JP2016169266A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent adhesiveness to a nonpolar resin such as polyolefin and transparency.SOLUTION: A curable resin composition comprises a urethane compound having two or more vinyl ether groups in a molecule, with a weight average molecular weight of 10,000 or less, a thiol compound having two or more thiol groups in a molecule, a monofunctional (meth) acrylic monomer, and a radical generator.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition.

  Polyolefins such as polypropylene and polyethylene are excellent in moldability, solvent resistance, mechanical properties, appearance, etc., so they are processed into various molded products, automotive interior and exterior parts, exterior parts of electrical equipment, stationery, daily necessities, containers, It is used for various purposes such as film.

A photo-curing adhesive is used as an adhesive having a polyolefin as an adherend. The photo-curing type adhesive has an advantage that the curing speed is high and the working time can be shortened.
However, since polyolefin is a nonpolar resin, there is a problem that it has a low affinity with an adhesive, which is a polar substance, and is difficult to adhere.
For this reason, various photocurable adhesives having improved adhesion to polyolefin have been proposed.

For example, a photocationic curable adhesive containing an oxetane compound, an epoxy compound, and a photocationic curing catalyst has been proposed (see, for example, Patent Document 1).
Also, a vinyl ether-based resin composition which is a photocationic curable adhesive containing a vinyl ether monomer having two or more vinyl ether groups, a compound having a urethane skeleton and having a vinyl ether group at a terminal, and a photocationic polymerization initiator Has been proposed (see, for example, Patent Document 2).
Furthermore, as a photo-curing adhesive having excellent adhesion to metal as well as thermoplastic resins, it has a urethane oligomer having two or more vinyl ether groups, a vinyl ether monomer having vinyl ether groups, and two or more thiol groups. A photocurable composition containing a thiol compound has been proposed (see, for example, Patent Document 3).

JP 2001-131516 A JP 2013-053297 A International Publication No. 2011/021363

However, in the photocation curable adhesive described in Patent Document 1, since the oxetane compound and the epoxy compound are cured with an acid generated by photodecomposition of the photocation curing catalyst, the curing speed is relatively slow and the productivity is increased. There is a problem that it is inferior and easily yellowed by heat.
In addition, the photocationically curable vinyl ether resin composition described in Patent Document 2 contains a vinyl ether monomer having two or more vinyl ether groups and a urethane skeleton and a compound having a vinyl ether group at the terminal, and therefore has a curing rate. Is relatively fast, but has a problem that it is easily yellowed by heat.
Moreover, in the photocurable composition described in patent document 3, in order to harden the urethane oligomer which has 2 or more vinyl ether groups, and the vinyl ether monomer which has vinyl ether groups, the thiol compound which has 2 or more thiol groups Therefore, the adhesion to polyolefin, which is a nonpolar resin, is not sufficient.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the curable resin composition excellent in the adhesiveness with respect to nonpolar resins, such as polyolefin, and transparency.

Specific means for solving the problems include the following aspects.
<1> A urethane compound having two or more vinyl ether groups in the molecule and a weight average molecular weight of 10,000 or less, a thiol compound having two or more thiol groups in the molecule, and monofunctional (meta) A curable resin composition comprising an acrylic monomer and a radical generator.

<2> The urethane compound is at least a polyol compound having two or more hydroxy groups in the molecule, an isocyanate compound having two or more isocyanate groups in the molecule, a monovinyl ether compound having a hydroxy group in the molecule, <1> The curable resin composition according to <1>.
<3> The curable resin composition according to <2>, wherein the polyol compound has a number average molecular weight of less than 3,000.
<4> Curing according to <2> or <3>, wherein at least one compound selected from the polyol compound, the isocyanate compound, and the monovinyl ether compound is a compound having an alkyl group having 1 to 4 carbon atoms. Resin composition.

<5> The curable resin composition according to <4>, wherein the alkyl group is a methyl group.
<6> The curable resin composition according to any one of <1> to <5>, wherein the monofunctional (meth) acrylic monomer has a cyclic structure.
<7> The curable resin composition according to <6>, wherein the cyclic structure is an aromatic ring.
<8> The curable resin composition according to any one of <1> to <7>, wherein the monofunctional (meth) acrylic monomer is an acrylic monomer.

<9> The content of the monofunctional (meth) acrylic monomer in the curable resin composition is 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of the urethane compound <1> to <8>. The curable resin composition as described in any one of these.
<10> The curable resin composition according to any one of <2> to <9>, wherein the isocyanate compound is isophorone diisocyanate.
<11> The curable resin composition according to any one of <1> to <10>, which is used for adhesion to an olefin resin.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition excellent in the adhesiveness with respect to nonpolar resins, such as polyolefin, and transparency can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

In the present specification, a numerical range indicated using “to” means a range including the numerical values described before and after “to” as a minimum value and a maximum value, respectively.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.

  In the present specification, “(meth) acrylate” is a term including both acrylate and methacrylate, “(meth) acryl” is a term including both acrylic and methacrylic, and “(meth) acryloyl group” "Is a term that encompasses both acryloyl and methacryloyl groups.

  In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

[Curable resin composition]
The curable resin composition of the present invention is a urethane compound having two or more vinyl ether groups in the molecule and a weight average molecular weight of 10,000 or less (hereinafter referred to as “vinyl ether group-containing urethane compound” as appropriate). ), A thiol compound having two or more thiol groups in the molecule (hereinafter appropriately referred to as “polyfunctional thiol compound”), a monofunctional (meth) acrylic monomer, and a radical generator. It is a composition.
The curable resin composition of the present invention includes a vinyl ether group-containing urethane compound, a polyfunctional thiol compound, a monofunctional (meth) acrylic monomer, and a radical generator. Excellent in properties.
The reason why the curable resin composition of the present invention can exhibit such an effect is not clear, but the present inventors presume as follows.

Since the curable resin composition of the present invention includes a vinyl ether group-containing urethane compound, a polyfunctional thiol compound, a monofunctional (meth) acrylic monomer, and a radical generator, the following curing reaction is exhibited.
When the curable resin composition of the present invention is irradiated with light or heat, radicals are generated from the radical generator. The generated radical causes the enethiol reaction between the vinyl ether group-containing urethane compound and the polyfunctional thiol compound and the radical polymerization reaction of the monofunctional (meth) acrylic monomer to be almost simultaneously and independently in the reaction system. The cured product containing two types of reactants is generated.

The curable resin composition of the present invention contains a urethane compound (vinyl ether group-containing urethane compound) having two or more vinyl ether groups in the molecule and having a weight average molecular weight of 10,000 or less. In the composition, the molecule attracts molecules due to the urethane skeleton, the shrinkage during curing (curing shrinkage) is reduced, and the network structure formed during curing becomes dense (that is, the crosslinking density increases). And the cohesive strength after curing is increased. As a result, it is considered that the adhesion to the adherend is excellent.
In addition, since the curable resin composition of the present invention includes a urethane compound having a vinyl ether group which is a reactive group having low polarity, the wettability to a nonpolar resin such as polyolefin is improved, and the nonpolar resin such as polyolefin is obtained. It is considered that the adhesiveness to is excellent.

  The curable resin composition of the present invention contains a monofunctional (meth) acrylic monomer as a radical polymerizable monomer, and this monofunctional (meth) acrylic monomer has a relatively small curing shrinkage, and therefore the adherend It is thought that it contributes to the excellent adhesiveness to.

In cationic curing, which is a general curing method for vinyl ether group-containing compounds, polyene is generated by the acid used as the cationic polymerization initiator and the heat of curing, and the cured product is colored, so it is used for applications where transparency is required. There is a problem that you can not.
However, since the curable resin composition of the present invention contains a radical generator and is cured by radicals, the problem of coloring does not occur.
From the above, it is considered that the curable resin composition of the present invention is excellent in adhesiveness and transparency to nonpolar resins such as polyolefin.

<Vinyl ether group-containing urethane compound>
The curable resin composition of the present invention contains a urethane compound (vinyl ether group-containing urethane compound) having two or more vinyl ether groups in the molecule and having a weight average molecular weight of 10,000 or less.
The vinyl ether group-containing urethane compound has two or more vinyl ether groups in the molecule, preferably 2 to 4, more preferably 2 or 3.
Since the vinyl ether group-containing urethane compound has two or more vinyl ether groups which are reactive groups with low polarity in the molecule, the curable resin composition of the present invention has good wettability to nonpolar resins such as polyolefins. Thus, the adhesiveness to nonpolar resins such as polyolefin is excellent. Further, the curable resin composition of the present invention contains a urethane compound having two or more vinyl ether groups in the molecule, so that the network structure formed when the curable resin composition is cured becomes dense (that is, , The crosslink density is increased) and the cohesive force is increased, so that the adhesion to the adherend is excellent.

  The vinyl ether group-containing urethane compound is preferably a urethane compound represented by the following formula (1). The urethane compound represented by the following formula (1) has a urethane bond [—NH (CO) O—] in its structure, and has vinyl ether groups at both ends of the molecule.

In the formula (1), —X ¹ — and —X ² — are each independently —C ₄ H ₈ —, —C ₂ H ₄ —, —C ₂ H ₄ OC ₂ H ₄ —, —C ₂ H. ₄ OC ₂ H ₄ OC ₂ H ₄ —, —C ₃ H ₆ —, —C ₃ H ₆ OC ₃ H ₆ —, —C ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ —, or the following formula (2 ) Represents one of the linking groups represented by
-Z- represents a linking group represented by Formula (3).
L represents at least one skeleton selected from an ester skeleton, a caprolactone skeleton, an ether skeleton, and a carbonate skeleton.

  The linking group represented by the formula (2) has a cyclohexyl skeleton, and the linking group represented by the formula (3) has a skeleton derived from isophorone.

  The vinyl ether group-containing urethane compound is preferably at least one urethane compound selected from a urethane compound represented by the following formula (4) and a urethane compound represented by the following formula (5).

The vinyl ether group-containing urethane compound represented by the formula (4) has a carbonate skeleton as a repeating structure in the molecule. Incidentally, ^-X 1 in the formula ^{(4) -, - X 2} -, and -Z- is, ^-X 1 in the formula ^{(1) -, - X 2} -, and -Z- as synonymous.
The vinyl ether group-containing urethane compound represented by the formula (5) has an ether skeleton having 3 carbon atoms as a repeating structure in the molecule. Incidentally, ^-X 1 in the formula ^{(5) -, - X 2} -, and -Z- is, ^-X 1 in the formula ^{(1) -, - X 2} -, and -Z- as synonymous.

In formula (4), n represents the number of repeating structural units. n represents a positive integer, preferably 1 to 200, and more preferably 1 to 50 from the viewpoint of handling during synthesis.
In formula (5), m represents the number of repeating structural units. m represents a positive integer, preferably 1 to 700, and more preferably 1 to 100 from the viewpoint of handling during synthesis.

(Method for synthesizing vinyl ether group-containing urethane compound)
The vinyl ether group-containing urethane compound includes at least a polyol compound having two or more hydroxy groups in the molecule (hereinafter referred to as “polyol compound” as appropriate) and an isocyanate compound having two or more isocyanate groups in the molecule (hereinafter referred to as “polyol compound”). And a monovinyl ether compound having a hydroxy group in the molecule (hereinafter, appropriately referred to as a “hydroxy group-containing monovinyl ether compound”).
The method for synthesizing the vinyl ether group-containing urethane compound is not particularly limited, and at least a polyol compound, a polyfunctional isocyanate compound, and a hydroxy group-containing monovinyl ether compound are used. If necessary, a known polymerization catalyst is used. It can be synthesized by heating and mixing in the presence. For example, a vinyl ether group-containing urethane compound can be suitably synthesized by the following method. However, the method for synthesizing the vinyl ether group-containing urethane compound in the present invention is not limited to the following method.
A polyol compound, a polyfunctional isocyanate compound, and a polymerization catalyst such as dibutyltin dilaurate (DBTDL) are placed in a reaction vessel, and the temperature of the contents in the reaction vessel is raised to 60 ° C. and reacted for 2 hours. A polymerization catalyst and a hydroxy group-containing monovinyl ether compound are charged into the reaction vessel after the reaction, and further reacted for 2 hours to synthesize a vinyl ether group-containing urethane compound. The completion of the reaction can be confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
Hereinafter, the polyol compound, the polyfunctional isocyanate compound, and the hydroxy group-containing monovinyl ether compound will be described in detail.

-Polyol compound-
The polyol compound in the present invention is not particularly limited as long as it is a polyol compound having two or more hydroxy groups in the molecule.
Examples of the polyol compound include polycarbonate polyol, polyoxypropylene glycol, polycaprolactone polyol, polyester polyol, polytetramethylene ether glycol, polyoxyethylene-bisphenol A ether, and the like.
In the synthesis of the vinyl ether group-containing urethane compound, the polyol compound may be used alone or in combination of two or more.

  The number of hydroxy groups that the polyol compound has in the molecule is preferably 2 to 4, more preferably 2 or 3, from the viewpoint of handling during synthesis.

The number average molecular weight of the polyol compound is preferably less than 3,000, more preferably from 100 to 2,000, and still more preferably from 300 to 1,000.
When the polyol compound has a number average molecular weight of less than 3,000, the vinyl ether group-containing urethane compound to be synthesized is more attracted to molecules by the urethane skeleton in the curable resin composition, and the curing shrinkage is further eased. Therefore, the adhesion to the adherend becomes more excellent.

  The number average molecular weight (Mn) of the polyol compound can be calculated by a standard polystyrene conversion method using the following gel permeation chromatography (GPC). In addition, a commercial item can be used as a polyol compound as mentioned later. When the polyol compound is a commercial product, the catalog data of the commercial product is preferentially adopted.

~conditions~
Measuring device: High-speed GPC (HLC-8220 GPC (Tosoh Corporation))
Detector: differential refractometer (RI) RI-8220 (Tosoh Corporation)
Column: TSK-GEL GMHXL (4 used) (Tosoh Corporation)
Column size: 7.8 mm ID x 30 cm
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Sample concentration: 0.6 mg / mL
Injection volume: 100 μL
Flow rate: 0.8mL / min

The polyol compound preferably has an alkyl group having 1 to 4 carbon atoms in the molecule. Examples of the alkyl group having 1 to 4 carbon atoms include linear chains such as a methyl group having 1 carbon atom, an ethyl group having 2 carbon atoms, and a 1-propyl group having 3 carbon atoms [— (CH ₂ ) ₂ —CH ₃ ]. In addition to the alkyl group, branched alkyl groups such as a 1-methylethyl group having 3 carbon atoms [—CH (CH ₃ ) ₂ ] can be mentioned. The polyol compound more preferably has a methyl group having 1 carbon atom in the molecule.
When the polyol compound has a methyl group in the molecule, the wettability of the curable resin composition to a nonpolar resin such as polyolefin is further improved, and the adhesiveness is further improved.

The polyol compound more preferably has a branched alkyl group in the molecule.
When the polyol compound has a branched alkyl group in the molecule, the wettability of the curable resin composition to a nonpolar resin such as polyolefin is further improved, and the adhesiveness is further improved.

  A commercially available product may be used as the polyol compound. Examples of commercially available polyol compounds include Plaxel (registered trademark) CD205PL (Mn = 500, catalog value), CD210 (Mn = 1,000, catalog value), CD220PL (Mn = 2,000, catalog value) and the like ( All are trade names, Daicel Corporation), Sannix (registered trademark) PP-400 (Mn = 400, catalog value), PP-1000 (Mn = 1,000, catalog value), PP-2000 (Mn = 2). (All are trade names, Sanyo Chemical Industries, Ltd.), Uniol (registered trademark) DA-700 (trade names, NOF Corporation, Mn = 700, catalog values), Kuraray Polyol P -510 (trade name, Kuraray Co., Ltd., Mn = 500, catalog value), Plaxel (registered trademark) 205U (trade name, Daicel Corp., Mn = 530) Catalog value), PTMG650 (trade name, Mitsubishi Chemical (Co., Ltd.), Mn = 650, catalog value), and the like.

-Polyfunctional isocyanate compound-
The polyfunctional isocyanate compound in the present invention is not particularly limited as long as it is an isocyanate compound having two or more isocyanate groups in the molecule.
Examples of the polyfunctional isocyanate compound include a diisocyanate compound having two isocyanate groups in the molecule, a triisocyanate compound having three isocyanate groups in the molecule, and a tetraisocyanate compound having four isocyanate groups in the molecule. .

Examples of the diisocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), and naphthalene. Examples include diisocyanate (NDI), norbornene diisocyanate (NBDI), tetramethylxylene diisocyanate (TMXDI), dicyclohexylmethane 4,4′-diisocyanate (H12MDI), trimethylhexamethylene diisocyanate (TMDI), and the like.
Examples of the triisocyanate compound include triphenylmethane triisocyanate and 1-methylbenzole-2,4,6-triisocyanate.
Examples of the tetraisocyanate compound include dimethyltriphenylmethane tetraisocyanate.
Among these, as the polyfunctional isocyanate compound, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, naphthalene diisocyanate, norbornene diisocyanate, tetramethylxylene diisocyanate, dicyclohexylmethane 4, At least one compound selected from 4′-diisocyanate and trimethylhexamethylene diisocyanate is preferable, and the polyol compound and the hydroxy group-containing monovinyl ether compound react well, and the linear chain has a weight average molecular weight of 10,000 or less. From the viewpoint of efficient synthesis of vinyl ether group-containing urethane compounds Diisocyanate is more preferred.
In the synthesis of the vinyl ether group-containing urethane compound, the polyfunctional isocyanate compound may be used alone or in combination of two or more.

The polyfunctional isocyanate compound preferably has an alkyl group having 1 to 4 carbon atoms in the molecule. Examples of the alkyl group having 1 to 4 carbon atoms include linear chains such as a methyl group having 1 carbon atom, an ethyl group having 2 carbon atoms, and a 1-propyl group having 3 carbon atoms [— (CH ₂ ) ₂ —CH ₃ ]. In addition to the alkyl group, branched alkyl groups such as a 1-methylethyl group having 3 carbon atoms [—CH (CH ₃ ) ₂ ] can be mentioned. More preferably, the polyfunctional isocyanate compound has a methyl group having 1 carbon atom in the molecule.
When the polyfunctional isocyanate compound has a methyl group in the molecule, the wettability of the curable resin composition to a nonpolar resin such as polyolefin is further improved, and the adhesiveness is further improved.
Examples of the polyfunctional isocyanate compound having a methyl group in the molecule include tolylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, trimethylhexamethylene diisocyanate, 1-methylbenzole-2,4,6-triisocyanate, dimethyltriphenyl. And methane tetraisocyanate.

The polyfunctional isocyanate compound more preferably has a branched alkyl group in the molecule.
When the polyfunctional isocyanate compound has a branched alkyl group in the molecule, the wettability of the curable resin composition to a nonpolar resin such as polyolefin is further improved, and the adhesiveness is further improved.
Examples of the polyfunctional isocyanate compound having a branched alkyl group in the molecule include isophorone diisocyanate and dicyclohexylmethane 4,4′-diisocyanate.

  The amount of the polyfunctional isocyanate compound to be used is preferably 1.5 mol to 2.5 mol, more preferably 1.8 mol to 2.2 mol, per 1 mol of the polyol compound.

-Monovinyl ether compound containing hydroxy group-
The hydroxy group-containing monovinyl ether compound in the present invention is not particularly limited as long as it is a monovinyl ether compound having a hydroxy group in the molecule.
Examples of the hydroxy group-containing monovinyl ether compound include 2-hydroxyethyl vinyl ether (HEVE), 2-hydroxypropyl vinyl ether (HPVE), 4-hydroxybutyl vinyl ether (HBVE), 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether ( DEGMVE), triethylene glycol monovinyl ether (TEGDVE), dipropylene glycol monovinyl ether (DPGMVE), and the like.
In the synthesis of the vinyl ether group-containing urethane compound, the hydroxy group-containing monovinyl ether compound may be used alone or in combination of two or more.

The hydroxy group-containing monovinyl ether compound preferably has an alkyl group having 1 to 4 carbon atoms in the molecule. Examples of the alkyl group having 1 to 4 carbon atoms include linear chains such as a methyl group having 1 carbon atom, an ethyl group having 2 carbon atoms, and a 1-propyl group having 3 carbon atoms [— (CH ₂ ) ₂ —CH ₃ ]. In addition to the alkyl group, branched alkyl groups such as a 1-methylethyl group having 3 carbon atoms [—CH (CH ₃ ) ₂ ] can be mentioned.
When the hydroxy group-containing monovinyl ether compound has an alkyl group having 1 to 4 carbon atoms in the molecule, the alkyl group is preferably a methyl group having 1 carbon atom.
When the hydroxy group-containing monovinyl ether compound has a methyl group in the molecule, the wettability of the curable resin composition to a nonpolar resin such as polyolefin is further improved, and the adhesiveness is further improved.

When the hydroxy group-containing monovinyl ether compound has a hydroxyalkyl group in the molecule, the hydroxyalkyl group may be linear or branched.
When the hydroxy group-containing monovinyl ether compound has a linear hydroxyalkyl group in the molecule, the number of carbon atoms of the hydroxyalkyl group is preferably 1 to 4, more preferably 1 to 3. 1 or 2 is more preferable, and 2 is particularly preferable.
When the carbon number of the carbon chain of the linear hydroxyalkyl group is within the above range, the vinyl ether group-containing urethane compound to be synthesized is more attracted to molecules by the urethane skeleton in the curable resin composition. Further, since the curing shrinkage is further eased, the adhesiveness becomes more excellent.

When the hydroxy group-containing monovinyl ether compound has a branched hydroxyalkyl group in the molecule, the number of carbon atoms in the carbon chain of the hydroxyalkyl group is preferably 3-6, and particularly preferably 3.
When the hydroxyalkyl group is branched, the wettability of the curable resin composition to a nonpolar resin such as polyolefin is further improved, and the adhesiveness is further improved.
Examples of the monovinyl ether compound having a branched hydroxyalkyl group in the molecule include 2-hydroxypropyl vinyl ether and dipropylene glycol monovinyl ether.
In addition, it is more preferable that a hydroxyl group containing monovinyl ether compound has a C1-C4 alkyl group in a molecule | numerator among a polyol compound, a polyfunctional isocyanate compound, and a hydroxyl group containing monovinyl ether compound.

  The amount of the hydroxy group-containing monovinyl ether compound to be used is preferably 1.5 mol to 2.5 mol, more preferably 1.8 mol to 2.2 mol, with respect to 1 mol of the polyol compound.

-Other ingredients-
In the method for synthesizing the vinyl ether group-containing urethane compound, other components may be used as necessary in addition to the polyol compound, the polyfunctional isocyanate compound, and the hydroxy group-containing monovinyl ether compound.
Examples of other components include a polymerization catalyst and a diluent.

Examples of the polymerization catalyst include triethylamine, tetramethylethylenediamine, triethylenediamine (TEDA), bis (N, N-dimethylamino-2-ethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, Examples thereof include amine catalysts such as bis (2-dimethylaminoethyl) ether, carboxylic acid metal salts such as potassium acetate and potassium octylate, and organometallic compounds such as dibutyltin dilaurate.
Among these, as a polymerization catalyst, dibutyltin dilaurate is preferable.
In the synthesis of the vinyl ether group-containing urethane compound, the polymerization catalyst may be used alone or in combination of two or more.

  The amount of the polymerization catalyst used is preferably 0.01 parts by mass to 0.3 parts by mass with respect to 100 parts by mass in total of the polyol compound, the polyfunctional isocyanate compound, and the hydroxy group-containing monovinyl ether compound. It is more preferable that it is 05 mass part-0.1 mass part.

The weight average molecular weight (Mw) of the vinyl ether group-containing urethane compound is 10,000 or less, preferably 500 or more and 8,000 or less, more preferably 1,000 or more and 5,000 or less, and still more preferably 1. 500 to 3,200.
If the weight average molecular weight (Mw) of the vinyl ether group-containing urethane compound is 10,000 or less, the attracting between the molecules due to the urethane skeleton in the curable resin composition becomes strong and the cure shrinkage is alleviated. Adhesiveness to is excellent. Further, the network structure formed upon curing of the curable resin composition becomes dense (that is, the crosslink density increases) and the cohesive force becomes high, so that the adhesion to the adherend is excellent. .

  The weight average molecular weight (Mw) of the vinyl ether group-containing urethane compound is a value calculated by a standard polystyrene conversion method using the following gel permeation chromatography (GPC).

~conditions~
Measuring device: High-speed GPC HLC-8220 GPC (Tosoh Corporation)
Detector: differential refractometer (RI) RI-8220 (Tosoh Corporation)
Column: TSK-GEL GMHXL (4 used) (Tosoh Corporation)
Column size: 7.8 mm ID x 30 cm
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Sample concentration: 0.6 mg / mL
Injection volume: 100 μL
Flow rate: 0.8mL / min

  The curable resin composition of the present invention may contain a vinyl ether group-containing urethane compound alone or in combination of two or more.

The content of the vinyl ether group-containing urethane compound in the curable resin composition of the present invention is preferably 20% by mass to 80% by mass, and preferably 30% by mass to the total solid content of the curable resin composition. More preferably, it is 70 mass%, and it is still more preferable that it is 40 mass%-60 mass%.
When the content of the vinyl ether group-containing urethane compound in the curable resin composition is within the above range, the curing shrinkage relaxation effect of the vinyl ether group-containing urethane compound is maintained, and the viscosity of the curable resin composition is moderate. Since good wettability is obtained, the adhesive strength is more excellent.

<Multifunctional thiol compound>
The curable resin composition of the present invention contains a thiol compound (polyfunctional thiol compound) having two or more thiol groups in the molecule.
The polyfunctional thiol compound contributes to the curing of the curable resin composition of the present invention.
The curable resin composition of the present invention is cured by the progress of the enethiol reaction between the polyfunctional thiol compound and the vinyl ether group-containing urethane compound.

The polyfunctional thiol compound is not particularly limited. Examples of the polyfunctional thiol compound include bifunctional thiol compounds such as tetraethylene glycol bis (3-mercaptopropionate) and 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3- Mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2, Trifunctional thiol compounds such as 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercapto) Propionate), pentaerythritol tetrakis And tetrafunctional thiol compounds such as di (3-mercaptobutyrate) and hexafunctional thiol compounds such as dipentaerythritol hexakis (3-mercaptopropionate).
As a polyfunctional thiol compound, at least 1 sort (s) selected from a trifunctional thiol compound and a tetrafunctional thiol compound is preferable from a solvent-resistant viewpoint, and a tetrafunctional thiol compound is more preferable.

  A commercially available product may be used as the polyfunctional thiol compound. Examples of commercially available products of polyfunctional thiol compounds include, for example, Karenz MT (registered trademark) BD (trade name, bifunctional thiol compound, 1,4-bis (3-mercaptobutyryloxy) butane, Showa Denko KK ), Karenz MT (registered trademark) NR (trade name, trifunctional thiol compound, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, Showa Denko KK), Karenz MT (registered trademark) PE (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko KK), EGMP -4 (trade name, bifunctional thiol compound, tetraethylene glycol bis (3-mercaptopropionate), SC Organic Chemical Co., Ltd.), TMMP (trade name) Trifunctional thiol compound, trimethylolpropane tris (3-mercaptopropionate, SC Organic Chemical Co., Ltd.), TEMPIC (trade name, trifunctional thiol compound, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanate Nurate, SC Organic Chemical Co., Ltd.), PEMP (trade name, tetrafunctional thiol compound, pentaerythritol tetrakis (3-mercaptopropionate), SC Organic Chemical Co., Ltd.), DPMP (trade name, hexafunctional thiol compound, And dipentaerythritol hexakis, (3-mercaptopropionate), SC Organic Chemical Co., Ltd.) and the like.

  The curable resin composition of the present invention may contain a polyfunctional thiol compound alone or in combination of two or more.

The content of the polyfunctional thiol compound in the curable resin composition of the present invention is preferably 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, and 10 parts by mass to 50 parts by mass. More preferably, it is 15 parts by mass to 35 parts by mass.
When the content of the polyfunctional thiol compound in the curable resin composition is 5 parts by mass or more with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, the curable resin composition has a sufficient crosslinking point and is sufficient. Since a good cohesive force can be obtained, the adhesiveness becomes better.
When the content of the polyfunctional thiol compound in the curable resin composition is 100 parts by mass or less with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, the polarity of the curable resin composition due to the influence of the polyfunctional thiol compound Since the increase is suppressed, the adhesion to nonpolar resins such as polyolefin becomes better.

In the curable resin composition of the present invention, the ratio between the number of equivalents of thiol groups possessed by the polyfunctional thiol compound and the number of equivalents of vinyl ether groups possessed by the vinyl ether group-containing urethane compound (equivalents of vinyl ether groups possessed by the vinyl ether group-containing urethane compound) Number: equivalent number of thiol groups of the polyfunctional thiol compound) is preferably 1: 0.5 to 1: 1.5, more preferably 1: 0.7 to 1: 1.3. 1: 0.9 to 1: 1.1 is more preferable.
When the ratio between the number of equivalents of thiol groups possessed by the polyfunctional thiol compound and the number of equivalents of vinyl ether groups possessed by the vinyl ether group-containing urethane compound is within the above range, the adhesive strength is reduced due to the influence of unreacted thiol compounds. Further, since the decrease in cohesive force due to the decrease in the number of crosslinking points is suppressed, the adhesiveness becomes better.

<Monofunctional (meth) acrylic monomer>
The curable resin composition of the present invention contains a monofunctional (meth) acrylic monomer.
The monofunctional (meth) acrylic monomer is not particularly limited as long as it is a (meth) acrylic monomer having one (meth) acryloyl group in the molecule. For example, as the monofunctional (meth) acrylic monomer, monofunctional (meth) acrylate is preferable from the viewpoint of adhesiveness.
The monofunctional (meth) acrylate is not particularly limited. Examples of monofunctional (meth) acrylates include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate. , Stearyl (meth) acrylate, isostearyl (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, methoxydipropylene glycol acrylate, and the like.
Moreover, as a monofunctional (meth) acrylic-type monomer, the monofunctional (meth) acrylic-type monomer which has a cyclic structure from a viewpoint that the curable resin composition which has the more excellent adhesiveness is obtained is preferable.
Since the monofunctional (meth) acrylic monomer having a cyclic structure has a bulky three-dimensional structure, in the curable resin composition containing the monofunctional (meth) acrylic monomer having a cyclic structure, the curing shrinkage is alleviated, It is considered that the adhesion to the body is improved.
In addition, when a monofunctional (meth) acrylic-type monomer is monofunctional (meth) acrylate and has a cyclic structure, it is preferable to have a cyclic structure in the ester site | part of (meth) acrylic acid ester.

  When the monofunctional (meth) acrylic monomer has a cyclic structure, the cyclic structure may be an aliphatic ring structure represented by a cyclohexyl group or the like, or an aromatic ring structure represented by a phenyl group or the like. Alternatively, it may be a heterocyclic structure represented by a tetrahydrofurfuryl group, a piperidyl group or the like, or may be a plurality of cyclic structures (polycyclic structures) represented by an isobornyl group or the like. The cyclic structure may have various substituents such as an alkyl group.

Specific examples of the monofunctional (meth) acrylic monomer having an aliphatic ring structure include adamantyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. And dicyclopentenyloxyethyl (meth) acrylate.
Specific examples of the monofunctional (meth) acrylic monomer having an aromatic ring structure include phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and naphthyl (meth) ) Acrylate and the like.

Specific examples of the monofunctional (meth) acrylic monomer having a heterocyclic structure include pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, 2-tetrahydrofurfuryl (meth) acrylate, 2 -Tetrahydropyranyl (meth) acrylate etc. are mentioned.
Specific examples of the monofunctional (meth) acrylic monomer having a polycyclic structure include norbornyl (meth) acrylate and isobornyl (meth) acrylate.

  From the viewpoint of adhesion, the monofunctional (meth) acrylic monomer having a cyclic structure is a monofunctional (meth) acrylic monomer represented by the following formula (6) and a monofunctional represented by the formula (7). It is preferably at least one monofunctional (meth) acrylic monomer selected from (meth) acrylic monomers.

In the formula (6), R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

T ¹ represents an alkylene group having 1 to 10 carbon atoms or an alkylene oxide group.
Examples of the alkylene group having 1 to 10 carbon atoms represented by T ¹ include a methylene group having 1 carbon atom [—CH ₂ —], an ethylene group having 2 carbon atoms [— (CH ₂ ) ₂ —], and a carbon number. 3 trimethylene group [— (CH ₂ ) ₃ —], tetramethylene group having 4 carbon atoms [— (CH ₂ ) ₄ —], pentamethylene group having 5 carbon atoms [— (CH ₂ ) ₅ —], carbon number 6 hexamethylene group [— (CH ₂ ) ₆ —], heptamethylene group having 7 carbon atoms [— (CH ₂ ) ₇ —], octamethylene group having 8 carbon atoms [— (CH ₂ ) ₈ —], carbon In addition to a nonamethylene group [-(CH ₂ ) ₉ —] having 9 and a linear alkylene group having a decamethylene group [— (CH ₂ ) ₁₀ —] having ₁₀ carbon atoms, a 1-methylethylene group having 3 carbon atoms [ _{-CH (CH 3) -CH 2 -} ], 2- methylethylene _{[-CH 2 -CH (CH 3)} -] and the like, Prime 4 1,1-dimethylethylene group _{[-C (CH 3) 2 -CH} 2 -], 1,2- dimethylethylene group _{[-CH (CH 3) -CH (} CH 3) -], 2,2 - dimethylethylene group _{[-CH 2 -C (CH 3)} 2 -], 1- ethyl ethylene group _{[-CH (C 2 H 5)} -CH 2 -], 2- ethyl ethylene group _[-CH 2 -CH ( And various branched alkylene groups such as C ₂ H ₅ ) —].
Examples of the alkylene oxide group having 1 to 10 carbon atoms represented by T ¹ include an oxymethylene group [—O—CH ₂ —] having 1 carbon atom and an oxyethylene group [—O— (CH ₂₎ having 2 carbon atoms. ₂ )], methyleneoxymethylene group [—CH ₂ —O—CH ₂ —], oxytrimethylene group having 3 carbon atoms [—O— (CH ₂ ) ₃ —], methyleneoxyethylene group [—CH ₂ — In addition to linear alkylene oxide groups such as O— (CH ₂ ) ₂ —] and ethyleneoxymethylene group [— (CH ₂ ) ₂ —O—CH ₂ —], [—O—CH (CH _{3) -CH 2 -], [} - O-CH 2 -CH (CH 3) -], [- CH 2 -O-CH (CH 3) -] and various branched alkylene oxide groups and the like. These alkylene oxide groups have a structure in which other alkylene oxide groups are combined, for example, [—C ₅ H ₁₀ —O—CH ₂ —O—C ₄ H ₈ — ] Or the like.

T ² represents an aliphatic ring skeleton or an aromatic ring skeleton.
Examples of the aliphatic ring skeleton represented by T ² include monocyclic rings such as a cyclobutylene group having 4 carbon atoms, a cyclopentylene group having 5 carbon atoms, a cyclohexylene group having 6 carbon atoms, and a cycloheptylene group having 7 carbon atoms. In addition to the structure, various polycyclic structures such as an adamantane skeleton, a norbornane skeleton, a norbornene skeleton, an isobornene skeleton, a dicyclopentane skeleton, and the like can be given.
Examples of the aromatic ring skeleton represented by T ² include a phenylene group [—C ₆ H ₄ —], a xylylene group [—CH ₂ —C ₆ H ₄ —CH ₂ —], and a naphthylene group [—C ₁₀ H]. _6- ] and the like.

R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that substitutes for a hydrogen atom contained in an aliphatic ring skeleton or an aromatic ring skeleton represented by T ² .
Examples of the alkyl group having 1 to 10 carbon atoms include linear chains such as a methyl group having 1 carbon atom, an ethyl group having 2 carbon atoms, and a 1-propyl group having 3 carbon atoms [— (CH ₂ ) ₂ —CH ₃ ]. In addition to the alkyl group, branched alkyl groups such as a 1-methylethyl group having 3 carbon atoms [—CH (CH ₃ ) ₂ ] can be mentioned.

p represents an integer of 0 to 5, and q represents an integer of 1 to 5.
The case where p represents 0 means that the monofunctional (meth) acrylic monomer represented by the formula (6) has neither an alkylene group nor an alkylene oxide group represented by T ¹ ( A structure in which the (meth) acryloyl group and the cyclic structure (T ² ) are directly bonded to each other is obtained.

Examples of the monofunctional (meth) acrylic monomer represented by the formula (6) include phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and the like. Is mentioned.
When the monofunctional (meth) acrylic monomer represented by formula (6) is phenoxyethyl acrylate, R ¹ and R ² are both hydrogen atoms, T ¹ is an ethylene group, and T ² is phenylene. A group, p is 2 and q is 1.

In the formula (7), R ³ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

T ³ represents an alkylene group having 1 to 10 carbon atoms or an alkylene oxide group.
Since description of the alkylene group and an alkylene oxide group having 1 to 10 carbon atoms represented by T ³ has the same meaning as the alkylene group and the alkylene oxide group having 1 to 10 carbon atoms represented by T ¹ of the above Omitted.

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Examples of the alkyl group having 1 to 3 carbon atoms include, for example, a linear alkyl group having 1 carbon atom, a methyl group having 2 carbon atoms, an ethyl group having 2 carbon atoms, and a 1-propyl group having 3 carbon atoms. -Branched alkyl groups such as a methylethyl group [—CH (CH ₃ ) —CH ₃ ] and the like.

  A represents an oxygen atom or an NR group. R in the NR group represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

u and w each independently represent an integer of 0 to 5, and v represents an integer of 1 to 5.
The case where u represents 0 represents that the monofunctional (meth) acrylic monomer represented by the formula (7) has neither an alkylene group nor an alkylene oxide group represented by T ³ ( A (meth) acryloyl group and a cyclic structure are directly bonded.

  Examples of the monofunctional (meth) acrylic monomer represented by the formula (7) include tetrahydrofurfuryl (meth) acrylate and 2-piperidyl (meth) acrylate.

From the viewpoint of solvent resistance, the cyclic structure of the monofunctional (meth) acrylic monomer is preferably an aromatic ring.
When the curable resin composition of the present invention contains a monofunctional (meth) acrylic monomer having an aromatic ring, an intermolecular interaction derived from the aromatic ring occurs, for example, a solvent molecule such as an alcohol molecule. It is considered that the solvent resistance is improved because it becomes difficult to penetrate.

  From the viewpoint of odor and flash point, monofunctional (meth) acrylic monomers having a cyclic structure are benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl acrylate, and isobornyl ( It is preferably at least one monofunctional (meth) acrylic monomer selected from (meth) acrylates.

The monofunctional (meth) acrylic monomer contained in the curable resin composition of the present invention is preferably a monofunctional acrylic monomer.
The monofunctional acrylic monomer has high reactivity during radical curing, and the cohesive force after curing of the curable resin composition becomes strong. Adhesion is further improved.

  A commercially available product may be used as the monofunctional (meth) acrylic monomer. Examples of commercially available monofunctional (meth) acrylates include, for example, Kyoeisha Chemical Co., Ltd. light acrylate PO-A (trade name, phenoxyethyl acrylate (PHEA)), light acrylate IB-XA (trade name, Isobol). Nyl acrylate), light acrylate EC-A (trade name, ethoxy-diethylene glycol acrylate), light acrylate THF-A (trade name, tetrahydrofurfuryl acrylate), and the like.

  The curable resin composition of the present invention may contain a monofunctional (meth) acrylic monomer alone or in combination of two or more.

The content of the monofunctional (meth) acrylic monomer in the curable resin composition of the present invention is preferably 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, and 30 parts by mass. Part to 100 parts by weight, more preferably 40 parts by weight to 70 parts by weight.
The vinyl ether group-containing urethane compound contained in the curable resin composition of the present invention has a relatively high viscosity. In the curable resin composition of the present invention, the monofunctional (meth) acrylic monomer functions not only as a radical polymerizable monomer but also as a diluent.
When the content of the monofunctional (meth) acrylic monomer in the curable resin composition of the present invention is 20 parts by mass or more with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, the viscosity of the curable resin composition is It becomes moderate, and workability at the time of application to the adherend is further improved.
When the content of the monofunctional (meth) acrylic monomer in the curable resin composition of the present invention is 200 parts by mass or less with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, the viscosity of the curable resin composition is Adhesiveness is further improved because moderate wettability is obtained without becoming too low.
In addition, when the content of the monofunctional (meth) acrylic monomer contained in the curable resin composition of the present invention is high, oxygen inhibition occurs during curing, and the radical polymerization reaction of the monofunctional (meth) acrylic monomer Does not proceed well, it is difficult to obtain good curability.
When the content of the monofunctional (meth) acrylic monomer is 200 parts by mass or less with respect to 100 parts by mass of the vinyl ether group-containing urethane compound, oxygen inhibition is unlikely to occur at the time of curing, so that the curable resin composition is cured. The property becomes better.

<Radical generator>
The curable resin composition of the present invention contains a radical generator.
In the curable resin composition of the present invention, radicals are generated from the radical generator. The generated radical causes the enethiol reaction between the vinyl ether group-containing urethane compound and the polyfunctional thiol compound and the radical polymerization reaction of the monofunctional (meth) acrylic monomer to be almost simultaneously and independently in the reaction system. The curable resin composition of the present invention is cured.

The radical generator is not particularly limited, and those known to those skilled in the art can be used without limitation. The radical generator used in the present invention is at least one radical generator selected from a thermal radical generator (thermal polymerization initiator), a redox initiator, and a photoradical generator (photopolymerization initiator). From the viewpoint of simplicity of operation, a photo radical generator is preferable.
The curable resin composition of the present invention may contain a radical generator alone or in combination of two or more.

  Examples of the thermal radical generator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-n-propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, organic peroxides such as t-butylperoxy-2-ethylhexanate, 2,2′-azobis-isobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′- And azo compounds such as azobis-4-methoxy-2,4-dimethylvaleronitrile.

  As a redox initiator, for example, a combination of Permec N (trade name, methyl ethyl ketone peroxide, NOF Corporation) and cobalt naphthenate, Parkmill H (trade name, cumene hydroperoxide, NOF Corporation) and Combination with vanadium pentoxide, Niper BMT (trade name, di (3-methylbenzoyl) peroxide + benzoyl (3-methylbenzoyl) peroxide + dibenzoyl peroxide, NOF Corporation) and dimethylaniline , Niper PMB (trade name, di (4-methylbenzoyl) peroxide, NOF Corporation) and dimethylaniline, NIPER BW (trade name, dibenzoyl peroxide, NOF Corporation) and dimethylaniline And the like.

Examples of the photoradical generator include benzoin derivative compounds, benzyl ketal compounds, α-hydroxyacetophenone compounds, thioxanthone compounds, acylphosphine oxide compounds, and the like.
Specifically, as a photo radical generator, 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, BASF Japan Ltd.), 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl ] Propanol oligomer (trade name: Esacure ONE, Lamberti Co., Ltd.), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure) 2959, BASF Japan Ltd.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (product) Name: Irgacure 127, BASF Japan Ltd., 2,2-dimethoxy-2-phenylacetophenone (quotient) Name: Irgacure 651, BASF Japan Ltd.), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Darocur 1173, BASF Japan Ltd.), 2-methyl-1- [ (4-Methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone -1,2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl Phosphine oxide, bis (2,6-dimetho Shibenzoiru) -2,4,4-trimethyl pentyl phosphine oxide and the like.

  Among these, α-hydroxyacetophenone is used as a photoradical generator from the viewpoint of good compatibility with a vinyl ether group-containing urethane compound, hardly causing yellowing of the curable resin composition, and little odor. Compounds are preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred.

When the curable resin composition of the present invention contains a photoradical generator as a radical generator, the content of the photoradical generator in the curable resin composition is such that the vinyl ether group-containing urethane compound, the polyfunctional thiol compound, It is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 3 parts by mass with respect to 100 parts by mass in total with the functional (meth) acrylic monomer.
The content of the photo radical generator in the curable resin composition is 0.05 parts by mass with respect to a total of 100 parts by mass of the vinyl ether group-containing urethane compound, the polyfunctional thiol compound, and the monofunctional (meth) acrylic monomer. When it is above, since photocuring of the curable resin composition proceeds sufficiently during light irradiation, it is difficult for curing failure to occur.
The content of the photo radical generator in the curable resin composition is 5 parts by mass or less with respect to 100 parts by mass in total of the vinyl ether group-containing urethane compound, the polyfunctional thiol compound, and the monofunctional (meth) acrylic monomer. When it exists, since the photoradical generator does not absorb light excessively, poor curing of the curable resin composition hardly occurs. In addition, the photo radical generator hardly precipitates over time, and the storage stability of the curable resin composition becomes better.

<Other ingredients>
The curable resin composition of the present invention is a range other than the vinyl ether group-containing urethane compound, the polyfunctional thiol compound, the monofunctional (meth) acrylic monomer, and the radical generator, as necessary, within a range not impairing the effects of the present invention. Other components may also be included.
Examples of other components include various additives such as polymerization inhibitors, sensitizers, antioxidants, flame retardants, antistatic agents, leveling agents, antifoaming agents, and pigments.

  Examples of the polymerization inhibitor include methylhydroquinone, t-butylhydroquinone, 4-methoxynaphthol, 1,4-benzoquinone, methoquinone, dibutylhydroxytoluene, N-nitrosophenylhydroxylamine aluminum salt, 1,4-naphthoquinone, 4 -Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy TEMPO) and the like.

The curable resin composition of the present invention may contain a bifunctional or higher polyfunctional (meth) acrylic monomer having two or more (meth) acryloyl groups in the molecule as long as the effects of the present invention are not impaired. .
In the curable resin composition containing a polyfunctional (meth) acrylic monomer, the cross-linking reaction is promoted and the curing shrinkage is increased as compared with the case of containing only a monofunctional (meth) acrylic monomer. descend.
From the viewpoint of adhesiveness, the curable resin composition of the present invention has a ratio of the content of the monofunctional (meth) acrylic monomer to the content of the polyfunctional (meth) acrylic monomer (monofunctional (meth) acrylic monomer Content / polyfunctional (meth) acrylic monomer content) is preferably 60/40 to 100/0, more preferably 70/30 to 100/0, and more preferably 80 on a mass basis. More preferably, it is / 20-100 / 0.

[Use]
Since the curable resin composition of this invention is excellent in adhesiveness and transparency, it can be used suitably as an adhesive agent. The curable resin composition of the present invention has excellent adhesion to not only polar substances such as metals, glass, ceramics, wood, and ceramics, but also nonpolar resins, and is particularly suitable for adhesion to olefinic resins. it can.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

  The weight average molecular weight (Mw) of the urethane compound produced in this example was measured as follows.

-Measurement of weight average molecular weight-
The weight average molecular weight (Mw) of the urethane compound was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). The measurement by GPC was performed under the following conditions.

~conditions~
Measuring device: High-speed GPC HLC-8220 GPC (Tosoh Corporation)
Detector: differential refractometer (RI) RI-8220 (Tosoh Corporation)
Column: TSK-GEL GMHXL (4 used) (Tosoh Corporation)
Column size: 7.8 mm ID x 30 cm
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Sample concentration: 0.6 mg / mL
Injection volume: 100 μL
Flow rate: 0.8mL / min

-Production of urethane compounds-
[Production Example 1]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) CD205PL (polycarbonate diol (n = 3) represented by the following structural formula (A), number average molecular weight (Mn) = 500 (catalog value), Daicel Co., Ltd.) 100 parts by mass, isophorone diisocyanate (IPDI) 89 parts by mass, and dibutyltin dilaurate (DBTDL) 0.03 parts by mass, and the contents of the reaction vessel under stirring The temperature was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.16 parts by mass of dibutyltin dilaurate (DBTDL) and 44 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 2,900 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 2]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) CD210 (polycarbonate diol (n = 6) represented by the above structural formula (A), number average molecular weight (Mn) = 1,000 (catalog value), 100 parts by mass of Daicel Co., Ltd., 45 parts by mass of isophorone diisocyanate (IPDI), and 0.01 parts by mass of dibutyltin dilaurate (DBTDL) were added. The temperature of the contents was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.08 parts by mass of dibutyltin dilaurate (DBTDL) and 22 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 4,200 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 3]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) CD220PL (polycarbonate diol (n = 13) represented by the above structural formula (A), number average molecular weight (Mn) = 2,000 (catalog value), 100 parts by mass of Daicel Corporation, 22 parts by mass of isophorone diisocyanate (IPDI), and 0.01 parts by mass of dibutyltin dilaurate (DBTDL). The temperature of the contents was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.04 parts by mass of dibutyltin dilaurate (DBTDL) and 11 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
When the weight average molecular weight (Mw) of the obtained urethane compound was measured, it was 8,500.

[Production Example 4]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Sanix (registered trademark) PP-400 (polyoxypropylene glycol (n = 7) represented by the following structural formula (B), number average) 100 parts by mass of molecular weight (Mn) = 400 (catalog value), Sanyo Chemical Industries, Ltd., 112 parts by mass of isophorone diisocyanate (IPDI) and 0.03 parts by mass of dibutyltin dilaurate (DBTDL) were added and stirred. The temperature of the contents of the reaction vessel was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.20 part by mass of dibutyltin dilaurate (DBTDL) and 56 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 2,200 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 5]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Sanix (registered trademark) PP-1000 (polyoxypropylene glycol (n = 17) represented by the above structural formula (B), number average) 100 parts by mass of molecular weight (Mn) = 1,000 (catalog value), Sanyo Chemical Industries, Ltd., 45 parts by mass of isophorone diisocyanate (IPDI), 0.01 parts by mass of dibutyltin dilaurate (DBTDL), Under stirring, the temperature of the contents of the reaction vessel was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.08 parts by mass of dibutyltin dilaurate (DBTDL) and 22 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 3,500 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 6]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Sanix (registered trademark) PP-2000 (polyoxypropylene glycol (n = 34) represented by the above structural formula (B), number average) 100 parts by mass of molecular weight (Mn) = 2,000 (catalog value), Sanyo Chemical Industries, Ltd., 22 parts by mass of isophorone diisocyanate (IPDI), 0.01 parts by mass of dibutyltin dilaurate (DBTDL), Under stirring, the temperature of the contents of the reaction vessel was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.04 parts by mass of dibutyltin dilaurate (DBTDL) and 11 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 6,200 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 7]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Uniol (registered trademark) DA-700 (polyoxyethylene-bisphenol A ether (n = 5) represented by the following structural formula (C)), Number average molecular weight (Mn) = 700 (catalog value), 100 parts by mass of NOF Corporation, 64 parts by mass of isophorone diisocyanate (IPDI) and 0.02 parts by mass of dibutyltin dilaurate (DBTDL) are added and stirred. The temperature of the contents of the reaction vessel was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.11 part by mass of dibutyltin dilaurate (DBTDL) and 32 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and further reacted for 2 hours, so that a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 3,000 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 8]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Kuraray polyol P-510 (polyester of 3-methyl-1,5-pentanediol and adipic acid represented by the following structural formula (D) Diol, number average molecular weight (Mn) = 500 (catalog value), 100 parts by mass, isophorone diisocyanate (IPDI) 89 parts by mass, dibutyltin dilaurate (DBTDL) 0.03 parts by mass, Under stirring, the temperature of the contents of the reaction vessel was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.16 parts by mass of dibutyltin dilaurate (DBTDL) and 44 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 2,800 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 9]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) 205U (polycaprolactone diol (n = 2) represented by the following structural formula (E), number average molecular weight (Mn)) = 530 (catalog value), Daicel Co., Ltd.) 100 parts by mass, isophorone diisocyanate (IPDI) 89 parts by mass, dibutyltin dilaurate (DBTDL) 0.03 parts by mass, and the contents of the reaction vessel under stirring The temperature of the product was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.16 parts by mass of dibutyltin dilaurate (DBTDL) and 44 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 2,900 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 10]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, PTMG650 (polytetramethylene ether glycol (n = 9) represented by the following structural formula (F), number average molecular weight (Mn) = 650 ( Catalog value), 100 parts by mass of Mitsubishi Chemical Co., Ltd., 69 parts by mass of isophorone diisocyanate (IPDI) and 0.02 parts by mass of dibutyltin dilaurate (DBTDL). The temperature was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.12 parts by mass of dibutyltin dilaurate (DBTDL) and 34 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and the reaction is further performed for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 3,500 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 11]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) CD205PL (polycarbonate diol (n = 3) represented by the above structural formula (A), number average molecular weight (Mn) = 500 (catalog value), 100 parts by mass of Daicel Co., Ltd., 89 parts by mass of isophorone diisocyanate (IPDI), and 0.03 parts by mass of dibutyltin dilaurate (DBTDL). The temperature was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.16 parts by mass of dibutyltin dilaurate (DBTDL) and 34 parts by mass of 2-hydroxyethyl vinyl ether (HEVE) were added, and the reaction was further continued for 2 hours, and a urethane compound having vinyl ether groups at both ends of the molecular chain. Got. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 2,900 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 12]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) CD205PL (polycarbonate diol (n = 3) represented by the above structural formula (A), number average molecular weight (Mn) = 500 (catalog value), 100 parts by mass of Daicel Co., Ltd., 89 parts by mass of isophorone diisocyanate (IPDI), and 0.03 parts by mass of dibutyltin dilaurate (DBTDL). The temperature was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.16 parts by mass of dibutyltin dilaurate (DBTDL) and 67 parts by mass of dipropylene glycol monovinyl ether (DPGMVE, a hydroxy group-containing monovinyl ether compound having a methyl group having 1 carbon atom in the molecule) were added, and The reaction was carried out for 2 hours to obtain a urethane compound having vinyl ether groups at both ends of the molecular chain. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 3,200 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 13]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Sanix (registered trademark) PP-4000 (polyoxypropylene glycol (n = 68) represented by the above structural formula (B), number average) 100 parts by mass of molecular weight (Mn) = 4,000 (catalog value), Sanyo Chemical Industries, Ltd., 11 parts by mass of isophorone diisocyanate (IPDI), 0.003 parts by mass of dibutyltin dilaurate (DBTDL), Under stirring, the temperature of the contents of the reaction vessel was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.02 parts by mass of dibutyltin dilaurate (DBTDL) and 5.6 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and further reacted for 2 hours to have vinyl ether groups at both ends of the molecular chain. A urethane compound was obtained. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 12,400 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 14]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) 230 (polycaprolactone diol (n = 13) represented by the above structural formula (E), number average molecular weight (Mn)) = 3,000 (catalog value), Daicel Co., Ltd.) 100 parts by mass, isophorone diisocyanate (IPDI) 15 parts by mass, and dibutyltin dilaurate (DBTDL) 0.004 parts by mass. The temperature of the contents was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.03 parts by mass of dibutyltin dilaurate (DBTDL) and 7.4 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and further reacted for 2 hours to have vinyl ether groups at both ends of the molecular chain. A urethane compound was obtained. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 15,000 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 15]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) 240 (polycaprolactone diol (n = 17) represented by the above structural formula (E), number average molecular weight (Mn)) = 4,000 (catalog value), 100 parts by mass of Daicel Corporation, 11 parts by mass of isophorone diisocyanate (IPDI), and 0.003 parts by mass of dibutyltin dilaurate (DBTDL). The temperature of the contents was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.02 parts by mass of dibutyltin dilaurate (DBTDL) and 5.6 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and further reacted for 2 hours to have vinyl ether groups at both ends of the molecular chain. A urethane compound was obtained. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
When the weight average molecular weight (Mw) of the obtained urethane compound was measured, it was 28,000.

[Production Example 16]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, PTMG3000 (polytetramethylene ether glycol (n = 41) represented by the above structural formula (F), number average molecular weight (Mn) = 3, 000 (catalog value), 100 parts by mass of Mitsubishi Chemical Co., Ltd., 15 parts by mass of isophorone diisocyanate (IPDI), and 0.004 parts by mass of dibutyltin dilaurate (DBTDL). The temperature of the product was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.03 parts by mass of dibutyltin dilaurate (DBTDL) and 7.4 parts by mass of 4-hydroxybutyl vinyl ether (HBVE) are added, and further reacted for 2 hours to have vinyl ether groups at both ends of the molecular chain. A urethane compound was obtained. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 16,000 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

[Production Example 17]
In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, Plaxel (registered trademark) CD205PL (polycarbonate diol (n = 3) represented by the above structural formula (A), number average molecular weight (Mn) = 500 (catalog value), 100 parts by mass of Daicel Co., Ltd., 89 parts by mass of isophorone diisocyanate (IPDI), and 0.03 parts by mass of dibutyltin dilaurate (DBTDL). The temperature was raised to 60 ° C. and reacted for 2 hours. Thereafter, 0.16 parts by mass of dibutyltin dilaurate (DBTDL) and 18 parts by mass of ethanol (EtOH) were added and further reacted for 2 hours to obtain a urethane compound. The completion of the reaction was confirmed by the disappearance of the 2250 cm ⁻¹ peak derived from isocyanate in the infrared absorption spectrum (IR).
It was 3,010 when the weight average molecular weight (Mw) of the obtained urethane compound was measured.

  Tables 1 and 2 show the types, amounts, and the like of the polyol compounds, isocyanate compounds, and monovinyl ether compounds used in Production Examples 1-17.

-Production of curable resin composition-
[Example 1]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 22 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 1 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 2]
Brown 100 parts by mass of the urethane compound obtained in Production Example 2 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko (Co)) 16 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 2 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 3]
Brown 100 parts by mass of the urethane compound obtained in Production Example 3 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 10 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 3 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 4]
100 parts by mass of the urethane compound obtained in Production Example 4 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 25 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 4 was obtained by stirring and mixing later with a spatula for 5 minutes.

[Example 5]
Brown 100 parts by mass of the urethane compound obtained in Production Example 5 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko (Co)) 16 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 5 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 6]
Brown 100 parts by mass of the urethane compound obtained in Production Example 6 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 10 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 6 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 7]
100 parts by mass of the urethane compound obtained in Production Example 7 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 20 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 7 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 8]
Brown 100 parts by mass of the urethane compound obtained in Production Example 8 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 23 parts by weight and 65 parts by weight of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 8 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 9]
100 parts by mass of the urethane compound obtained in Production Example 9 and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 22 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 9 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 10]
Brown 100 parts by mass of the urethane compound obtained in Production Example 10 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 22 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 10 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 11]
Brown 100 parts by mass of the urethane compound obtained in Production Example 11 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 24 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 11 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 12]
Brown 100 parts by mass of the urethane compound obtained in Production Example 12 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 21 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 12 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 13]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko (Co)) 22 parts by weight and 20 parts by weight of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 13 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 14]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Ltd.) 22 parts by mass and 100 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 14 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 15]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 22 parts by mass and 200 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 15 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 16]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 10 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 16 was obtained by stirring and mixing later with a spatula for 5 minutes.

[Example 17]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 15 parts by weight and 65 parts by weight of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 17 was obtained by stirring and mixing later with a spatula for 5 minutes.

[Example 18]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 30 parts by weight and 65 parts by weight of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 18 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 19]
50 parts by mass of the urethane compound obtained in Production Example 1 above, 50 parts by mass of Aronix (registered trademark) M-1100 (bifunctional urethane acrylate, Toagosei Co., Ltd.), Irgacure (registered trademark) 184 (photoradical) The generator, 1-hydroxycyclohexyl phenyl ketone, and 2 parts by mass of BASF Japan Ltd. were weighed into a brown sample bottle, heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 18 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 19 was obtained by stirring and mixing with a spatula for 5 minutes later.

[Example 20]
20 parts by mass of the urethane compound obtained in Production Example 1 above, 80 parts by mass of Aronix (registered trademark) M-1100 (bifunctional urethane acrylate, Toagosei Co., Ltd.), Irgacure (registered trademark) 184 (photoradical) The generator, 1-hydroxycyclohexyl phenyl ketone, and 2 parts by mass of BASF Japan Ltd. were weighed into a brown sample bottle, heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko (Co)) 16 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Example 20 was obtained by stirring and mixing for 5 minutes later with a spatula.

[Example 21]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 22 parts by weight and 65 parts by weight of light acrylate IB-XA (monofunctional acrylic monomer, isobornyl acrylate, Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes, then 5 The curable resin composition of Example 21 was obtained by stirring and mixing with a spatula for minutes.

[Example 22]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Co., Ltd.) 22 parts by weight and 20 parts by weight of light acrylate EC-A (monofunctional acrylic monomer, ethoxy-diethylene glycol acrylate, Kyoeisha Chemical Co., Ltd.), and after heating at 40 ° C. for 10 minutes, 5 The curable resin composition of Example 22 was obtained by stirring and mixing with a spatula for minutes.

[Example 23]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Ltd.) 22 parts by mass, light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) 50 parts by mass, and light acrylate BP-4PA (bifunctional acrylic monomer) , 15 parts by mass of PO (propylene oxide) adduct diacrylate of bisphenol A, Kyoeisha Chemical Co., Ltd.), heated at 40 ° C. for 10 minutes, and then stirred and mixed with a spatula for 5 minutes to obtain Example 23. A curable resin composition was obtained.

[Example 24]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko Ltd.) 22 parts by mass, light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) 40 parts by mass, and light acrylate BP-4PA (bifunctional acrylic monomer) , 25 parts by mass of PO (propylene oxide) adduct diacrylate of bisphenol A, Kyoeisha Chemical Co., Ltd.), heated at 40 ° C. for 10 minutes, and then stirred and mixed for 5 minutes with a spatula. A curable resin composition was obtained.

[Example 25]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MTNR (thiol compound having three thiol groups in the molecule (trifunctional thiol compound), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Showa Denko KK 32 parts by weight, light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA) ), 65 parts by mass of Kyoeisha Chemical Co., Ltd., was heated at 40 ° C. for 10 minutes, and then stirred and mixed with a spatula for 5 minutes to obtain a curable resin composition of Example 25.

[Comparative Example 1]
Brown 100 parts by mass of the urethane compound obtained in Production Example 13 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 5.8 parts by weight and 65 parts by weight of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) and weighed at 40 ° C. for 10 minutes. The curable resin composition of Comparative Example 1 was obtained by stirring and mixing with a spatula for 5 minutes after heating.

[Comparative Example 2]
Brown 100 parts by mass of the urethane compound obtained in Production Example 14 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 7.4 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) and weighed at 40 ° C. for 10 minutes. The curable resin composition of Comparative Example 2 was obtained by stirring and mixing with a spatula for 5 minutes after heating.

[Comparative Example 3]
Brown 100 parts by mass of the urethane compound obtained in Production Example 15 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 5.8 parts by weight and 65 parts by weight of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) and weighed at 40 ° C. for 10 minutes. The curable resin composition of Comparative Example 3 was obtained by stirring and mixing with a spatula for 5 minutes after heating.

[Comparative Example 4]
Brown 100 parts by weight of the urethane compound obtained in Production Example 16 above and 2 parts by weight of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 7.4 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) and weighed at 40 ° C. for 10 minutes. The curable resin composition of Comparative Example 4 was obtained by stirring and mixing with a spatula for 5 minutes after heating.

[Comparative Example 5]
100 parts by mass of the urethane compound obtained in Production Example 1 above and 3 parts by mass of CPI (registered trademark) -100P (photoacid generator, San Apro Co., Ltd.) are weighed in a brown sample bottle, and 60 ° C. For 20 minutes and then stirred with a spatula for 5 minutes. Next, in a brown sample bottle after stirring, 50 parts by mass of TEGDVE (triethylene glycol divinyl ether, vinyl ether monomer, Nippon Carbide Industries, Ltd.) and DPGDVE (dipropylene glycol divinyl ether, vinyl ether monomer, Nippon Carbide Industries, Inc.) )) Weighed 50 parts by mass, heated at 40 ° C. for 10 minutes, and then stirred and mixed with a spatula for 5 minutes to obtain a curable resin composition of Comparative Example 5.

[Comparative Example 6]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 110 parts by mass and 65 parts by mass of TEGDVE (triethylene glycol divinyl ether, vinyl ether monomer, Nippon Carbide Industry Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes, and then stirred and mixed with a spatula for 5 minutes. By doing so, the curable resin composition of Comparative Example 6 was obtained.

[Comparative Example 7]
Brown 100 parts by mass of the urethane compound obtained in Production Example 1 above and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 22 parts by mass of light acrylate BP-4PA (bifunctional acrylic monomer, PO (propylene oxide) adduct diacrylate of bisphenol A, Kyoeisha Chemical Co., Ltd.) 65 parts by mass, 40 parts by weight The curable resin composition of Comparative Example 7 was obtained by heating and stirring at 0 ° C. for 10 minutes and then stirring and mixing with a spatula for 5 minutes.

[Comparative Example 8]
Brown 100 parts by mass of the urethane compound obtained in Production Example 17 and 2 parts by mass of Irgacure (registered trademark) 184 (photo radical generator, 1-hydroxycyclohexyl phenyl ketone, BASF Japan Ltd.) The sample bottle was weighed and heated at 60 ° C. for 20 minutes, and then stirred with a spatula for 5 minutes. Next, in the brown sample bottle after stirring, Karenz MT (registered trademark) PE (thiol compound having four thiol groups in the molecule (tetrafunctional thiol compound), pentaerythritol tetrakis (3-mercaptobutyrate), Showa Denko 22 parts by mass and 65 parts by mass of light acrylate PO-A (monofunctional acrylic monomer, phenoxyethyl acrylate (PHEA), Kyoeisha Chemical Co., Ltd.) were weighed and heated at 40 ° C. for 10 minutes. The curable resin composition of Comparative Example 8 was obtained by stirring and mixing with a spatula for 5 minutes later.

-Evaluation-
About the curable resin composition of Examples 1-25 and Comparative Examples 1-7, adhesiveness, transparency, and solvent resistance were evaluated. The results are shown in Tables 3-5. The curable resin composition of Comparative Example 8 was not evaluated because it was not cured under any of the evaluation test conditions.

1. Adhesive After the curable resin composition is applied on a polypropylene plate (PP plate) using a 30 μm applicator, the surface of the applied curable resin composition is subjected to a corona-treated polyethylene terephthalate film (corona-treated PET). Film) was laminated to prepare a sheet having a configuration of PP plate / curable resin composition / corona-treated PET film. Next, ultraviolet rays were irradiated from the surface side of the corona-treated PET film of this sheet using a high-pressure mercury lamp with an irradiation intensity of 160 W under the condition of an irradiation amount of 500 mJ / cm ² to cure the curable resin composition. And the sheet | seat after hardening was cut | disconnected in the strip shape of width 250mm, and it was set as the test piece.
This test piece was 180 ° with respect to the bonding surface using a tensile tester (STA-1225, Orientec Co., Ltd.) at 23 ° C. and 50% RH in a peeling speed of 300 mm / min. The PP plate and the corona-treated PET film were peeled from each other, the adhesive force (unit: N / 25 mm) was measured, and the adhesion to the PP plate was evaluated according to the following evaluation criteria.
In addition, the thing classified into [A], [B], and [C] was determined to be acceptable.

<Evaluation criteria>
A: Adhesive strength is 10 N / 25 mm or more.
B: Adhesive strength is 8 N / 25 mm or more and less than 10 N / 25 mm.
C: Adhesive strength is 5 N / 25 mm or more and less than 8 N / 25 mm.
D: Adhesive strength is 2 N / 25 mm or more and less than 5 N / 25 mm.
E: Adhesive strength is less than 2 N / 25 mm.

2. Transparency After applying the curable resin composition onto a glass plate using a 50 μm applicator, using a high-pressure mercury lamp with an irradiation intensity of 160 W, irradiating with ultraviolet rays under an irradiation dose of 500 mJ / cm ² , The curable resin composition was cured to obtain a test piece.
The yellowing degree (YI value) of this test piece was measured using a spectral color difference meter SE6000 (Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following evaluation criteria.
In addition, it means that transparency of a curable resin composition was excellent, so that yellowing degree (YI value) was low, and what was classified into [A], [B], and [C] was determined to be a pass.

<Evaluation criteria>
A: The degree of yellowing of the test piece is less than 0.5.
B: The yellowing degree of the test piece is 0.5 or more and less than 1.0.
C: The yellowing degree of the test piece is 1.0 or more and less than 3.0.
D: The yellowing degree of the test piece is 3.0 or more and less than 8.0.
E: The yellowing degree of the test piece is 8.0 or more.

3. Solvent resistance The curable resin composition was applied to a synthetic paper (trade name: YUPO IHC75, YUPO Corporation) using a 5 μm applicator, and then biaxially applied to the surface of the applied curable resin composition. A stretched polypropylene film (OPP (Oriented Polypropylene) film) was bonded to produce a sheet having a composition of synthetic paper / curable resin composition / OPP film. Next, from the surface side of the OPP film of this sheet, ultraviolet rays were irradiated under the condition of an irradiation amount of 170 mJ / cm ² using a high-pressure mercury lamp with an irradiation intensity of 160 W to cure the curable resin composition. And the sheet | seat after hardening was cut | disconnected to the size of width 2cm x length 2cm, and it was set as the test piece.
This test piece was immersed in isopropyl alcohol (IPA) for 24 hours, and after immersion, the peeled width (unit: mm) of the OPP film was measured and evaluated according to the following evaluation criteria.

<Evaluation criteria>
A: The peeled width of the test piece is less than 0.6 mm.
B: The peeled width of the test piece is 0.6 mm or more and less than 1.0 mm.
C: The peeled width of the test piece is 1.0 mm or more and less than 2.0 mm.
D: The peeled width of the test piece is 2.0 mm or more.

In Tables 3 to 5, “ene: thiol” means the ratio of the number of equivalents of thiol groups possessed by the thiol compound in the curable resin composition to the number of equivalents of vinyl ether groups possessed by the urethane compound (of the vinyl ether groups possessed by the urethane compound). Equivalent number: means the equivalent number of thiol groups of a thiol compound.
In Tables 3 to 5, “-” means that the corresponding component is not blended.

  From the results described in Tables 3 to 5, the curable resin composition has two or more vinyl ether groups in the molecule and has a weight average molecular weight of 10,000 or less (vinyl ether group-containing urethane compound). And a thiol compound having two or more thiol groups in the molecule, a monofunctional (meth) acrylic monomer, and a radical generator, and adhesion to a PP plate formed of a nonpolar resin and It has become clear that the effect of excellent transparency can be achieved.

The curable resin composition of Example 1 containing a monofunctional acrylic monomer having an aromatic ring was more resistant to curable resin composition of Example 21 containing a monofunctional acrylic monomer having no aromatic ring. Excellent solvent resistance.
The curable resin composition of Example 1 containing a monofunctional acrylic monomer having a cyclic structure was more resistant to curable resin composition of Example 22 containing a monofunctional acrylic monomer having no cyclic structure. The solvent property was remarkably excellent.
The curable resin composition of Example 1 containing a monofunctional acrylic monomer was compared with the curable resin compositions of Examples 23 to 24 in which a part of the monofunctional acrylic monomer was replaced with a bifunctional acrylic monomer. Excellent adhesion to PP plates formed of nonpolar resin.
The curable resin composition of Example 11 containing a vinyl ether group-containing urethane compound synthesized using a hydroxy group-containing monovinyl ether compound having a linear hydroxyalkyl group (carbon number of carbon chain: 2) in the molecule, Comparison with the curable resin composition of Example 1 containing a vinyl ether group-containing urethane compound synthesized using a hydroxy group-containing monovinyl ether compound having a linear hydroxyalkyl group (carbon number of carbon chain: 4) in the molecule And it was excellent in the adhesiveness with respect to PP board formed with nonpolar resin.
The curable resin composition of Example 12 containing a vinyl ether group-containing urethane compound synthesized using a hydroxy group-containing monovinyl ether compound having a branched hydroxyalkyl group (carbon number of carbon chain: 3) in the molecule is Compared with the curable resin composition of Example 1 containing a vinyl ether group-containing urethane compound synthesized using a hydroxy group-containing monovinyl ether compound having no branched hydroxyalkyl group, it is formed of a nonpolar resin. Excellent adhesion to PP plates.

The curable resin compositions of Comparative Examples 1 to 4 containing a urethane compound having a weight average molecular weight exceeding 10,000 are hardly yellowed and excellent in transparency, but have an adhesive force to a PP plate formed of a nonpolar resin. It was low.
The curable resin composition of Comparative Example 5 that does not contain a monofunctional (meth) acrylic monomer, a thiol compound, and a radical generator showed high adhesion to a PP plate formed of a nonpolar resin. However, since it contained a photoacid generator, it yellowed significantly.
The curable resin compositions of Comparative Examples 6 to 7 that do not contain a monofunctional (meth) acrylic monomer are difficult to yellow and have excellent transparency, but have low adhesion to PP plates formed of nonpolar resins. .

Claims (11)

  A urethane compound having two or more vinyl ether groups in the molecule and a weight average molecular weight of 10,000 or less, a thiol compound having two or more thiol groups in the molecule, and a monofunctional (meth) acrylic monomer And a radical generator.   The urethane compound is synthesized from at least a polyol compound having two or more hydroxy groups in the molecule, an isocyanate compound having two or more isocyanate groups in the molecule, and a monovinyl ether compound having a hydroxy group in the molecule. The curable resin composition according to claim 1.   The curable resin composition according to claim 2, wherein the number average molecular weight of the polyol compound is less than 3,000.   The curable resin composition according to claim 2 or 3, wherein at least one compound selected from the polyol compound, the isocyanate compound, and the monovinyl ether compound is a compound having an alkyl group having 1 to 4 carbon atoms. object.   The curable resin composition according to claim 4, wherein the alkyl group is a methyl group.   The curable resin composition according to claim 1, wherein the monofunctional (meth) acrylic monomer has a cyclic structure.   The curable resin composition according to claim 6, wherein the cyclic structure is an aromatic ring.   The curable resin composition according to any one of claims 1 to 7, wherein the monofunctional (meth) acrylic monomer is an acrylic monomer.   The content of the monofunctional (meth) acrylic monomer in the curable resin composition is 20 parts by mass to 200 parts by mass with respect to 100 parts by mass of the urethane compound. The curable resin composition according to Item 1.   The curable resin composition according to any one of claims 2 to 9, wherein the isocyanate compound is isophorone diisocyanate.   The curable resin composition according to any one of claims 1 to 10, which is used for adhesion to an olefin resin.