JP2020029543A - Resin composition and method for producing resin composition - Google Patents

Abstract

To provide a resin composition that contains a vinyl ester resin and is excellent in high-temperature stability and a method for producing the resin composition.SOLUTION: A resin composition contains: a resin component containing one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, and a vinyl ester resin; a radical-polymerizable unsaturated monomer; and a nitroso compound. The nitroso compound may be one or more selected from N-nitroso-N-methyl aniline, N-nitroso phenyl hydroxylamine aluminum salt, N-nitroso-N-cyclohexyl aniline.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and a method for producing the resin composition.

  Vinyl ester resins have excellent properties such as mechanical properties, chemical resistance, heat resistance, and oxidation resistance. For this reason, vinyl ester resins are used in a wide range of fields. In particular, vinyl ester resins are frequently used as materials for adhesives.

Vinyl ester resins tend to gel during storage. Therefore, conventionally, a polymerization inhibitor such as a hydroquinone or a quinone has been added to the vinyl ester resin to prevent the vinyl ester resin from gelling.
As a technique for stabilizing a vinyl ester resin, a resin composition excellent in high-temperature stability in which a specific nitroso compound is added in an amount of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of a vinyl ester resin has been proposed. (For example, see Patent Document 1).

JP-A-3-243610

  However, the conventional method for stabilizing a vinyl ester resin has insufficient stability under high temperature conditions. For this reason, there is a demand for a method for stabilizing a vinyl ester resin capable of obtaining sufficiently high stability even under high temperature conditions.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a resin composition containing a vinyl ester resin and having good high-temperature stability and a method for producing the same.

The present inventors have intensively studied to solve the above problems.
As a result, a resin composition containing one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, a vinyl ester resin, a radically polymerizable unsaturated monomer, and a nitroso compound is obtained. The present inventors have found that what is necessary is to achieve the present invention.
The present invention has been completed based on the above findings, and the gist is as follows.

[1] a resin component containing one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, and a vinyl ester resin;
A radically polymerizable unsaturated monomer,
A resin composition comprising a nitroso compound.

[2] The above [1], wherein the nitroso compound is one or more selected from N-nitroso-N-methylaniline, N-nitrosophenylhydroxylamine aluminum salt, and N-nitroso-N-cyclohexylaniline. Resin composition.
[3] The resin composition according to [1] or [2], wherein the nitroso compound is contained in an amount of 0.005 to 5.0 parts by mass based on 100 parts by mass of the resin component.

[4] The resin composition according to any one of [1] to [3], wherein the resin component comprises a urethane (meth) acrylate resin and a vinyl ester resin.
[5] The resin composition according to [4], wherein the resin component contains 10 to 80% by mass of a urethane (meth) acrylate resin.

[6] The resin composition according to any one of [1] to [3], wherein the resin component comprises an unsaturated polyester resin and a vinyl ester resin.
[7] The resin composition according to [6], wherein the resin component contains 5 to 80% by mass of an unsaturated polyester resin.

[8] The resin composition according to any one of [1] to [3], wherein the resin component comprises a urethane (meth) acrylate resin, an unsaturated polyester resin, and a vinyl ester resin.
[9] The resin composition according to any one of [1] to [8], wherein the resin component contains 20 to 95% by mass of a vinyl ester resin.

[10] The resin composition according to any one of [1] to [9], which contains a polymerization inhibitor.
[11] The resin composition according to [10], wherein the polymerization inhibitor is trimethylhydroquinone.

[12] a step of producing a mixture of a resin component containing one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, a vinyl ester resin, a radically polymerizable unsaturated monomer, and a nitroso compound; A method for producing a resin composition, comprising:
[13] The method for producing a resin composition according to [12], wherein 0.005 to 5.0 parts by mass of the nitroso compound is mixed with 100 parts by mass of the resin component.

  The resin composition of the present invention contains one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, a resin component containing a vinyl ester resin, a radically polymerizable unsaturated monomer, and a nitroso compound. . Therefore, the storage stability at high temperatures is good.

Hereinafter, the resin composition of the present invention and the method for producing the resin composition will be described in detail.
[Resin composition]
The resin composition of the present embodiment contains a resin component, a radical polymerizable unsaturated monomer, and a nitroso compound as essential components. The resin composition of the present embodiment can contain a polymerization inhibitor, a radical polymerization initiator, and other additives in addition to the resin component and the nitroso compound.

"Resin component"
The resin component contains, as essential components, one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, and a vinyl ester resin (epoxy (meth) acrylate resin). Specifically, the resin component is composed of a urethane (meth) acrylate resin and a vinyl ester resin, one composed of an unsaturated polyester resin and a vinyl ester resin, and one composed of a urethane (meth) acrylate resin, an unsaturated polyester resin and a vinyl ester. Any one selected from those comprising an ester resin.
The resin component in the resin composition of the present embodiment does not contain styrene.

More preferably, the resin component contains an unsaturated polyester resin for the following reasons.
The urethane (meth) acrylate resin, the unsaturated polyester resin, and the vinyl ester resin are all cured by a radical polymerization reaction. Vinyl ester resins have a carbon-carbon double bond as a crosslinking point at the end of the molecule. The urethane (meth) acrylate resin has a (meth) acryloyloxy group as a crosslinking point at the terminal of the molecule, similarly to the vinyl ester resin. On the other hand, the unsaturated polyester resin has a carbon-carbon double bond as a crosslinking point in the middle of the molecular structure. For this reason, the unsaturated polyester resin has low copolymerizability with the vinyl ester resin which is an essential component. As a result, when the resin component contains an unsaturated polyester resin, it is presumed that a resin composition having better high-temperature stability can be obtained.

  As used herein and in the claims, "(meth) acrylate" refers to acrylate or methacrylate.

(Vinyl ester resin)
As the vinyl ester resin, those obtained by reacting an unsaturated monobasic acid with an epoxy resin or a modified epoxy resin can be used.
Examples of the epoxy resin include bisphenol A diglycidyl ether, its high-molecular-weight homologues, and novolak-type glycidyl ethers.
Specifically, bisphenol type epoxy resins (for example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin and / or methyl epichlorohydrin, or glycidyl of bisphenol A Biphenyl-type epoxy resins (for example, those obtained by reacting biphenol with epichlorohydrin and / or methyl epichlorohydrin), such as those obtained by reacting a condensate of ether and the above-mentioned bisphenols with epichlorohydrin and / or methyl epichlorohydrin. , Naphthalene type epoxy resins (for example, those obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methyl epichlorohydrin), Aralkyl diphenol type epoxy resins (for example, those obtained by reacting aralkyl phenol with epichlorohydrin and / or methyl epichlorohydrin), diglycidyl type epoxy resins (for example, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester) Alicyclic epoxy resin (for example, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, etc.), having an oxazolidone ring obtained by reacting the epoxy resin with a diisocyanate. Epoxy resin (specific examples: Araldite AER4152 made by Asahi Kasei Epoxy), novolak type epoxy resin (for example, phenol novolak or cresol novolak and epichlorohydrin) And / or methyl epichlorohydrin), trisphenolmethane-type epoxy resins (for example, those obtained by reacting trisphenolmethane, triscresol methane with epichlorohydrin and / or methyl epichlorohydrin, etc.), Epicron N-740 (manufactured by DIC Corporation, phenol novolak type epoxy resin), Araldite AER-2603 (manufactured by Asahi Kasei E-materials Corporation, bisphenol A type epoxy resin) and the like.

The modified epoxy resin is obtained, for example, by reacting an epoxy resin with a compound selected from bisphenol A, bisphenol F, bisphenol S or other adipic acid, sebacic acid, dimer acid, or liquid nitrile rubber. Things.
By using a modified epoxy resin as a material of the vinyl ester resin, a resin composition can be obtained from which a cured product having good flexibility and toughness can be obtained.

Known unsaturated monobasic acids can be used. For example, unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, and cinnamic acid.
Further, instead of the unsaturated monobasic acid, a reaction product of a compound having one hydroxy group and one or more (meth) acryloyl groups and a polybasic anhydride may be used. The polybasic acid in the above polybasic acid anhydride is used for increasing the molecular weight of the epoxy resin, and known polybasic acids can be used. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol / 2 mol maleic anhydride adduct, polyethylene Glycol / 2 mol maleic anhydride adduct, propylene glycol / 2 mol maleic anhydride adduct, polypropylene glycol / 2 mol maleic anhydride adduct, dodecandioic acid, tridecandioic acid, octadecandioic acid, 1,16- (6 -Ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name: Hycar CTBN), and the like.

  When synthesizing the vinyl ester resin contained in the resin component of the present embodiment, a catalyst can be used for reacting the epoxy resin or the modified epoxy resin with the unsaturated monobasic acid. Examples of the catalyst include compounds containing a tertiary nitrogen such as triethylamine, pyridine derivative, imidazole derivative and imidazole derivative; amine salts such as tetramethylammonium chloride, tetradecyldimethylbenzylammonium chloride and triethylamine; and trimethylphosphine and trimethylamine. And phosphorus compounds such as phenylphosphine. The catalyst used in synthesizing the vinyl ester resin may remain in the resin composition.

  The content of the vinyl ester resin in the resin component is preferably from 20 to 95% by mass, more preferably from 25 to 80% by mass, and most preferably from 30 to 70% by mass. When the content of the vinyl ester resin is 20% by mass or more, excellent properties such as mechanical properties, chemical resistance, heat resistance, and oxidation resistance are exhibited by including the vinyl ester resin, which is preferable. When the content of the vinyl ester resin is 95% by mass or less, it is easy to secure the content of one or both of the urethane (meth) acrylate resin and the unsaturated polyester resin in the resin component, which is preferable.

(Unsaturated polyester resin)
As the unsaturated polyester resin, those obtained by subjecting an unsaturated dibasic acid and, if necessary, a dibasic acid component containing a saturated dibasic acid and a polyhydric alcohol component to an esterification reaction can be used. .
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride, and these may be used alone or in combination of two or more. May be used.

  Examples of the saturated dibasic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, isobaric acid and other aliphatic dibasic acids, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid , Tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4 , 4'-biphenyldicarboxylic acid, aromatic dibasic acids such as dialkyl esters thereof, halogenated saturated dibasic acids, etc., which may be used alone or in combination of two or more. May be used.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6. -Hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl -1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2-cyclohexyl Glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, para-xylene glycol, bicyclohexyl-4,4′-diol, 2,6-decalin glycol, 2,7- Dihydric alcohols such as decalin glycol;
Dihydric alcohols such as adducts of dihydric phenols represented by hydrogenated bisphenol A, cyclohexane dimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and alkylene oxides represented by propylene oxide or ethylene oxide ;
Examples thereof include trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

  As the unsaturated polyester resin, a resin modified with a dicyclopentadiene-based compound may be used as long as the effects of the present invention are not impaired. As a modification method using a dicyclopentadiene-based compound, for example, a method in which dicyclopentadiene and a maleic acid addition product (sidecanol monomalate) are obtained, and this is used as a monobasic acid to introduce a dicyclopentadiene skeleton. And other known methods.

  When the resin component contains an unsaturated polyester resin, the content of the unsaturated polyester resin in the resin component is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, and Most preferably, it is 50% by mass. It is preferable that the content of the unsaturated polyester resin be 5% by mass or more, because a resin composition having better high-temperature stability can be obtained. It is preferable that the content of the unsaturated polyester resin be 80% by mass or less, because the content of the vinyl ester resin in the resin component can be easily secured.

  In the vinyl ester resin and / or the unsaturated polyester resin used in the present embodiment, an oxidative polymerization group such as an allyl ether group may be introduced. The method for introducing the oxidized polymer group is not particularly limited. For example, addition of an oxidized polymer group-containing polymer, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether A method of adding a reaction product of a compound having a hydroxyl group and an allyl ether group to an acid anhydride.

[Urethane (meth) acrylate resin]
As the urethane (meth) acrylate resin, for example, a poly (isocyanate) obtained by reacting a polyisocyanate and a polyhydric alcohol with isocyanate groups at both ends of a polyurethane obtained by reacting a hydroxyl group-containing (meth) acrylate ester with a polyisocyanate is used. Can be used. The polyhydric alcohol used as a material of the urethane (meth) acrylate resin is not particularly limited, and for example, a polyol such as a polyester polyol, a polycarbonate polyol, and a polyether polyol can be used.

  When synthesizing the urethane (meth) acrylate contained in the resin component of the present embodiment, a step of reacting a polyisocyanate with a polyhydric alcohol to obtain a polyurethane, and an isocyanato group at both ends of the obtained polyurethane, In the step of reacting the (meth) acrylic acid ester containing a hydroxyl group, a catalyst can be used. As the catalyst, a known catalyst such as dibutyltin dilaurate, tertiary amines and phosphones can be used. The catalyst used at this time may remain in the resin composition.

  When the resin component contains a urethane (meth) acrylate resin, the content of the urethane (meth) acrylate resin in the resin component is preferably from 10 to 80% by mass, more preferably from 15 to 70% by mass. Preferably, 20 to 50% by mass is most preferable. When the content of the urethane (meth) acrylate resin is 10% by mass or more, a cured product excellent in impact resistance and flexibility is obtained, which is preferable. When the content of the urethane (meth) acrylate resin is 80% by mass or less, it is easy to secure the content of the vinyl ester resin in the resin component, which is preferable.

(Other resin components)
The resin component includes one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, a vinyl ester resin, and a resin that is not a urethane (meth) acrylate resin, an unsaturated polyester resin, or a vinyl ester resin. And at least one resin such as polyester (meth) acrylate resin and (meth) acrylate resin.

[Polyester (meth) acrylate resin]
As the polyester (meth) acrylate resin, for example, a resin obtained by reacting a polyvalent carboxylic acid with a polyhydric alcohol can be used. Specifically, as the polyester (meth) acrylate resin, a resin obtained by reacting (meth) acrylic acid with hydroxyl groups at both ends, such as polyethylene terephthalate, can be used.

[(Meth) acrylate resin]
Examples of the (meth) acrylate resin include a poly (meth) acrylic resin having at least one substituent selected from a hydroxyl group, an isocyanato group, a carboxy group, and an epoxy group, and a monomer having the substituent and a (meth) acrylate resin. A) A resin obtained by reacting a (meth) acrylic ester having a hydroxyl group with a substituent of a polymer with an acrylate can be used.

`` Residual catalyst ''
In the resin composition of the present embodiment, the catalyst used for synthesizing various resins contained in the resin component may remain.

"Nitroso compounds"
A nitroso compound is a compound having a nitroso group (-N = O). The nitroso compound preferably contains a compound in which a nitroso group is bonded to a nitrogen atom, since a resin composition having better high-temperature stability can be obtained. Examples of the nitroso compound having a nitroso group bonded to a nitrogen atom include N-nitroso-N-methylaniline represented by the following formula (1), ammonium N-nitrosophenylhydroxylamine represented by the following formula (2) N, N'-dinitrosopentamethylenetetramine represented by the following formula (3), N-nitrosodiphenylamine represented by the following formula (4), aluminum salt of N-nitrosophenylhydroxylamine represented by the following formula (5), Examples include N-nitroso-N-cyclohexylaniline represented by the following formula (6).

  As the nitroso compound, one or more selected from N-nitroso-N-methylaniline, N-nitrosophenylhydroxylamine aluminum salt, and N-nitroso-N-cyclohexylaniline among the above nitroso compounds It is particularly preferable to use N-nitroso-N-methylaniline for the following reasons. By using N-nitroso-N-methylaniline as the nitroso compound, a resin composition having better high-temperature stability can be obtained. This effect is presumed to be due to the fact that the nitroso group contained in N-nitroso-N-methylaniline is released and traps radicals in the resin composition, thereby suppressing gelling of the resin composition. You. In addition, N-nitroso-N-methylaniline does not affect the curability of the resin composition and does not affect the curing delay of the resin composition. In addition, N-nitroso-N-methylaniline is liquid at room temperature, so that it can be easily dissolved in the resin composition as compared with a solid (powder) at room temperature, and has good workability. It is.

  The resin composition of the present embodiment preferably contains the nitroso compound in an amount of 0.005 to 5.0 parts by mass based on 100 parts by mass of the resin component. When the content of the nitroso compound is 0.005 parts by mass or more, the effect of improving the high-temperature stability by including the nitroso compound is remarkably obtained. More preferably, the content of the nitroso compound is 0.05 parts by mass or more. Further, when the content of the nitroso compound is 5 parts by mass or less, the content of the resin component can be sufficiently increased, so that a resin composition having characteristics according to the intended use can be obtained. The content of the nitroso compound is more preferably 1 part by mass or less because curing failure is less likely to occur and the resin composition has good curability.

  The presence of the nitroso compound in the resin composition of the present embodiment can be confirmed by, for example, a spectrum obtained by measuring the resin composition by nuclear magnetic resonance (1H-NMR) spectroscopy. Specifically, for example, when the nitroso compound is N-nitroso-N-methylaniline, a proton derived from a methyl group is detected as a peak at around 3.39 ppm.

"Radically polymerizable unsaturated monomer"
As the radical polymerizable unsaturated monomer, for example, styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl isocyanurate , And (meth) acrylic acid esters.

  Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t- (meth) acrylate. -Butyl, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl Ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) Acrylate, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate and the like can be mentioned.

  Further, as the polyfunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythri Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, etc. Is mentioned.

  These radically polymerizable unsaturated monomers may be used alone or in combination of two or more.

  Among these radically polymerizable unsaturated monomers, styrene, methyl (meth) acrylate, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate are preferred from the viewpoint of workability and curability. Of these, styrene is particularly preferred because of good workability and curability and low cost.

  The amount of the radical polymerizable unsaturated monomer used is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass, based on the total of the resin component and the radical polymerizable unsaturated monomer. Is more preferable, and more preferably 40 to 55% by mass. When the use amount of the radical polymerizable unsaturated monomer is 20% by mass or more, the viscosity of the resin composition decreases, and the workability is improved. On the other hand, when the use amount of the radical polymerizable unsaturated monomer is 80% by mass or less, a required resin viscosity is obtained, and workability is improved.

`` Polymerization inhibitor ''
Examples of the polymerization inhibitor include those commonly known and used, for example, piperidine derivatives such as 4H-2,2,6,6-tetramethylpiperidino-1-oxyl, hydroquinone, methylhydroquinone, trimethylhydroquinone, and trihydrobenzene. Benzoquinone, P-benzoquinone, hydroquinone monomethyl ether, t-butylhydroquinone, catechol, t-butylcatechol, 2,6-di-t-butyl-4-methylphenol and the like.

  As the polymerization inhibitor, among the above, it is particularly preferable to use trimethylhydroquinone for the following reasons. Quinone compounds such as hydroquinone and trimethylhydroquinone have a retarding effect of slowing down the curing of the resin composition. Trimethylhydroquinone has a sufficient retarding effect and also has an effect of improving the high-temperature stability of the resin composition. This effect is presumed to be due to the fact that the three methyl groups of the trimethylhydroquinone serve as steric hindrance, so that the radicals in the resin composition trapped by the trimethylhydroquinone are difficult to leave.

Part or all of the polymerization inhibitor may be a residue of the polymerization inhibitor used when synthesizing various resins contained in the resin component.
The content of the polymerization inhibitor in the resin composition can be confirmed by, for example, a method of analyzing using a gas chromatography method.

  When a polymerization inhibitor is used, the content of the polymerization inhibitor in the resin composition is preferably from 0.01 to 1% by mass, and more preferably from 0.03 to 0.8% by mass. When the content of the polymerization inhibitor in the resin composition is 0.01% by mass or more, the effect of retarding the curing of the resin composition and the effect of improving the high-temperature stability by the polymerization inhibitor can be more effectively obtained. When the content of the polymerization inhibitor in the resin composition is 1% by mass or less, the resin composition hardly causes poor curing, which is preferable.

"Radical polymerization initiator"
Examples of the radical polymerization initiator include diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, and dialkyl peroxides such as dicumyl peroxide. Organic peroxides such as oxides, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters and percarbonates; benzoin ethers such as benzoin alkyl ethers, benzophenone, benzyl, Benzophenones such as methylorthobenzoylbenzoate, benzyldimethylketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiopheno Radical polymerization such as acetophenones such as 1,4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone, and thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone Initiators.
Among these, methyl ethyl ketone peroxide, benzoyl peroxide, t-butyl peroxybenzoate, and cumene hydroperoxide are desirable from the viewpoints of cost, availability, stability, and curability. These radical polymerization initiators may be used alone or in a combination of two or more.

  When the resin composition of the present embodiment contains a radical polymerization initiator, the content is preferably 0.1 to 10 parts by mass, based on a total of 100 parts by mass of the resin component and the radically polymerizable unsaturated monomer. Parts, more preferably 0.5 to 8 parts by mass, still more preferably 0.5 to 5 parts by mass.

"Other additives"
The resin composition of the present embodiment can include other additives as necessary. Examples of the additives include a curing accelerator, a curing accelerator, a filler, a thixotropic agent, a wax, a coloring agent, a drying agent, and the like. These additives may be used alone or in combination of a plurality of types.

`` Curing accelerator ''
Known curing accelerators such as cobalt metal salts can be used. The cobalt metal salt used as the curing accelerator is not particularly limited, and includes, for example, cobalt naphthenate, cobalt octylate, cobalt hydroxide and the like, and uses cobalt naphthenate and / or cobalt octylate Is preferred.

  The content of the curing accelerator is 0.02 to 10 parts by mass, preferably 0.1 to 3.0 parts by mass, based on 100 parts by mass of the total of the resin component and the radical polymerizable unsaturated monomer. When the content of the curing accelerator is 0.02 parts by mass or more, the curing time is sufficiently shortened, and poor curing can be prevented, which is preferable. In addition, when the content of the curing accelerator is 10 parts by mass or less, it is preferable to prevent the curing time from being excessively accelerated and the pot life from being insufficient or the storage stability from being poor.

"Curing accelerator"
Examples of the curing accelerator include amines. Specifically, aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxy Ethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) Benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylimorpholine, piperidine, N, N-bis ( N, N-substituted anilines such as hydroxyethyl) aniline and diethanolaniline, and N, N-substituted- - toluidine, 4- (N, N- disubstituted amino) amines, such as benzaldehyde can be used.

`` Filling material ''
The resin composition of the present embodiment may include a filler for the purpose of improving workability and adjusting physical properties. Examples of the filler include an inorganic filler and an organic filler.
Examples of the inorganic filler include cement, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, sand containing silica as a main component, ceramics, artificial aggregates such as glass chips, talc, and water. Known materials such as aluminum oxide, calcium carbonate and cement can be used. These may be used alone or in combination.

"Thixotropic agent"
The resin composition of the present embodiment can include a thixotropic agent from the viewpoint of adjusting the mixing property and the fluidity of the adhesive composition. As the thixotropic agent, an inorganic thixotropic agent such as fumed silica and talc may be used, or an organic thixotropic agent such as a special amide type may be used. As the thixotropic agent, only one type may be used, or a plurality of types may be used in combination.

"wax"
The resin composition of the present embodiment may contain wax for the purpose of improving the drying property. Examples of the wax include paraffin waxes and polar waxes. These waxes may be used alone or in combination of two or more.
Known paraffin waxes having various melting points can be used. Further, as the polar waxes, those having both a polar group and a non-polar group in the structure can be used. Specifically, NPS-8070, NPS-9125 (manufactured by Nippon Seiro Co., Ltd.), Emanon 3199 And 3299 (manufactured by Kao Corporation).

"Colorant"
As the colorant, an inorganic pigment such as titanium oxide can be used.
"desiccant"
Molecular sieves or the like can be used as the desiccant.

[Method for producing resin composition]
The resin composition of the present embodiment includes, for example, the above resin component, a radical polymerizable unsaturated monomer, a nitroso compound, and a polymerization inhibitor, a radical polymerization initiator, and other additives contained as necessary. It can be manufactured by mixing the agent with a known method.
The method for producing the resin composition of the present embodiment may be any method including a step of producing a mixture of the above resin component, a radical polymerizable unsaturated monomer, and a nitroso compound. The mixing order of the unsaturated monomer and the nitroso compound is not particularly limited. For example, a radical polymerizable unsaturated monomer may be added to a mixture obtained by mixing a resin component and a nitroso compound, or a resin component and a radical polymerizable unsaturated monomer may be mixed. A nitroso compound may be added to the mixture.
In the resin composition of the present embodiment, 0.005 to 5 parts by mass of a nitroso compound is preferably mixed with 100 parts by mass of the above resin component.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

"Preparation of resin component"
<Synthesis of vinyl ester resin (epoxy (meth) acrylate resin)>
Araldite AER-2603 (manufactured by Asahi Kasei E-Materials Co., Ltd., bisphenol A type epoxy resin: epoxy equivalent: 189): 1890 g, and bisphenol A: 570 g were added to a reactor equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer. And triethylamine as a catalyst: 12.3 g, and reacted at 150 ° C. for 2 hours in a nitrogen gas atmosphere, and then cooled to 90 ° C. to obtain a modified epoxy resin. To the obtained modified epoxy resin, 430 g of methacrylic acid, 9 g of tetradecyldimethylbenzylammonium chloride as a catalyst, 0.9 g of hydroquinone as a polymerization inhibitor, and 1000 g of styrene are added, and air is blown therein. The reaction was terminated at 90 ° C. for 20 hours, and the reaction was terminated when the acid value became 10 mgKOH / g, to obtain a vinyl ester resin diluted with styrene. 1912 g of styrene was further added to the vinyl ester resin diluted with styrene to obtain a vinyl ester resin composition containing styrene as a radically polymerizable unsaturated monomer and containing 50% by mass of a vinyl ester resin.

<Synthesis of urethane (meth) acrylate resin>
A reaction apparatus equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer was charged with 500 g of diphenylmethane diisocyanate, 76 g of propylene glycol, and 0.5 g of dibutyltin dilaurate as a catalyst, and was heated at 60 ° C. for 4 hours. The reaction was carried out with stirring. The obtained reaction product was stirred while dropping 260 g of 2-hydroxyethyl methacrylate over 2 hours. After the dropping was completed, the mixture was stirred and reacted for 5 hours to synthesize a urethane methacrylate resin. By adding 836 g of styrene to the obtained urethane methacrylate resin, a urethane (meth) acrylate resin composition containing styrene as a radically polymerizable unsaturated monomer and containing 50% by mass of a urethane acrylate resin was obtained.

<Synthesis of unsaturated polyester resin>
556 g of propylene glycol, 540 g of phthalic anhydride, and 358 g of maleic anhydride were charged into a reactor equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, and the temperature was raised while flowing nitrogen. The reaction water began to be discharged from the point in time when the temperature in the reactor reached 171 ° C, but the temperature was gradually raised to 215 ° C. The temperature in the reactor was maintained at 215 ° C., and when the acid value of the reaction product reached 70, the pressure was reduced. This reduced pressure was maintained for 2 hours to obtain an unsaturated polyester resin having an acid value of 17 mgKOH / g. Was. The temperature of the resulting unsaturated polyester was lowered to 150 ° C. and dissolved in a flask containing 1454 g of styrene and 0.3 g of hydroquinone as a polymerization inhibitor. Thus, an unsaturated polyester resin composition containing styrene as a radical polymerizable unsaturated monomer and containing 50% by mass of the unsaturated polyester resin was obtained.

[Examples 1 to 11, Comparative Examples 1 to 16]
The urethane (meth) acrylate resin composition, the unsaturated polyester resin composition, and the vinyl ester resin composition thus obtained were mixed at the ratios shown in Tables 1 to 3, and 11. The compositions containing the resin components of Comparative Examples 1 to 16 were obtained.
Next, the compositions containing the resin components of Examples 1 to 11 and Comparative Examples 1 to 16, the nitroso compounds and the polymerization inhibitors shown in Tables 1 to 3 were mixed at the contents shown in Tables 1 to 3, respectively. Then, the resin compositions of Examples 1 to 11 and Comparative Examples 1 to 16 were obtained.

The numerical values in parentheses of the vinyl ester resin, urethane (meth) acrylate resin, and unsaturated polyester resin shown in Tables 1 to 3 are the contents (% by mass) in the resin components, respectively.
The numerical value in parentheses of the radical polymerizable unsaturated monomer shown in Tables 1 to 3 is the content (mass) of the radical polymerizable unsaturated monomer with respect to the total of the resin component and the radical polymerizable unsaturated monomer. %).
The numerical values of the nitroso compound shown in Tables 1 to 3 are the content (parts by mass) of the nitroso compound with respect to 100 parts by mass of the resin component (the total of the urethane (meth) acrylate resin, the unsaturated polyester resin, and the vinyl ester resin).
The numerical values of the polymerization inhibitors shown in Tables 1 to 3 are the content (% by mass) of the polymerization inhibitors in the resin composition.
“Polystop 7300P” in Tables 1 to 3 is a trade name of a piperidine derivative manufactured by Hakuto Corporation.

With respect to the resin compositions of Examples 1 to 11 and Comparative Examples 1 to 16, the storage stability at 80 ° C. in a state before mixing the curing agent was evaluated by the method described below. The results are shown in Tables 1 to 3.
"Evaluation method for storage stability at 80 ° C"
80 g of the resin composition was put into a tin-made push-top round can having a capacity of 105 ml, and the round can was allowed to stand in a thermostatic dryer in which the temperature of the gas layer was set to 80 ° C. The time when the mixing of the composition containing the resin component, the nitroso compound, and the polymerization inhibitor is completed in the production process of the resin composition is regarded as the production end of the resin composition, and the temperature of the resin composition after the production is completed is set to 25. C. and stored in a round can. The can was allowed to stand in a thermostatic drier within 6 hours after the production was completed.
Tilt the round can every day (every 24 hours) after the end of production, and check by hearing whether or not the test specimen has gelled (state in which fluidity is lost), and measure the number of days until the test specimen gels did.

  As shown in Tables 2 and 3, Comparative Example 14 containing a nitroso compound and having a resin component of only a vinyl ester resin had higher high-temperature stability at 80 ° C. than Comparative Example 1 of containing only a vinyl ester resin. It was good. Comparative Example 15 containing a nitroso compound and containing only a urethane (meth) acrylate resin as the resin component had better high-temperature stability at 80 ° C. than Comparative Example 2 containing only the urethane (meth) acrylate resin. there were. Comparative Example 16 containing a nitroso compound and containing only an unsaturated polyester resin as the resin component had better high-temperature stability at 80 ° C. than Comparative Example 3 containing only the unsaturated polyester resin.

  However, Comparative Examples 14 to 16 shown in Table 2 still have insufficient high-temperature stability at 80 ° C, and have a higher high-temperature stability at 80 ° C as compared with Examples 1 to 11 shown in Table 1. It was inferior. This is presumed to be due to the difference in polymerizability obtained when the resin component contains one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin and a vinyl ester resin.

Example 1 is a resin composition containing a resin component containing a urethane (meth) acrylate resin and a vinyl ester resin, and a nitroso compound. As shown in Tables 1 and 2, Example 1 had better high-temperature stability at 80 ° C. as compared with Comparative Example 4 which had the same resin component as Example 1 but did not contain a nitroso compound.
Example 9 did not contain trimethylhydroquinone, and the high-temperature stability at 80 ° C. was better than Example 1 in which the proportion of the vinyl ester resin was smaller than that in Example 9.

  Example 2 is a resin composition containing an unsaturated polyester resin and a vinyl ester resin, and a resin composition containing a nitroso compound. As shown in Tables 1 and 2, Example 2 had better high-temperature stability at 80 ° C. as compared with Comparative Example 5 which had the same resin component as Example 2 but did not contain a nitroso compound.

Example 3 is a resin composition containing a urethane (meth) acrylate resin, an unsaturated polyester resin, and a vinyl ester resin, and a nitroso compound. As shown in Tables 1 and 2, Example 3 had better high-temperature stability at 80 ° C. as compared with Comparative Example 6 which had the same resin component as Example 3 but did not contain a nitroso compound.
Example 3 has better high-temperature stability at 80 ° C. than Example 10 in which the proportions of the urethane (meth) acrylate resin and the unsaturated polyester resin are lower and the proportion of the vinyl ester resin is higher than in Example 3. Met.

Example 4 has the same resin component and resin ratio as Example 3, and contains a nitroso compound and trimethylhydroquinone. As shown in Tables 1 and 2, Example 4 had better high-temperature stability at 80 ° C. as compared with Comparative Example 7 which had the same composition as Example 4 except that no nitroso compound was contained. Was.
Example 4 had better high-temperature stability at 80 ° C. as compared with Example 3 containing no trimethylhydroquinone.
Example 4 has better high-temperature stability at 80 ° C. than Example 11 in which the proportions of the urethane (meth) acrylate resin and the unsaturated polyester resin are smaller and the proportion of the vinyl ester resin is larger than in Example 4. Met.

  Example 11 has the same resin component and resin ratio as Example 10, and contains a nitroso compound and trimethylhydroquinone. As shown in Table 1, Example 11 had better high-temperature stability at 80 ° C. as compared to Example 10 containing no trimethylhydroquinone.

  In Example 5, the resin component was the same as that of Example 3, and the content of the nitroso compound was larger than that of Example 3. Example 5 had better high-temperature stability at 80 ° C. as compared with Example 3. Further, Example 6 has the same resin component as Example 5, and the content of the nitroso compound is larger than that of Example 5. Example 6 had better high-temperature stability at 80 ° C. as compared to Examples 3 and 5.

  Example 6 including N-nitroso-N-methylaniline as a nitroso compound has the same resin component as that of Example 6, and has a higher temperature at 80 ° C. than Examples 7 and 8 in which the type of nitroso compound is different. The stability was better.

  Example 3 includes a resin component containing a urethane (meth) acrylate resin, an unsaturated polyester resin, and a vinyl ester resin, and a nitroso compound. Example 4 has the same resin component as Example 3, but contains a nitroso compound, and contains trimethylhydroquinone as a polymerization inhibitor. As shown in Tables 1 to 3, Examples 3 and 4 contain no nitroso compound, contain trimethylhydroquinone, and are compared with Comparative Examples 8 to 10 in which the resin component is the same as Examples 3 and 4. Thus, the high temperature stability at 80 ° C. was good.

The room temperature curing characteristics of the resin compositions of Examples 9 and 11 were evaluated by the following method. Table 4 shows the results.
"Cooling characteristics at room temperature (exothermic method)"
The evaluation was carried out in accordance with JIS K6901: 2008, 5.9 “Cooling at room temperature (exothermic method)”.
As a curing agent, trade name “Permec N” (methyl ethyl ketone peroxide type, manufactured by NOF Corporation) was used. The amount of the curing agent used was 1.0 part by mass with respect to the total of 100 parts by mass of the resin component and the radical polymerizable unsaturated monomer.
As the accelerator, trade name "hexoate cobalt 8%" (cobalt octylate, Toei Kako Co., Ltd.) was used. The amount of the accelerator used was 0.3 parts by mass with respect to 100 parts by mass in total of the resin component and the radical polymerizable unsaturated monomer.

As shown in Table 4, the resin compositions of Examples 9 and 11 had a gelling time of 30 minutes or more and a minimum curing time of 130 minutes or less, and were found to be excellent in workability. In addition, the resin compositions of Examples 9 and 11 had a maximum heat generation temperature of 60 ° C. or higher, and were found to have excellent curability.
From the results in Tables 1 and 4, it was confirmed that the resin compositions of Examples 9 and 11 had excellent high-temperature stability at 80 ° C and good room-temperature curability.

Claims (13)

A resin component containing one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, and a vinyl ester resin;
A radically polymerizable unsaturated monomer,
A resin composition comprising a nitroso compound.   The resin composition according to claim 1, wherein the nitroso compound is one or more selected from N-nitroso-N-methylaniline, N-nitrosophenylhydroxylamine aluminum salt, and N-nitroso-N-cyclohexylaniline. object.   3. The resin composition according to claim 1, wherein the resin composition contains 0.005 to 5.0 parts by mass of the nitroso compound based on 100 parts by mass of the resin component. 4.   The resin composition according to any one of claims 1 to 3, wherein the resin component comprises a urethane (meth) acrylate resin and a vinyl ester resin.   The resin composition according to claim 4, wherein the resin component contains 10 to 80% by mass of a urethane (meth) acrylate resin.   The resin composition according to any one of claims 1 to 3, wherein the resin component comprises an unsaturated polyester resin and a vinyl ester resin.   The resin composition according to claim 6, wherein the resin component contains 5 to 80% by mass of an unsaturated polyester resin.   The resin composition according to any one of claims 1 to 3, wherein the resin component comprises a urethane (meth) acrylate resin, an unsaturated polyester resin, and a vinyl ester resin.   The resin composition according to any one of claims 1 to 8, wherein the resin component contains 20 to 95% by mass of a vinyl ester resin.   The resin composition according to any one of claims 1 to 9, further comprising a polymerization inhibitor.   The resin composition according to claim 10, wherein the polymerization inhibitor is trimethylhydroquinone.   A step of producing a mixture of one or both of a urethane (meth) acrylate resin and an unsaturated polyester resin, a resin component containing a vinyl ester resin, a radically polymerizable unsaturated monomer, and a nitroso compound. A method for producing a resin composition characterized by the following.   The method for producing a resin composition according to claim 12, wherein 0.005 to 5.0 parts by mass of the nitroso compound is mixed with 100 parts by mass of the resin component.