JP2019085402A - Thiol compound, method for synthesizing the same and use of the thiol compound - Google Patents

Abstract

To provide a novel thiol compound, a method for the synthesis of the compound, a curing agent containing the compound, a resin composition containing the compound and an epoxy compound, a resin composition containing the compound and an ene compound having a carbon-carbon double bond in the molecule, and an adhesive and a sealant containing the resin composition as a component.SOLUTION: The present invention provides a thiol compound illustrated by the following formulae.SELECTED DRAWING: None

Description

  The present invention relates to novel thiol compounds, methods for synthesizing the thiol compounds and the use of the thiol compounds.

Compounds having a plurality of thiol groups in the molecule are known as curing agents for epoxy compounds (note: epoxy resin before curing).
For example, Patent Document 1 proposes an epoxy resin composition that uses a polythiol compound as a curing agent and contains a reaction product of an amine and an epoxy compound as a curing accelerator. The epoxy resin composition is considered to have a long pot life and to be rapidly cured at a relatively low temperature.
Patent Document 2 promotes the cure of a reaction product of an isocyanate compound having one or more isocyanate groups in the molecule and a compound having at least one primary and / or secondary amino group in the molecule. An epoxy resin composition containing as an agent has been proposed. This epoxy resin composition also has a long pot life and is considered to have excellent curability.

In addition, a compound having a plurality of thiol groups in the molecule and an ene compound having a carbon-carbon double bond in the molecule are rapidly polymerized (resinified) by the polymerization initiator, so that they can be used in various applications. Utilization is being considered.
For example, Patent Document 3 discloses that tris [(3-mercaptopropionyloxy) ethyl] isocyanurate having three thiol groups in the molecule as a thiol compound rapidly reacts with an ene compound and cures having excellent properties. It is believed that things can be obtained.

  However, since these thiol compounds have an ester bond in the molecule, the ester bond is hydrolyzed in a humidified environment, and there is a problem in the moisture resistance of the obtained cured product.

  In addition to these documents, Patent Document 4 is cited as a document in which the invention related to the present invention is described.

Japanese Patent Application Laid-Open No. 6-21919 JP-A-6-211970 JP, 2014-58667, A Japanese Patent Application Publication No. 2014-526575

The present invention provides a novel thiol compound, a synthesis method of the thiol compound, a curing agent containing the thiol compound, a resin composition containing the thiol compound and an epoxy compound, and carbon-carbon in the molecule with the thiol compound. An object of the present invention is to provide a resin composition containing an ene compound having a double bond.
Furthermore, it aims at providing an adhesive agent and sealing agent which use these resin compositions as a component.

As a result of extensive research to solve the above-mentioned problems, the present inventors have recognized that the reaction product of a certain dialkene compound and a thiol compound can achieve the intended purpose, and the present invention It came to complete the
That is, the first invention is a thiol compound represented by the chemical formula (I).

  The second invention is characterized in that one selected from dialkene compounds represented by the chemical formula (II) to the chemical formula (V) is reacted with a thiol compound represented by the chemical formula (VI) It is a synthesis method of a thiol compound.

（式中、Ｒ_１は、前記と同様である。）

(Wherein, R ₁ is as defined above)

A third invention is a curing agent containing the thiol compound of the first invention.
A fourth invention is a resin composition containing the thiol compound of the first invention and an epoxy compound (hereinafter sometimes referred to as "first resin composition").
5th invention is resin composition of 4th invention which contains amines as a hardening accelerator.
A sixth invention is the resin composition of the fourth invention, which contains a reaction product of an epoxy compound and an amine as a curing accelerator.
A seventh invention accelerates the cure of a reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule. It is a resin composition of the 4th invention contained as an agent.
The eighth invention is a resin composition containing the thiol compound of the first invention and an ene compound having a carbon-carbon double bond in the molecule (hereinafter referred to as "second resin composition" There is
The ninth invention is an adhesive comprising the resin composition of any of the fourth invention to the eighth invention as a component.
The tenth invention is a sealing agent containing the resin composition of any of the fourth invention to the eighth invention as a component.

The thiol compound of the present invention is a novel compound having two or more thioether bonds in the molecule. Such thiol compounds are expected to be used as intermediate materials for various sulfur-containing compounds and as curing agents for resins. In addition, the thiol compound of the present invention is expected to have low volatility, and is further expected to have excellent compatibility (low crystallinity) with epoxy compounds, ene compounds and the like.
And since the thiol compound of this invention does not have an ester bond in the molecule | numerator, when it uses as a raw material of resin, compared with the case where the conventional polythiol compound is used, the hardened | cured material excellent in hydrolysis resistance is used. It is expected to give. Also, it is expected to give a low elasticity cured product.
Furthermore, the adhesive and the sealing agent of the present invention are expected to be excellent in moisture resistance, water resistance and the like.

3 is an IR spectrum chart of the pale yellow liquid obtained in Example 1.

The present invention relates to a thiol compound represented by the above chemical formula (I). Preferably, the thiol compound is synthesized by reacting one selected from the dialkene compounds represented by the chemical formula (II) to the chemical formula (V) with the thiol compound represented by the chemical formula (VI) described above. Can. The compound represented by the chemical formula (II) is vinylcyclohexene, the compound represented by the chemical formula (III) is limonene, and the compound represented by the chemical formula (IV) is tetrahydroindene The compound represented by the chemical formula (V) of is dicyclopentadiene.
Examples of the thiol compound represented by the chemical formula (I) include thiol compounds represented by the chemical formula (I-1) to the chemical formula (I-39).

Examples of the thiol compound represented by the above chemical formula (VI) include thiol compounds represented by chemical formula (VI-1) to chemical formula (VI-10). Note that by using a combination of these thiol compounds can be synthesized a thiol compound R ₁ are different from each other in the formula (I).

  The use amount (feed amount) of the thiol compound represented by the chemical formula (VI) is preferably in an appropriate ratio in a range of 2 to 100 times the molar amount (feed amount) of the dialkene compound.

In the synthesis reaction of the thiol compound of the present invention, a radical initiator (A) may be used to accelerate the reaction. In addition, a reaction solvent (ii) may be used to facilitate the reaction.
As a radical initiator (a), for example,
Azobisisobutyronitrile, t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t- Butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecano Aate, 1,1-bis (t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis (2-methylbutyronitrile) And dimethyl 2,2'-azobis (2-methyl propionate). That.

  The use amount (feed amount) of the radical initiator (i) is preferably in an appropriate ratio in the range of 0.0001 to 10 times the molar amount with respect to the use amount (feed amount) of the dialkene compound.

As the reaction solvent (ii), for example,
Water, methanol, ethanol, propanol, 2-propanol, butanol, ethyl acetate, propyl acetate, butyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl Solvents such as sulfoxide, hexamethyl phosphate triamide and the like can be mentioned. These may be used in combination as a reaction solvent (ii).

  The reaction temperature of this synthesis reaction is preferably set in the range of 0 to 200 ° C. Moreover, although reaction time is suitably set according to the set reaction temperature, it is preferable to set to the range of 1 to 120 hours.

After completion of this synthesis reaction, the desired thiol compound of the present invention is removed from the obtained reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by evaporation of the reaction solvent, solvent extraction method, etc. be able to.
Furthermore, if necessary, purification can be carried out using means such as washing with water or the like, activated carbon treatment, silica gel chromatography and the like.

  The thiol compound of the present invention is expected to be used as an intermediate raw material for various sulfur-containing compounds. It can also be used as a curing agent for resins, that is, the curing agent of the present invention contains the thiol compound of the present invention.

(First resin composition)
The first resin composition of the present invention is one in which the thiol compound of the present invention is contained as a curing agent in an epoxy compound (note: refers to the epoxy resin before curing).
Any epoxy compound can be used without particular limitation as long as it has an epoxy group (glycidyl group) in the molecule, for example,
Polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol or glycerin and polyethylene glycol (for example, bisphenol A epoxy resin);
Glycidyl ether esters obtained by reacting epichlorohydrin with a hydroxycarboxylic acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid;
Polyglycidyl esters obtained by reacting epichlorohydrin with a polycarboxylic acid such as phthalic acid or terephthalic acid;
Glycidyl glycoluril compounds having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril;
Cyclic cycloaliphatic epoxy resins such as 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate;
Nitrogen-containing cyclic epoxy resin such as triglycidyl isocyanurate, hydantoin type epoxy resin;
Furthermore, in addition to epoxidized phenol novolac resin (phenol novolac epoxy resin), epoxidized cresol novolac resin, epoxidized polyolefin, cyclic aliphatic epoxy resin, urethane-modified epoxy resin,
Epoxy-modified organopolysiloxane compound by hydrosilylation addition reaction of an organic compound having a carbon-carbon double bond and a glycidyl group with a silicon compound having an SiH group (for example, JP-A-2004-99751 or JP-A-2006-282988 Epoxy modified organopolysiloxane compounds disclosed in Japanese Patent Laid-Open Publication No. 11-345, etc. may be mentioned, and these may be used in combination.

  Regarding the content of the thiol compound of the present invention in the first resin composition of the present invention, the ratio (equivalent ratio) of the number of the same thiol groups to the number of epoxy groups in the composition is 0.1 It is preferable to set so as to be ̃10.0.

In the first resin composition of the present invention, another thiol compound may be used in combination with the thiol compound of the present invention as a curing agent. As other thiol compounds, for example,
Ethane dithiol, propane dithiol, hexamethylene dithiol, decamethylene dithiol, tolylene-2,4-dithiol, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, 2- (mercaptomethyl) -2-methyl- Aliphatic thiol compounds such as 1,3-propanedithiol, 2-ethyl-2- (mercaptomethyl) -1,3-propanedithiol;
Aromatic thiol compounds such as benzene dithiol, toluene dithiol, xylene dithiol (p-xylene dithiol);
Cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds represented by the chemical formula (VII);
Mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol;
Mercaptopropionic acid esters such as pentaerythritol tetrakis (3-mercaptopropionate);
Epoxy resin-terminated mercapto compound;
3,6-dioxa-1,8-octanedithiol, mercapto alkyl ether disulfide compound represented by the chemical formula (VIII),
2,2 '-[[2,2-bis [(2-mercaptoethoxy) methyl] -1,3-propanediyl] bis (oxy)] bisethanethiol,
3,3 '-[[2,2-bis [(3-mercaptopropoxy) methyl] -1,3-propanediyl] bis (oxy)] bis-1-propanethiol,
3- [2,2-bis [(3-mercaptopropoxy) methyl] butoxy] -1-propanethiol,
3- (3-Mercaptopropoxy) -2,2-bis [(3-mercaptopropoxy) methyl] -1-propanol,
Mercaptoalkylether compounds such as 2,2-bis [(3-mercaptopropoxy) methyl] -1-butanol;
1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril,
There may be mentioned 1,3,4,6-tetrakis (3-mercaptopropyl) glycoluril, which may be used in combination.

（式中、ｐは、１〜５の整数を表す。）

(Wherein, p represents an integer of 1 to 5)

（式中、ｑは、１〜２０の整数を表す。）

(Wherein, q represents an integer of 1 to 20)

  Regarding the content of the other thiol compound in the first resin composition of the present invention, the number of thiol groups derived from the other thiol compound in the composition is the thiol group derived from the thiol compound of the present invention It is preferable to set so that it may become a ratio (equivalent ratio) of 0-100 with respect to the number of.

The first resin composition of the present invention may contain a conventionally known curing agent together with the thiol compound of the present invention. As a conventionally known curing agent, for example,
Besides compounds and acid anhydrides with phenolic hydroxyl groups,
Organic phosphine compounds such as triphenylphosphine, diphenylnaphthyl phosphine, diphenylethyl phosphine and the like;
Aromatic phosphonium salt;
Aromatic diazonium salt;
Aromatic iodonium salts;
Aromatic selenium salts and the like can be mentioned.

Examples of compounds having a phenolic hydroxyl group include
Bisphenol A, bisphenol F, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol Novolak, resorcinol and the like.

As the acid anhydride, for example,
Methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic anhydride, hymic anhydride, methyl nadic anhydride , Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methyl norbornane-2,3-dicarboxylic acid Etc.

The first resin composition of the present invention may contain a conventionally known curing accelerator. As a curing accelerator, for example,
(I) amines, (ii) reaction products of epoxy compounds and amines, and (iii) compounds having one or more isocyanate groups in the molecule, and a primary amino group and a secondary in the molecule A reaction product with a compound having at least one of amino groups may, for example, be mentioned, and these may be used in combination.

(I) Amines, as conventionally known, having at least one amino group selected from a primary amino group, a secondary amino group and a tertiary amino group in the molecule I hope there is.
Examples of such amines are
Aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diaminodicyclohexylmethane, dimethylbenzylamine;
Aromatic amines such as 4,4'-diaminodiphenylmethane, o-methylaniline and the like;
Nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine and the like can be mentioned.

  The content of amines in the first resin composition of the present invention is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

  (Ii) The reaction product of the epoxy compound and the amine is a solid which is poorly soluble in the epoxy resin at room temperature and solubilizes (is easily solubilized) by heating to function as a curing accelerator. It is also referred to as a latent curing accelerator (hereinafter, the reaction product of an epoxy compound and an amine may be referred to as a "latent curing accelerator").

As an epoxy compound used as a raw material of a latent curing accelerator, a glycidyl amine compound obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane, m-aminophenol, etc. in addition to the above-mentioned epoxy compound;
Examples thereof include monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether and glycidyl methacrylate.

Examples of amines used as a raw material of the latent curing accelerator include the above-mentioned amines. Further, among these amines, amines having a tertiary amino group in the molecule are raw materials for providing a latent curing accelerator having excellent curing promoting properties. As such amines, for example,
Amines such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine and the like;
Amines having a tertiary amino group in the molecule such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like,
2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-) 3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-methylimidazole) Butoxypropyl) -2-methylimidazoline, 2- (dimethyl) Luaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylformolin, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole 4-Mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylglycine hydrazide, N, N-dimethylpropionic acid hydrazide, nicotine Examples thereof include alcohols having a tertiary amino group in the molecule, such as acid hydrazide and isonicotinic acid hydrazide, phenols, thiols, carboxylic acids, hydrazides and the like.

In order to further improve the storage stability of the first resin composition of the present invention, in addition to the above-mentioned epoxy compound and amines as a raw material of the latent curing accelerator, active hydrogen is contained in the molecule as a third component 2 You may use the active hydrogen compound which has one or more.
As an active hydrogen compound, for example,
Polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin;
Polyhydric alcohols such as trimethylolpropane;
Polyvalent carboxylic acids such as adipic acid and phthalic acid,
1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid and the like.

Furthermore, the latent curing accelerator may be surface-treated with an isocyanate compound or an acidic compound. As an isocyanate compound, for example,
Monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate and the like;
Hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate Etc. can be mentioned.

  Instead of the polyfunctional isocyanate compound, a terminal isocyanate group-containing compound obtained by the reaction of the polyfunctional isocyanate compound and the active hydrogen compound can also be used. Specific examples thereof include an addition reaction product having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and an addition reaction product having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol.

The acidic substance used for surface treatment of the latent curing accelerator may be any of gas, liquid or solid, and may be any of inorganic acid or organic acid. As this acidic substance, for example,
Carbon dioxide gas, sulfur dioxide gas, sulfuric acid, hydrochloric acid, oxalic acid, phosphoric acid, acetic acid, formic acid, propionic acid, adipic acid, caproic acid, lactic acid, oxalic acid, tartaric acid, sebacic acid, p-toluenesulfonic acid, salicylic acid, boric acid, Examples include tannic acid, alginic acid, polyacrylic acid, polymethacrylic acid, phenol, pyrogallol, phenol resin, resorcinol resin and the like.

  The latent curing accelerator is prepared by mixing an epoxy compound and an amine and, if necessary, an active hydrogen compound, reacting at a temperature from room temperature to 200 ° C., solidifying, grinding, or methyl ethyl ketone, dioxane, tetrahydrofuran The reaction can be easily obtained by trituration of the solid after reaction in a solvent such as

Also, commercially available latent curing accelerators can be used. As a commercial item, for example,
"Amicure PN-23 (trade name)", "Amicure PN-H (trade name)", "Amicure MY-24 (trade name)" manufactured by Ajinomoto Fine Techno Co., Ltd., "Novacua HX-3721" manufactured by Asahi Kasei Corp. Names), "Novacua HX-3742 (trade name)" and the like.

  The content of the latent curing accelerator in the first resin composition of the present invention is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

  (Iii) The reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule, both in dichloromethane and the like It can be obtained by reacting in an organic solvent.

As an isocyanate compound having one or more isocyanate groups in the molecule, for example,
n-Butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-bromophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 3,4-dichlorophenyl Isocyanate, 2,6-dimethylphenyl isocyanate, o-fluorophenyl isocyanate, p-fluorophenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, o-trifluoromethylphenyl isocyanate, m-trifluoromethylphenyl isocyanate, benzyl isocyanate , Hexamethylene diisocyanate, 2,4-toluylene diisocyanate , 2,6-Toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate 1,3-bis (isocyanate methyl) cyclohexane, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris- (3-isocyanato-4-methylphenyl) isocyanurate, tris- (6-isocyanatohexyl) isocyanurate etc. are mentioned.

As a compound having at least one of a primary amino group and a secondary amino group in the molecule, for example,
Dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-hexylamine, di-n-octylamine, di-n-ethanolamine, dimethylaminopropylamine, diethylaminopropylamine, morpholine, Piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, pyrrolidine, benzylamine, N-methylbenzylamine, cyclohexylamine, metaxylylenediamine, 1,3-bis (aminomethyl 2.) Cyclohexane, isophorone diamine, N-aminoethyl piperazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1,1-dimethylhydrazine and the like.

  Reaction of a compound having one or more isocyanate groups in the molecule with a compound having at least one of a primary amino group and a secondary amino group in the molecule in the first resin composition of the present invention The content of the product is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

In the first resin composition of the present invention, as long as the effects of the present invention are not impaired,
Pigments (titanium white, cyanine blue, watching red, bengala, carbon black, aniline black, manganese blue, iron black, ultramarine blue, hanza red, chrome yellow, chrome green etc.),
Inorganic filler (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopon, sikobo, zinc stearate, pearlite, quartz, quartz glass, fused silica, silica powder such as spherical silica, etc. spherical alumina, crushed alumina Oxides such as magnesium oxide, beryllium oxide and titanium oxide, nitrides such as boron nitride, silicon nitride and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, Metals and alloys such as copper, silver, iron, aluminum, nickel and titanium, carbon-based materials such as diamond and carbon, etc.)
Thermoplastic resin and / or thermosetting resin (high density, medium density, low density various polyethylene, homopolymers such as polypropylene, polybutene, polypentene, ethylene-propylene copolymer, nylon-6, nylon-6, 6 Polyamide resin such as vinyl chloride resin, nitrocellulose resin, vinylidene chloride resin, acrylic resin, acrylamide resin, styrene resin, vinyl ester resin, polyester resin, phenol resin (phenol compound), silicone Graft resins, such as various elastomer resins, such as system resin, fluorine resin, acrylic rubber and urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer, acrylonitrile-butadiene-styrene graft copolymer, etc.) ,
Reinforcing agent (glass fiber, carbon fiber etc.),
Anti-sagging agent (Hydrogenated castor oil, fine particle anhydrous boric acid etc.),
Matting agents (fine powder silica, paraffin wax, etc.),
Abrasive (zinc stearate etc),
Internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.),
Additives (modifiers) such as surfactants, leveling agents, antifoaming agents, diluents for viscosity adjustment (organic solvents), flexibility imparting agents, coupling agents, perfumes, flame retardants, antioxidants, etc. If necessary, it may be contained in a ratio of 0.01 to 50% by weight based on the total amount (total amount) of the first resin composition.
Further, in the first resin composition of the present invention, when an isocyanate group-containing compound is contained as an additive (modifier), the adhesive strength is improved while suppressing the decrease in the curability of the resin composition. Can.

As this isocyanate group containing compound, for example,
n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane Triisocyanate etc. are mentioned.

  The content of the isocyanate group-containing compound in the first resin composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

  There is no particular limitation on the method of preparing (mixing) the first resin composition of the present invention, and each component described above is weighed out by a predetermined amount, and an appropriate stirring and mixing apparatus such as a 3-roll or planetary mixer is used. If necessary, it can be mixed while heating.

  There is no restriction | limiting in particular in the method to harden | cure the 1st resin composition of this invention, Conventionally well-known hardening apparatuses, such as a tunnel-type hardening furnace and a tunnel furnace in which continuous hardening is possible, are employable. The heating source is also not particularly limited, and conventionally known means such as hot air circulation, infrared heating, high frequency heating and the like can be adopted. The curing temperature and the curing time may be set appropriately.

(Second resin composition)
The second resin composition of the present invention contains the thiol compound of the present invention and an ene compound having a carbon-carbon double bond in the molecule (hereinafter sometimes simply referred to as an "ene compound").
The ene compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

As this polymerizable monomer, for example,
(1) (meth) acrylic acid alkyl ester type monomers,
(2) Hydroxyl group containing monomer,
(3) Carboxyl group-containing monomers,
(4) Amino group-containing monomer,
(5) acetoacetyl group-containing monomer,
(6) Monomer containing isocyanate group
(7) Glycidyl group-containing monomer,
(8) a monomer containing one aromatic ring,
(9) a monomer containing an alkoxy group and an oxyalkylene group,
(10) Alkoxyalkyl (meth) acrylamide monomers,
(11) (meth) acrylamide monomers,
(12) monofunctional unsaturated compounds,
(13) A polyfunctional unsaturated compound etc. are mentioned.

(1) Examples of (meth) acrylic acid alkyl ester monomers include
Methyl (meth) acrylate,
Ethyl (meth) acrylate,
n-butyl (meth) acrylate,
iso-butyl (meth) acrylate,
tert-butyl (meth) acrylate,
n-propyl (meth) acrylate,
n-hexyl (meth) acrylate,
2-ethylhexyl (meth) acrylate,
n-octyl (meth) acrylate,
Isodecyl (meth) acrylate,
Lauryl (meth) acrylate,
Cetyl (meth) acrylate,
Stearyl (meth) acrylate,
Cyclohexyl (meth) acrylate,
Isobornyl (meth) acrylate etc. are mentioned.

(2) As a hydroxyl group containing monomer, for example,
2-hydroxyethyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate,
5-hydroxypentyl (meth) acrylate,
6-hydroxyhexyl (meth) acrylate,
(Meth) acrylic acid hydroxyalkyl esters such as 8-hydroxyoctyl (meth) acrylate;
Caprolactone modified monomers such as caprolactone modified 2-hydroxyethyl (meth) acrylate;
Diethylene glycol (meth) acrylate,
Oxyalkylene modified monomers such as polyethylene glycol (meth) acrylates;
In addition, 2-acryloyloxyethyl 2-hydroxyethyl phthalic acid,
N-methylol (meth) acrylamide,
Primary hydroxyl group-containing monomers such as hydroxyethyl acrylamide;
2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate,
3-chloro 2-hydroxypropyl (meth) acrylate,
Propylene glycol diglycidyl ether-epoxy di (meth) acrylate,
Phenol glycidyl ether-epoxy (meth) acrylate,
Secondary hydroxyl group-containing monomers such as bisphenol A diglycidyl ether-epoxydi (meth) acrylate;
Tertiary hydroxyl group containing monomers, such as 2, 2- dimethyl 2- hydroxyethyl (meth) acrylate, etc. are mentioned.

(3) As a carboxyl group-containing monomer, for example,
(Meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, cinnamic acid and the like.

(4) As the amino group-containing monomer, for example,
tert-butylaminoethyl (meth) acrylate,
Ethylaminoethyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate,
Diethylaminoethyl (meth) acrylate etc. are mentioned.

(5) As the acetoacetyl group-containing monomer, for example,
2- (acetoacetoxy) ethyl (meth) acrylate,
And allylacetoacetate.

(6) As the isocyanate group-containing monomer, for example,
2-acryloyloxyethyl isocyanate,
Examples thereof include 2-methacryloyloxyethyl isocyanate and their alkylene oxide adducts.

(7) As a glycidyl group containing monomer, for example,
Other than glycidyl (meth) acrylate,
Ethylene glycol diglycidyl ether-epoxy (meth) acrylate,
Resorcinol diglycidyl ether-epoxy (meth) acrylate,
Bis (4-hydroxyphenyl) sulfide diglycidyl ether-epoxy (meth) acrylate,
Phenolic novolac epoxy resin-(meth) acrylate,
Cresol novolac epoxy resin-(meth) acrylate,
Bisphenol (eg, bisphenol A, bisphenol F) type epoxy resin- (meth) acrylate,
Biphenol (eg, 3,3 ', 5,5'-tetramethylbiphenol) type epoxy resin- (meth) acrylate,
Epoxy (meth) acrylates which are reaction products of an epoxy compound such as tris (2,3-epoxypropyl) isocyanurate- (meth) acrylate and (meth) acrylic acid,
Glycidyl (meth) acrylates, such as 4-hydroxybutyl (meth) acrylate glycidyl ether, are mentioned.

(8) As a monomer containing one aromatic ring, for example,
Phenyl (meth) acrylate,
Benzyl (meth) acrylate,
Phenoxyethyl (meth) acrylate,
Phenoxydiethylene glycol (meth) acrylate,
2-hydroxy-3-phenoxypropyl (meth) acrylate,
styrene,
α-methylstyrene and the like can be mentioned.

(9) Examples of the monomer containing an alkoxy group and an oxyalkylene group include
2-methoxyethyl (meth) acrylate,
2-ethoxyethyl (meth) acrylate,
3-methoxybutyl (meth) acrylate,
2-butoxyethyl (meth) acrylate,
2-butoxydiethylene glycol (meth) acrylate,
Methoxy diethylene glycol (meth) acrylate,
Methoxy triethylene glycol (meth) acrylate,
Ethoxydiethylene glycol (meth) acrylate,
Methoxydipropylene glycol (meth) acrylate,
Methoxy polyethylene glycol (meth) acrylate,
Octoxy polyethylene glycol-polypropylene glycol-mono (meth) acrylate,
Lauroxy polyethylene glycol mono (meth) acrylate,
Stearoxy polyethylene glycol mono (meth) acrylate and the like can be mentioned.

(10) Alkoxyalkyl (meth) acrylamide monomers include, for example,
Methoxymethyl (meth) acrylamide,
Ethoxymethyl (meth) acrylamide,
Propoxymethyl (meth) acrylamide,
Isopropoxymethyl (meth) acrylamide,
n-butoxymethyl (meth) acrylamide,
Isobutoxymethyl (meth) acrylamide and the like can be mentioned.

(11) Examples of (meth) acrylamide monomers include
(Meth) acryloyl morpholine,
Dimethyl (meth) acrylamide,
Diethyl (meth) acrylamide,
(Meth) acrylamide N-methylol (meth) acrylamide and the like can be mentioned.

(12) Examples of monofunctional unsaturated compounds include biphenyl structure-containing (meth) acrylate compounds, and more specifically,
o-biphenyl (meth) acrylate,
m-biphenyl (meth) acrylate,
biphenyl (meth) acrylates such as p-biphenyl (meth) acrylate;
o-biphenyl oxymethyl (meth) acrylate,
m-biphenyl oxymethyl (meth) acrylate,
p-biphenyl oxymethyl (meth) acrylate,
o-biphenyl oxyethyl (meth) acrylate,
m-biphenyl oxyethyl (meth) acrylate,
p-biphenyl oxyethyl (meth) acrylate,
o-biphenyl oxypropyl (meth) acrylate,
m-biphenyl oxypropyl (meth) acrylate,
Biphenyl oxyalkyl (meth) acrylates such as p-biphenyl oxypropyl (meth) acrylate;
(O-biphenyloxy) diethylene glycol (meth) acrylate,
(M-biphenyloxy) diethylene glycol (meth) acrylate,
(P-biphenyloxy) diethylene glycol (meth) acrylate,
(O-biphenyloxy) dipropylene glycol (meth) acrylate,
(M-biphenyloxy) dipropylene glycol (meth) acrylate,
(P-biphenyloxy) dipropylene glycol (meth) acrylate,
(O-biphenyloxy) polyethylene glycol (meth) acrylate,
(M-biphenyloxy) polyethylene glycol (meth) acrylate,
(P-biphenyloxy) polyethylene glycol (meth) acrylate,
(O-biphenyloxy) polypropylene glycol (meth) acrylate,
(M-biphenyloxy) polypropylene glycol (meth) acrylate,
Examples include biphenyl oxypolyalkylene glycol (meth) acrylates such as (p-biphenyl oxy) polypropylene glycol (meth) acrylate.

  (13) Examples of polyfunctional unsaturated compounds include bifunctional monomers, trifunctional or higher monomers, urethane (meth) acrylates, epoxy (meth) acrylates as described above, polyester (meth) acrylates, poly Ether (meth) acrylates etc. are mentioned.

And as a specific example of a bifunctional monomer,
Ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate,
Dipropylene glycol di (meth) acrylate,
Polypropylene glycol di (meth) acrylate,
Butylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate,
Ethylene oxide modified bisphenol A type di (meth) acrylate,
Propylene oxide modified bisphenol A type di (meth) acrylate,
1,6-Hexanediol di (meth) acrylate,
1,6-Hexanediol ethylene oxide modified di (meth) acrylate,
Glycerin di (meth) acrylate,
Pentaerythritol di (meth) acrylate,
Ethylene glycol diglycidyl ether di (meth) acrylate,
Diethylene glycol diglycidyl ether di (meth) acrylate,
Phthalic acid diglycidyl ester di (meth) acrylate,
Hydroxypivalic acid modified neopentyl glycol di (meth) acrylate,
Isocyanuric acid ethylene oxide modified diacrylate,
2- (meth) acryloyloxyethyl acid phosphate diester etc. are mentioned.

Moreover, as a specific example of a trifunctional or more than trifunctional monomer,
Trimethylolpropane tri (meth) acrylate,
Pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate,
Dipentaerythritol tri (meth) acrylate,
Dipentaerythritol tetra (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
Tri (meth) acryloyloxyethoxy trimethylolpropane,
Glycerin polyglycidyl ether poly (meth) acrylate,
Tris (2- (meth) acryloyloxyethyl) isocyanurate,
Isocyanurate ethylene oxide modified tri (meth) acrylate,
Ethylene oxide modified dipentaerythritol penta (meth) acrylate,
Ethylene oxide modified dipentaerythritol hexa (meth) acrylate,
Ethylene oxide modified pentaerythritol tri (meth) acrylate,
Ethylene oxide modified pentaerythritol tetra (meth) acrylate,
Examples thereof include succinic acid-modified pentaerythritol tri (meth) acrylate and the like.

Besides the above mentioned polymerizable monomers,
Divinylbenzene, piperylene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether , Vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconic acid, fumaric acid dialkyl ester, allyl alcohol, acryloyl chloride, methyl vinyl ketone, N-acrylamidomethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl allyl vinyl ketone, 2- Chlorethyl vinyl ether, triallyl isocyanurate, tetraallyl Recall uril and,
N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid triallyl ester,
Trifluoroethyl (meth) acrylate,
Tribromobenzyl (meth) acrylate,
Perfluorooctylethyl (meth) acrylate,
Sulfur-containing (meth) acrylate,
Examples include (meth) acryloyloxypropyl tris (methoxy) silane and the like.

  In the second resin composition of the present invention, as the ene compound, the aforementioned polymerizable monomer and polymerizable oligomer may be used in combination, and as the polymerizable monomer, used in combination with the polymerizable monomers exemplified above. Different types of polymerizable monomers may be used in combination, and different types of polymerizable oligomers may be used in combination for the polymerizable oligomers.

  Regarding the ratio (ratio) of the content of the thiol compound of the present invention and the ene compound in the second resin composition of the present invention, the content of the ene compound is relative to the content of the thiol compound of the present invention It is preferable to set it as the appropriate ratio in the range of 0.01-1000 times amount (weight ratio), and it is more preferable to set it as the appropriate ratio in the range of 0.1-100 times amount (weight ratio).

In the second resin composition of the present invention, the other thiol compound described above may be used in combination with the thiol compound of the present invention.
With regard to the ratio (ratio) of the content of the thiol compound of the present invention and the other thiol compound in the second resin composition of the present invention, the content of the other thiol compound is the content of the thiol compound of the present invention It is preferable to set it as the suitable ratio in the range of 0-100 times amount (weight ratio) with respect to these, and it is more preferable to set it as the appropriate ratio in the range of 0.1-10 times amount (weight ratio).

Examples of the method of polymerizing (curing) the second resin composition of the present invention include methods of photocuring and thermosetting.
As a method of making it photocure, the method of irradiating an active energy ray, Preferably the method of using a photoinitiator together is mentioned. As an active energy ray, light, radiation, electromagnetic waves, an electron beam, etc. are mentioned, The light of an electron beam or the ultraviolet to infrared wavelength range is preferable. As a light source, for example, an ultra-high pressure mercury light source or a metal halide light source in the case of irradiation with ultraviolet light, a metal halide light source or a halogen light source in the case of irradiation with visible light, and a halogen light source in the case of infrared irradiation can do. Further, in recent years, light sources such as lasers and LEDs corresponding to light emission of various wavelengths, which are widely used, may be used.
The irradiation dose of the active energy ray can be appropriately set according to the type of the light source and the like.

  The photopolymerization initiator can be selected from a photo radical polymerization initiator and a photo anion polymerization initiator, and each may be contained in the second resin composition. In the photocuring, in order to enhance the production efficiency and the properties of the cured product, means of thermal polymerization (thermocuring) may be used in combination.

As a radical photopolymerization initiator, those generally used can be used without particular limitation, and, for example,
Acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one Kind;
Benzoines such as benzyl dimethyl ketal;
Benzophenones such as benzophenone, 4-phenylbenzophenone, hydroxybenzophenone and the like;
Thioxanthones such as isopropyl thioxanthone and 2,4-diethyl thioxanthone,
In addition, methylphenyl glyoxylate etc. may be mentioned, and these may be used in combination.
In addition, well-known photopolymerization promoters, such as benzoic acids, such as 4-dimethylamino benzoic acid, and tertiary amines, can be used together to an optical radical polymerization initiator as needed.

As a photoanion polymerization initiator, if used generally, it can be used without restriction, and onium salts, carbamates, etc. may be mentioned.
As onium salts, for example, 1,2-diisopropyl-3- (bis (dimethylamino) methylene) guanidinium 2- (3-benzoylphenyl) propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethyl Biguanidium n-butyl triphenyl borate etc. are mentioned,
As carbamates, for example, 2-nitrophenylmethylpiperidine-1-carboxylate, 1- (anthraquinone-2-yl) ethylimidazole carboxylate, 1- (3- (2-hydroxyphenyl) -2-propenoyl) piperidine , 9-anthranylmethyl diethyl carbamate and the like.

  Moreover, when photocuring the 2nd resin composition of this invention, sensitizers, such as pyrene, perylene, acridine orange, thioxanthone, 2-chloro thioxanthone, penzoflavin etc., can be used, for example.

  The content of the photopolymerization initiator in the second resin composition of the present invention is preferably a ratio of 0.001 to 20% by weight with respect to the entire second resin composition (total amount), More preferably, the proportion is 0.01 to 10% by weight.

On the other hand, as a method of thermally curing the second resin composition of the present invention, a method of using a thermal polymerization initiator in combination may be mentioned. The thermal polymerization initiator can be selected from a thermal radical polymerization initiator and a thermal anionic polymerization initiator, and each may be contained in the resin composition.
The heating temperature / heating time can be appropriately set for the condition of heat curing, but it is preferable to set in the range of 60 to 130 ° C./30 to 240 minutes, and the range of 70 to 125 ° C./30 to 120 minutes It is more preferable to set to.

  Any thermal radical polymerization initiator may be used without particular limitation as long as it is generally used, for example, diisopropyl peroxy dicarbonate, benzoyl peroxide, t-butyl peroxy isobutyrate, t-hexyl peroxy Oxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxy Pivalate, t-butyl peroxy neodecanoate, t-hexyl peroxy neo decanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1,1-bis (t-hexyl Peroxy) cyclohexane, benzoyl peroxide, 3,5,5-tri Peroxides such as ethyl hexanoyl peroxide and lauroyl peroxide, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropio) Azo compounds such as (Nate), and these may be used in combination.

Any thermal anion polymerization initiator may be used without particular limitation as long as it is generally used, and examples thereof include amines, imidazoles and the like, and these may be used in combination.
Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis (3-aminopropyl) glycoluril and the like.
The imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

  The content of the thermal polymerization initiator in the second resin composition of the present invention is preferably a ratio of 0.001 to 20% by weight with respect to the entire second resin composition (total amount), More preferably, the proportion is 0.01 to 10% by weight.

In the second resin composition of the present invention, when an epoxy resin (epoxy compound) is contained as an additive (modifier), a photo cationic polymerization initiator or a thermal cationic polymerization initiator may be used. .
As a photocationic polymerization initiator, if used generally, it can be used without restriction, and onium salts, organic metal complexes and the like can be mentioned.
Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts.
Examples of the organic metal complexes include iron-arene complexes, titanocene complexes, arylsilanol-aluminum complexes and the like.
As a commercially available photocationic polymerization initiator, for example, "ADEKA OPTOMER SP-150 (trade name)", "ADEKA OPTOMER SP-170 (trade name)" manufactured by ADEKA, "UVE-" manufactured by General Electronics Co., Ltd. 1014 (trade name), "CD-1012 (trade name)" manufactured by Sartmar, "CPI-100P (trade name)" manufactured by San-Apro, and the like.
Examples of the counter anion of the photocationic polymerization initiator include SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ^{− and the} like.

As a thermal cationic polymerization initiator, any commonly used one can be used without particular limitation, and, for example, various onium salts such as quaternary ammonium salts, phosphonium salts, sulfonium salts, organometallic complexes, etc. These may be used in combination.
Examples of commercially available onium salts include “ADEKA OPTON CP-66 (trade name)”, “ADEKA OPTON CP-77 (trade name)” manufactured by ADEKA, and “SAN AID SI-60L (trade name) manufactured by Sanshin Chemical Industry Co., Ltd. "", "San Aid SI-80L (trade name)", "San Aid SI-100 L (trade name)", "CI series (trade name)" manufactured by Nippon Soda Co., Ltd., and the like.
Moreover, as organometallic complexes, an alkoxysilane aluminum complex etc. are mentioned.

  The second resin composition of the present invention may further contain the above-mentioned additive (modifier) (see paragraph 0068), if necessary, in the entire second resin composition (as long as the effects of the present invention are not impaired). You may contain in the ratio of 0.01 to 50 weight% with respect to total amount.

  There is no particular limitation on the method of preparing (mixing) the second resin composition of the present invention, and, for example, the thiol compound of the present invention, an ene compound, another thiol compound, a photopolymerization initiator and / or thermal polymerization It can be prepared by mixing an initiator and an additive. As a mixing means, a known method (for example, the method described in paragraph 0071) can be adopted. The thiol compound of the present invention (in combination with other thiol compounds as required) may be dissolved or dispersed in a viscosity-adjusting diluent (organic solvent) in advance.

The first resin composition and the second resin composition of the present invention containing the thiol compound of the present invention (these resin compositions may be collectively referred to as “the resin composition of the present invention”) are It is expected to give a cured product excellent in hydrolysis resistance (moisture resistance).
That is, the resin composition of the present invention can be suitably used as an adhesive or a sealing agent because it gives a cured product having excellent moisture resistance as compared with a conventional resin composition containing a thiol compound. That is, the adhesive and sealing agent of the present invention contain the above-described resin composition of the present invention as a component.

  The adhesive and sealant of the present invention may contain an additive. Examples of additives include flow behavior modifiers such as silicic acid, magnesium silicate and barium sulfate, thermal conductivity imparting agents such as alumina, conductivity imparting agents such as silver and carbon, colorants such as pigments and dyes, etc. It can be mentioned. These additives can be blended at the time of preparation of the resin composition of the present invention. Also, it may be mixed with the already prepared resin composition of the present invention. As a mixing means, a known method (for example, the method described in paragraph 0071) can be adopted.

The adhesive and sealing agent of the present invention are not particularly limited in their use, and can be applied to various fields. As the application of the adhesive, for example, an adhesive for a flexible printed wiring board; an interlayer adhesive for a multilayer substrate such as a buildup substrate; an adhesive for bonding an optical component; an adhesive for bonding an optical disc; an adhesive for mounting a printed wiring board Die bonding adhesives; Adhesives for semiconductors such as underfills; Adhesives for mounting such as underfills for BGA reinforcement, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), etc. for optical pickups Adhesives; Adhesives for light path bonding; Adhesives used between exterior materials, base materials, ceiling materials and interior materials; Adhesives for bonding tiles and stones to outer wall materials and base materials; Wood flooring to various floors・ Adhesives for bonding high-polymer materials floor sheets and floor tiles; Structural materials for automobiles and aircraft, Adhesives for bodies and parts, Adhesives for automobile interiors, Adhesives for steel plate joints, etc. Gerare,
As the application of the sealing agent, for example, a sealing agent for joints of exterior materials such as various metal panels and siding boards; a sealing agent used between exterior materials, base materials, ceiling materials and interior materials; roads, bridges, tunnels, Sealing materials for joints of various concrete products such as breakwaters; Structural materials for automobiles and aircraft, Sealing agents for bodies and parts, Sealing agents for steel plate joints, Medical equipment sealing agents and the like.

  The resin composition of the present invention can be applied to products (parts and members) of various fields that may be made of resin, in addition to the above-mentioned adhesive and sealing agent, and may be used in electricity, electronics, optics, construction, civil engineering. It can be used as a raw material in the fields of automobiles, aircraft, medical care, and other daily use and sundries.

For example, examples of parts, members and materials in the field of electricity and electronics include copper foil with resin, prepreg, copper clad laminate, printed wiring board, solder resist ink, conductive paste, interlayer insulating material, sealing material, Sealing materials for LEDs, insulating materials, thermally conductive materials, materials for hot melt, paints, potting agents, etc., and more specifically, printed wiring such as interlayer insulating film, wiring covering film, etc. Sealing materials for plates and electronic parts, layer forming materials;
Materials for forming display devices such as color filters, films for flexible displays, resist materials, alignment films, etc.
Materials for forming semiconductor devices such as resist materials and buffer coat films;
Materials for forming optical components such as holograms, optical waveguides, optical circuits, optical circuit components, anti-reflection films and the like can be mentioned.
In addition, materials for forming rigid wiring boards and flexible printed wiring boards for mounting semiconductors, mounting materials for mounting semiconductors, sealing materials for semiconductors, sealing materials for solar cells, insulating films for semiconductors, coverlay films for protecting flexible printed circuits And coating agents for wiring coating.

  Examples of materials in the field of optics include core materials for optical fibers, cladding materials, lenses, wear-resistant coatings for lenses (e.g., hard coat-forming liquids), and the like.

  Examples of materials in the construction field include coating materials for exterior materials such as various metal panels and siding boards, primers; injection materials used between exterior materials, foundation materials, ceiling materials and interior materials, damping materials, soundproofing materials , Conductive materials for shielding electromagnetic waves, putty materials; adhesives for bonding wood flooring materials, polymer floor sheets, and floor tiles to various floors; injection materials for repairing cracks of various exterior materials and interior materials, etc. .

  Examples of materials in the field of civil engineering include coating materials for various concrete products such as roads, bridges, tunnels and breakwaters, primers, paints, putty materials, injection materials, spray materials, mold coverage, and the like.

  Examples of materials in the automobile and aircraft fields include structural materials, coating materials for bodies and parts, shock absorbing materials, damping materials, soundproofing materials, spray materials, adhesives for automotive interiors, coating materials, foam materials, steel plate joints And the like.

  Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives and the like.

Hereinafter, the present invention will be described in more detail by way of examples (synthetic test and evaluation test) and comparative examples (evaluation test), but the present invention is not limited thereto.
The main raw materials used in the synthesis test are as follows.

[Main raw material]
・ (±) -Limonene (manufactured by Tokyo Chemical Industry Co., Ltd., see chemical formula (III))
3-Thiapentane-1,5-dithiol (manufactured by Maruzen Yuka Co., Ltd., see chemical formula (VI-5))
・ Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.)

The main raw materials (except for the thiol compound of the present invention) used in the evaluation test are as follows.
[Main raw material]
(A) Hardening agent. 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril (trade name "TS-G" manufactured by Shikoku Kasei Kogyo Co., Ltd., see chemical formula (IX), thiol equivalent: 100.4 )
-Pentaerythritol tetrakis (3-mercapto propionate) (trade name "PEMP", manufactured by SC Organic Chemical Co., Ltd., see chemical formula (X), thiol equivalent: 122.2)

(B) Hardening accelerator, dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Microcapsule type amine adduct (Asahi Kasei Corporation, latent curing type, trade name "Novacua HXA3922HP")
(C) Epoxy compound (epoxy resin)
-Phenolic novolac epoxy resin (Mitsubishi Chemical Co., Ltd., trade name "jER152", epoxy equivalent: 174.0)
-Bisphenol A epoxy resin (Mitsubishi Chemical Co., Ltd., trade name "jER 828", epoxy equivalent: 187.0)

  The measuring method of the storage elastic modulus of the evaluation test employ | adopted in the Example and the comparative example and the measuring method of adhesive strength are as follows.

[Measurement of storage modulus]
The epoxy resin composition was cured (80 ° C./1 hour), and the obtained cured product (test piece: length 20 mm × width 5 mm × thickness 1 mm) was measured with a dynamic viscoelasticity measuring apparatus (manufactured by UBM, “Rheosol- The storage modulus E ′ (GPa) at 25 ° C. was measured (frequency: 1 Hz) using G5000 ′ ′).
It is determined that the cured product is more excellent in impact resistance as the storage elastic modulus is smaller (lower elasticity).

[Measurement of adhesive strength (moisture resistance test)]
For two blast-treated aluminum plates (length 100 mm x width 25 mm x thickness 1.6 mm), an area (length) in the range of 12.5 mm from either end (longitudinal direction) on one side of each aluminum plate The epoxy resin composition (adhesive agent) was applied to 12.5 mm × 25 mm in width.
Subsequently, two aluminum plates were pasted together such that the coated surfaces were in contact with each other, and then heating was performed (the epoxy resin composition was cured under the condition of 80 ° C./1 hour) to prepare a test piece.
Each tensile shear adhesive strength (MPa) before and after high-temperature, high-pressure steam treatment (PCT treatment, 121 ° C./48 hours) in an autoclave was measured for this test piece in accordance with JIS K 6850.
From the measured values obtained, the residual ratio of tensile shear adhesion strength after PCT treatment (hereinafter sometimes referred to as “the residual strength ratio”) was calculated by the following equation.
Residual strength ratio (%) = (tensile shear adhesion strength after PCT treatment) / (tensile shear adhesion strength before PCT treatment) × 100
It is judged that the moisture resistance of the cured product is better as the strength retention ratio is larger, and it is recognized that the epoxy resin composition is suitable as an adhesive.
In addition, when an adhesive layer eluted by PCT treatment and tensile shear adhesive strength could not be measured, it was described as "ND".

Example 1
Synthesis Example of Thiol Compound of the Present Invention
(±) -Limonene 20.43 g (150.0 mmol), 3-thiapentane-1,5-dithiol 115.74 g (750.0 mmol), azobisisobutyronitrile 0.25 g in a 500 ml four-necked eggplant flask (1.5 mmol) and 200.00 g of toluene were charged and stirred at 100 ° C. for 48 hours. The obtained reaction mixture was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate = 5/1 (v / v)) to obtain 50.72 g of pale yellow liquid (yield: 76.0%) ).

The ¹ H-NMR spectrum data of this pale yellow liquid are as follows.
¹ H-NMR (d ₆ -DMSO) δ: 2.70 (m, 16 H), 2.52 (t, 2 H), 2.38 (dt, 1 H), 2.10-1.30 (m, 8 H), 0.90 (m, 9 H).
Moreover, IR spectrum data of this pale yellow liquid were as the chart shown in FIG.
From these spectral data, the obtained pale yellow liquid was identified as the thiol compound represented by the above-mentioned chemical formula (I-4).

Example 2
209.4 parts by weight of the thiol compound (thiol equivalent: 209.4) synthesized in Example 1 as a curing agent, 12.2 parts by weight of dimethylbenzylamine as a curing accelerator, and 174.0 of jER 152 as an epoxy compound The epoxy resin composition was prepared by mixing with parts by weight. In addition, the usage-amount of a hardening accelerator was adjusted so that the gelation time (80 degreeC) of an epoxy resin composition might be 2 minutes +/- 20 second.
When an evaluation test (measurement of storage elastic modulus of cured product and measurement of adhesive strength when used as an adhesive agent) was performed on this epoxy resin composition, the test results obtained are as shown in Table 1. there were.

[Examples 3 to 6, Comparative Examples 1 to 2]
In the same manner as in Example 2, epoxy resin compositions having the compositions shown in Table 1 were prepared, and evaluation tests were carried out for those epoxy resin compositions. The obtained test results are shown in Table 1 As shown in.

The thiol compound of the present invention is expected to be used as an intermediate material for various sulfur-containing compounds and as a curing agent for resins.
Further, the resin composition containing the thiol compound of the present invention is suitable for various uses such as adhesion, sealing, sealing, casting, molding, coating, coating and the like.

Claims (10)

A thiol compound represented by a chemical formula (I).

The method for synthesizing a thiol compound according to claim 1, which comprises reacting one selected from dialkene compounds represented by the chemical formulas (II) to (V) with a thiol compound represented by the chemical formula (VI).

(Wherein, R ₁ is as defined above)   A curing agent containing the thiol compound according to claim 1.   A resin composition comprising the thiol compound according to claim 1 and an epoxy compound.   The resin composition according to claim 4, which contains an amine as a curing accelerator.   The resin composition according to claim 4, containing a reaction product of an epoxy compound and an amine as a curing accelerator.   The reaction product of a compound having one or more isocyanate groups in a molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule is contained as a curing accelerator. 4 resin composition.   A resin composition comprising the thiol compound according to claim 1 and an ene compound having a carbon-carbon double bond in the molecule.   An adhesive comprising the resin composition according to any one of claims 4 to 8 as a component.   A sealing agent comprising the resin composition according to any one of claims 4 to 8 as a component.

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