reaction solvent. It can be obtained by coating with an arbitrary film thickness by the printing method of the above, for example, heating to a temperature of 50 ° C. to 200 ° C. to remove the solvent, and then curing at a temperature of 20 ° C. to 200 ° C.

The resin layer and its laminate obtained by curing the curable resin composition (F) of the present invention are useful in the fields of film substrates, adhesives, coating agents, elastomers, medical materials, optical materials, and the like. is there.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention. Unless otherwise specified, "parts" in the examples represent "parts by weight" and "%" represents "% by weight". The methods for measuring the resin solid content concentration (NV), number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight dispersion (Mw / Mn) in the examples are as follows.

<Resin solid content concentration (NV)>
According to JISK5601-1-2, the resin solid content concentration (%) was defined as the heating residue when measured at a heating temperature of 150 ° C. and a heating time of 20 minutes.

<Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight dispersion (Mw / Mn)>
The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight dispersion (Mw / Mn) of the resin are polystyrene-equivalent values measured by GPC (gel permeation chromatography), and are GPC-manufactured by Tosoh Corporation. By 8020, polystyrene was used as the eluent, and three TSKgelSuperHM-M (manufactured by Tosoh Corporation) were used as the column, and the measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

The abbreviations of the compounds used in the examples are as follows.
PTG-2000SN; Polytetramethylene glycol, hydroxyl value 56, C-2090 manufactured by Hodoya Chemical Industry Co., Ltd .; Polycarbonate diol, hydroxyl value 56, IPDI: isophorone diisocyanate HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl Acrylate MAA: GMA methacrylate: Glycidyl methacrylate MMA: Methyl methacrylate BA: Normal butyl acrylate MEK: Methyl ethyl ketone AIBN: 2,2-azobisisophorone diisocyanate OTG: Normal octyl thioglycolate TDI-TMP: Trimethylol of tolylene diisocyanate Propane Adduct TETRAD-X: N, N, N', N'-Tetraglycidyl-m-xylylene diisocyanate, product name "TETRAD-X", Mitsubishi Gas Co., Ltd. T-403: Polyoxypropylene triamine, product name " JEFFAMINE T-403 ", manufactured by HUNTSMAN

<Synthesis of urethane unit (A)>
[Synthesis Example 1 (A-1)]
In a reaction vessel equipped with a nitrogen gas introduction tube, agitator, thermometer, and recirculator, first, 341.3 parts of PTG-2000SN (manufactured by Hodoya Chemical Industry Co., Ltd.) as a polyol and 58.7 parts of IPDI as an isocyanate group-containing compound. 0.02 part of titanium diisopropoxybiz (ethylacetacetate) was charged as a catalyst, and the mixture was uniformly stirred and then reacted at 110 ° C. for 5 hours in a nitrogen atmosphere to obtain a urethane prepolymer. Next, the mixture was cooled to 80 ° C., 100.0 parts of MEK was added as a solvent, 13.0 parts of 2-aminoethanethiol was added as a chain transfer agent, and the mixture was reacted at 75 ° C. for 2 hours to increase the resin solid content concentration to 80%. , A urethane unit (A-1) having a number average molecular weight (Mn) of 17,100 was obtained. The end point of the reaction was confirmed by FT-IR by disappearance of the peak derived from the isocyanate group (around 2270 cm-1).

[Synthesis Example 2 (A-2)]
A urethane unit (A-) having a resin solid content concentration of 80% and a number average molecular weight (Mn) of 16,400 was carried out in the same manner as in Synthesis Example 1 except that the polyol was changed to C-2090 (manufactured by Kuraray Co., Ltd.). 2) was obtained.

<Synthesis of urethane / acrylic composite resin (C)>
[Synthesis Example 3 (C-1)]
In a reaction vessel equipped with a nitrogen gas introduction pipe, a stirrer, a thermometer, and a recirculator, 21.3 parts of the urethane unit (A-1) obtained in Synthesis Example 1, 9.8 parts of MMA, and 39 parts of BA. After adding 1 part, 2.6 parts of HEMA and 98.7 parts of MEK as a solvent and stirring uniformly, the temperature was raised to 75 ° C. under a nitrogen atmosphere, and 0.1 part of AIBN as a polymerization initiator was added thereto for 30 minutes. It was added in 13 portions each time, and after the addition of the polymerization initiator, it was reacted for another 2 hours to form a (meth) acrylic unit to obtain a urethane-acrylic composite resin (C-1). Table 1 shows the ratio (%) of the (meth) acrylic unit (B) in the urethane-acrylic composite resin (C-1), the resin solid content concentration, the number average molecular weight, and the molecular weight dispersion.

[Synthesis Examples 4 to 16 (C-2 to C-14)]
The urethane unit (A), (meth) acrylic unit (B) and MEK were subjected to the same operations as in Synthesis Example 3 except that the composition was changed to the composition shown in Table 1, and the urethane / acrylic composite resin (C-2 to C-2 to C-14) was obtained. Table 1 shows the ratio (%) of the (meth) acrylic unit (B) in the obtained urethane-acrylic composite resin (C-2 to C-14), the resin solid content concentration, the number average molecular weight, and the molecular weight dispersion. Is.

<Synthesis of comparative resin (H)>
[Comparative Synthesis Example 1 (H-1)]
341.3 parts of C-2090 (manufactured by Kuraray Co., Ltd.) as a polyol, 58.7 parts of IPDI as an isocyanate group-containing compound, and titanium as a catalyst in a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, a thermometer, and a refluxer. 0.02 parts of diisopropoxybiz (ethylacetacetate) was charged, stirred uniformly, and then reacted at 110 ° C. for 5 hours in a nitrogen atmosphere to obtain a urethane prepolymer. After cooling to 80 ° C., adding 100.0 parts of MEK and 10.3 parts of 2-aminoethanol as a solvent, and reacting at 75 ° C. for 2 hours, the resin solid content concentration is 80% and the number average molecular weight (Mn). Obtained 19,400 comparative urethane resins (H-1). The end point of the reaction was confirmed by FT-IR by disappearance of the peak derived from the isocyanate group (around 2270 cm-1).

[Comparative Synthesis Example 2 (H-2)]
10.4 parts of OTG, 22.4 parts of MMA, 22.4 parts of BA, 11.2 parts of HEMA as a chain transfer agent in a reaction vessel equipped with a nitrogen gas introduction pipe, a stirrer, a thermometer, and a recirculator. After adding 99.3 parts of MEK as a solvent and stirring uniformly, the temperature was raised to 75 ° C. under a nitrogen atmosphere, and 0.1 part of AIBN as a polymerization initiator was added in 13 portions every 30 minutes. After the addition of the polymerization initiator, the mixture was further reacted for 2 hours to form a (meth) acrylic unit to obtain a comparative acrylic resin (H-2). The resin solid content concentration in the comparative acrylic resin (H-2) was 40%, the number average molecular weight was 17,600, and the molecular weight dispersion was 1.82.

[Comparative Synthesis Example 3 (H-3)]
In a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer, a thermometer, and a recirculator, 58.0 parts of the solution of the urethane unit (A-1) obtained in Synthesis Example 1, 20.0 parts of MMA, and a solvent. After adding 88.7 parts of MEK and stirring uniformly, the temperature was raised to 75 ° C. under a nitrogen atmosphere, and 0.1 part of AIBN as a polymerization initiator was added in 13 portions every 30 minutes to the polymerization initiator. After the addition of the above, the mixture was further reacted for 2 hours to form a (meth) acrylic unit to obtain a urethane-acrylic composite resin (H-3) for comparison. The ratio of the (meth) acrylic unit in the comparative urethane-acrylic composite resin (H-3) is 30%, the resin solid content concentration is 40%, the number average molecular weight is 27,500, and the molecular weight dispersion is 1.52. there were.

<Preparation of curable resin composition>
[Example 1]
After adding 30.0 parts of urethane / acrylic composite resin (C-1), 1.26 parts of TDI-TMP as a cross-linking agent (D), and if necessary, MEK so that the resin solid content concentration becomes 40%. The curable resin composition of Example 1 was prepared by stirring and mixing at room temperature.

[Examples 2 to 15, Comparative Examples 1 to 5]
With the compounding compositions shown in Table 2 or Table 3, the same operations as in Example 1 were carried out to prepare curable resin compositions of Examples 2 to 15 and Comparative Examples 1 to 5.

<Evaluation of curable resin composition>
The curable resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 5 were tested as follows. The determination results are shown in Tables 2 and 3.

(Evaluation of mechanical properties)
After curing, the film was placed in a silicone mold so as to have a thickness of 2 mm, cured in an environment of 50 ° C. for 3 days, and then a dumbbell-type cured film for punching evaluation was prepared with the dumbbell mold. The obtained cured film was pulled at a tensile speed of 50 mm / min using a tensile tester under the conditions of a temperature of 25 ° C. and a relative humidity of 65%, and the breaking stress (MPa) and breaking elongation (%) were measured and evaluated as follows. Judgment was made by criteria. The practical level is △ or higher.
(Evaluation criteria)
⊚: The breaking stress is 40 MPa or more and the breaking elongation is 600% or more.
◯: The breaking stress is 30 MPa or more and the breaking elongation is 200% or more and less than 600%, or the breaking stress is 25 MPa or more and less than 40 MPa and the breaking elongation is 600% or more.
Δ: The breaking stress is 25 MPa or more and less than 30 MPa and the breaking elongation is 200% or more and less than 600%, or the breaking stress is 20 MPa or more and less than 25 MPa and the breaking elongation is 500% or more.
X: The breaking stress is 20 MPa or more and less than 25 MPa and the breaking elongation is 200% or more and less than 500%, or the breaking stress is less than 20 MPa, or the breaking elongation is less than 200%.

The curable resin composition of the present invention gave good results in both breaking stress and breaking elongation. On the other hand, in the comparative curable resin composition, the breaking stress and / or the breaking elongation was inferior to that of the examples, and both physical properties could not be compatible.

Claims (7)

A curable resin composition (F) containing a urethane-acrylic composite resin (C) in which a urethane unit (A) and a (meth) acrylic unit (B) are linked by a chain transfer agent residue, and a cross-linking agent (D). And
The urethane unit (A) and the (meth) acrylic unit (B) are linked by a residue of a chain transfer agent having an amino group.
The (meth) acrylic unit (B) is an ethylenically unsaturated monomer having at least one cross-linking group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group and a block body thereof (meth). It has a structural unit derived from E)
The content of the (meth) acrylic unit (B) is 5 to 75 parts by weight out of 100 parts by weight of the urethane / acrylic composite resin (C).
A curable resin composition (D), wherein the cross-linking agent (D) contains at least one selected from the group consisting of a cross-linking agent having an isocyanate group, a cross-linking agent having an epoxy group, and a cross-linking agent containing an amino group. F). The curable resin according to claim 1, wherein the ethylenically unsaturated monomer (E) having one or more crosslinked groups is an ethylenically unsaturated monomer (E-1) having a hydroxyl group. Composition (F). The curable resin composition (F) according to claim 1 or 2, wherein the cross-linking agent (D) contains a polyisocyanate. The content of the structural unit derived from the ethylenically unsaturated monomer (E) having one or more cross-linking groups is 1 to 60 parts by weight out of 100 parts by weight of the (meth) acrylic unit (B). The curable resin composition (F) according to any one of claims 1 to 3 . The curable resin composition (F) according to any one of claims 1 to 4 , wherein the polyol constituting the urethane unit (A) is a polyether polyol. A resin layer obtained by curing the curable resin composition (F) according to any one of claims 1 to 5 . The resin layer according to claim 6 , wherein the breaking stress and breaking elongation at a thickness of 2 mm satisfy any of the following (1) and (2).
(1) The breaking stress is 25 MPa or more, and the breaking elongation is 200% or more.
(2) The breaking stress is 20 MPa or more, and the breaking elongation is 500% or more.