JP2016108467A - Method for producing resin composition, resin composition, curable resin composition, cured product, prepreg, and fiber-reinforced plastic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composition having excellent storage stability while maintaining high speed curability.SOLUTION: A method for producing a resin composition includes step 1 of blending (A) a compound having at least one thiirane ring with (B) an ester compound, and step 2 of heating them at 50°C or more after the step 1.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a resin composition, a resin composition, a curable resin composition, a cured product, a prepreg, and a fiber reinforced plastic.

Compared with epoxy resin and other oxirane ring-containing resin compositions, the resin composition containing a thiirane ring-containing compound can be cured at a high speed, which improves productivity and saves energy in manufacturing processes. It is known as a useful resin composition.
However, a compound containing a thiirane ring has a problem in storage stability, and it is difficult to industrially manufacture a product having a stable quality, so that improvement in storage stability is a major issue.

As a means for improving the storage stability of a compound containing a thiirane ring, a method of improving the storage stability by adding a storage stabilizer to a compound containing a thiirane ring such as an episulfide resin has been attempted.
For example, Patent Document 1 proposes a method of blending a phosphite ester or a borate ester with an episulfide resin.
Patent Document 2 proposes a method of blending a phosphite with a compound containing a thiirane ring.

International Publication No. 2010/035459 JP 2001-011183 A

However, in the case of the methods described in Patent Documents 1 and 2, there is still a problem that a sufficient storage stabilization effect cannot be obtained yet and it is difficult to industrially manufacture a product with stable quality. Yes.
In addition, when a storage stabilizer is blended, there is a problem of inducing undesirable phenomena such as promoting crystallization and discoloration of the resin.

  In view of the above-described problems of the prior art, an object of the present invention is to provide a method for producing a resin composition having excellent storage stability while maintaining high-speed curability.

As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have blended a predetermined compound with a compound (A) having at least one thiirane ring as the main agent, and a predetermined treatment. As a result, it was found that a resin composition excellent in storage stability while maintaining high-speed curability can be produced, and the present invention has been completed.
That is, the present invention is as follows.

[1]
(Step 1): (A) a step of blending (B) an ester compound with a compound having at least one thiirane ring;
(Step 2): After the (Step 1), a step of performing heat treatment at 50 ° C. or higher,
Having
A method for producing a resin composition.
[2]
In the compound (A) having at least one thiirane ring,
The method for producing a resin composition according to [1] above, wherein a compound having at least one oxirane ring is contained.
[3]
(A) the compound having at least one thiirane ring,
The manufacturing method of the resin composition as described in said [1] or [2] which has a polyphenol skeleton.
[4]
The method for producing a resin composition according to any one of [1] to [3], wherein the compound (A) having at least one thiirane ring has a S conversion ratio of 5% or more.
[5]
The method for producing a resin composition according to any one of [1] to [4], wherein the (B) ester compound is an inorganic acid ester compound.
[6]
The resin composition according to any one of [1] to [5], wherein the (B) ester compound is at least one compound selected from the group consisting of a phosphite ester or a borate ester. Manufacturing method.
[7]
The method for producing a resin composition according to [6], wherein the (B) ester compound has an aromatic ring.
[8]
The method for producing a resin composition according to [6] or [7], wherein the (B) ester compound has an alkyl group having 4 or more carbon atoms.
[9]
With respect to 100 parts by mass of the compound (A) having at least one thiirane ring,
The blending amount of the (B) ester compound is 0.1 to 5 parts by mass.
The method for producing a resin composition according to any one of [1] to [8].
[10]
The method for producing a resin composition according to any one of [1] to [9], wherein the temperature of the heat treatment in (Step 2) is 80 to 120 ° C.
[11]
A resin composition obtained by the method for producing a resin composition according to any one of [1] to [10],
A resin composition having a viscosity at 25 ° C. of 50 Pa · s or less.
[12]
The resin composition according to [11], wherein the storage stability index β is 5 or less.
[13]
The resin composition according to [11] or [12] above, wherein the haze after storage at 25 ° C for 30 days is 50% or less.
[14]
The resin composition according to any one of [11] to [13], wherein the haze after storage at 60 ° C for 7 days is 50% or less.
[15]
The resin composition according to any one of [11] to [14];
(C) a curing agent;
A curable resin composition.
[16]
The curable resin composition according to [15], wherein the (C) curing agent is a latent curing agent.
[17]
The curable resin composition according to [15] or [16], wherein the (C) curing agent is a microcapsule-type latent curing agent.
[18]
The curable resin composition according to any one of [15] to [17], wherein the (C) curing agent is an imidazole compound-containing microcapsule type latent curing agent having a core and a shell.
[19]
Curable resin composition as described in any one of said [15] thru | or [18] whose gel time in 150 degreeC is 60 second or less.
[20]
Hardened | cured material obtained by thermosetting the curable resin composition as described in any one of said [15] thru | or [19].
[21]
The curable resin composition according to any one of [15] to [19],
Reinforcing fibers,
Comprising a prepreg.
[22]
The curable resin composition according to any one of [15] to [19],
Reinforcing fibers,
Comprising
A prepreg having a multi-layer structure.
[23]
The curable resin composition according to any one of [15] to [19],
Reinforcing fibers,
Comprising
A fiber-reinforced plastic that has been cured.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the resin composition which is excellent in storage stability can be provided, maintaining high-speed curability.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist.

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is as follows:
(Step 1): (A) a step of blending (B) an ester compound with a compound having at least one thiirane ring;
(Step 2): After the (Step 1), a step of performing heat treatment at 50 ° C. or higher,
Have

((A) Compound having at least one thiirane ring)
In the method for producing a resin composition of the present embodiment, (A) a compound having at least one thiirane ring is used.
In addition, “a compound having at least one thiirane ring” means that “a compound having at least one thiirane ring” is included as an essential component, and a compound having no thiirane ring may also be included. To do.
The “compound having at least one thiirane ring” is not particularly limited, and may further have an oxirane ring.
In addition, (A) the compound having at least one thiirane ring is obtained by converting a part or all of the oxirane ring of the raw material epoxy compound into a thiirane ring, but remains without being converted into a thiirane ring. “Compounds having no thiirane ring and having an oxirane ring” may be included.
(A) A compound having at least one thiirane ring may be used alone or in combination.

(A) The viscosity at 25 ° C. of the compound having at least one thiirane ring is not particularly limited, but is preferably 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa. · S or less, still more preferably 50 Pa · s or less, and even more preferably 20 Pa · s or less.
When the viscosity at 25 ° C. is 1000 Pa · s or less, good fluidity is obtained, and compatibility with other raw materials becomes good.
(A) The viscosity at 25 ° C. of a compound having at least one thiirane ring can be measured by the method described in the examples described later.

The compound (A) having at least one thiirane ring is composed of a basic skeleton composed of an aromatic skeleton, an alicyclic skeleton, an aliphatic skeleton, and the like, and a substituent containing a thiirane ring portion.
The structure of the substituent containing the thiirane ring in the compound (A) having at least one thiirane ring will be described below.
The thiirane ring moiety is represented by the following formula (I).
The thiirane ring moiety represented by the following formula (I) is a terminal thiirane ring in which any carbon is unsubstituted except that a group connected to the basic skeleton is bonded to one carbon atom.

The group for linking the basic skeleton and the thiirane ring moiety is not limited to the following. Examples thereof include 1 to 10 divalent acyclic saturated hydrocarbon groups, ether bonds, ester bonds, and amide bonds, and a structure in which two to three of these are combined.
A preferred example of the substituent containing the thiirane ring moiety is shown in the following formula (II).
Among these, 2,3-epithiopropoxy group, 3,4-epithiobutoxy group, and 2,3-epithiopropoxymethyl group are particularly preferable from the viewpoint of reactivity and ease of production.
When two or more substituents containing the thiirane ring moiety are present in the molecule, they may have the same structure or different structures.
2-10 are preferable and, as for the number of the substituents containing the said thiirane ring part, 2-4 are more preferable.

The basic skeleton of the “(A) compound having at least one thiirane ring” is not particularly limited. For example, it preferably has an aromatic skeleton or an alicyclic skeleton, and has an aromatic skeleton. Is more preferable.
When the basic skeleton has an aromatic skeleton or an alicyclic skeleton, the position at which the substituent containing the thiirane ring portion is bonded to the basic skeleton includes the aromatic skeleton or the alicyclic skeleton included in the structure of the basic skeleton. It is preferably any one of the carbon atoms constituting
When the molecule of “(A) compound having at least one thiirane ring” has a plurality of substituents containing a thiirane ring moiety, the substituent containing the thiirane ring moiety is bonded to a separate carbon atom. In addition, when there are two or more aromatic skeletons or alicyclic skeletons, it is preferable that they are bonded to separate aromatic skeletons or alicyclic skeletons.

Furthermore, in addition to the substituent containing a thiirane ring part, other substituents may be bonded to the basic skeleton.
The other substituent is not limited to the following, but for example, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms; 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Examples include alkoxy groups; substituents containing halogen elements such as Br and F, and the like, and methyl, ethyl, methoxy, and ethoxy groups are particularly preferable.

When the basic skeleton has a polyphenol skeleton or its nuclear hydrogenated skeleton, the repeating unit (n in the following formula (VI) and the following formula (VIII)) is not particularly limited, but preferably It is less than 20, more preferably 0.001 to 5, and still more preferably 0.01 to 2.
When the basic skeleton has a polyphenol skeleton or a nuclear hydrogenated skeleton, the repeating unit n of the basic skeleton is 0.001 or more, which is used when producing a prepreg or fiber reinforced plastic described later. The reactivity with the fiber is good, and good fluidity is obtained when the repeating unit n is 20 or less.
In view of the balance between the reactivity with the above-described reinforcing fibers and the fluidity, the repeating unit n is particularly preferably 0.01 to 2.

(A) Examples of the compound having at least one thiirane ring include monofunctional episulfide compounds; polyfunctional episulfide compounds; aromatic episulfide compounds such as polyphenol episulfide compounds and novolak episulfide compounds; and nuclear hydrogen of aromatic episulfide compounds Alicyclic episulfide compound; heterocyclic episulfide compound; thioglycidyl ester episulfide compound; thioglycidylamine episulfide compound; episulfide compound obtained by thioglycidylation of halogenated phenols; A silicone compound having a thiirane ring in the molecule; and a heteropolymerizable functional group-containing episulfide compound.
These may be used alone or in combination.

<Monofunctional episulfide compound>
The monofunctional episulfide compound is not particularly limited as long as it is a compound having one thiirane ring, and is not limited to the following. For example, ethylene sulfide, propylene sulfide, 1-butene sulfide, 2- Butene sulfide, butadiene sulfide, butadiene dithioepoxide, cyclobutene sulfide, 1,3-cyclobutadiene dithioepoxide, 1-pentene sulfide, 2-pentene sulfide, 1,3-pentadiene dithioepoxide, 1,4-pentadiene dithioepoxide, 2 -Methyl-2-butene sulfide, 2-methyl-3-butene sulfide, cyclopentene sulfide, 1,3-cyclopentadiene dithioepoxide, 1-methyl-cyclobutene sulfide, 3-methyl-1-cyclobute Sulfide, 1-hexene sulfide, 2-hexene sulfide, 3-hexene sulfide, 1,3-hexadiene dithioepoxide, 1,4-hexadiene dithioepoxide, 1,5-hexadiene dithioepoxide, 1,3,5-hexatrientthio Epoxide, cyclohexene sulfide, 1,3-cyclohexadiene dithioepoxide, 1,3,5-cyclohexatrienethioepoxide, 1-methyl-cyclopentene sulfide, 3-methyl-cyclopentene sulfide, 1-methyl-1,3-cyclopentadiene Dithioepoxide, 2-methyl-1,3-cyclopentadiene dithioepoxide, 5-methyl-1,3-cyclopentadiene dithioepoxide, 3,4-dimethyl-cyclobutene sulfide, 2,3-dimethyl Ru-cyclobutene sulfide, 1,2-dimethyl-cyclobutene sulfide, 1,2-dimethyl-1,3-cyclobutadiene dithioepoxide, 2,3-dimethyl-1,3-cyclobutadiene dithioepoxide, 3,3- Dimethyl-1,2-thioepoxybutane, 1-heptene sulfide, 2-heptene sulfide, 3-heptene sulfide, 1,3-heptadiene dithioepoxide, 1,4-heptadiene dithioepoxide, 1,5- Heptadiene dithioepoxide, 1,5-heptadiene dithioepoxide, 1,6-heptadiene dithioepoxide, 1,3,5-heptatrientioepoxide, 1,3,6-heptatrienethioepoxide, 1,4,6 -Heptatrientiothiopoxide, cycloheptene sulfide, 1- Methyl-cyclohexene sulfide, 3-methyl-cyclohexene sulfide, 4-methyl-cyclohexene sulfide, 1-methyl-1,3-cyclohexadiene dithioepoxide, 1-methyl-1,4-hexadiene dithioepoxide, 1-methyl-1, 3,5-hexatrienethioepoxide, 1,2-thioepoxy-5-hexene, 1,2-thioepoxy-4-vinylcyclohexene, 2-norbornene sulfide, 7-methyl-2-norbornene sulfide, 7,7-dimethyl- 2-norbornene sulfide, 2-methyl-2-norbornene sulfide, 2,3-dimethyl-2-norbornene sulfide, 2,7-dimethyl-2-norbornene sulfide, 2,7,7-trimethyl-2-norbornene sulfide, 2 , 3-chi Epoxy-bicyclo [2,2,2] octane, 2,3-thioepoxy-2-methyl-bicyclo [2,2,2] octane, 2,3-thioepoxy-2,3-dimethyl-bicyclo [2,2, 2] octane, 2,3-thioepoxy-2,5-dimethyl-bicyclo [2,2,2] octane, 2,3-thioepoxy-2,6-dimethyl-bicyclo [2,2,2] octane, 2, 3-thioepoxy-2,3,5-trimethyl-bicyclo [2,2,2] octane, 2,3-thioepoxy-2,5,6-trimethyl-bicyclo [2,2,2] octane, 2,3- Thioepoxy-2,3,5,6-tetramethyl-bicyclo [2,2,2] octane, dioctyl thioepoxyhexahydrophthalate, di-2-ethylhexyl thioepoxyhexahydrophthalate, Thibene sulfide, phenylthioglycidyl ether, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-thioepoxypropane, pinene sulfide, isoprene monosulfide, 1,2-thioepoxyethylbenzene, naphthylthioglycidyl Ether, 3- (2-biphenyloxy) -1,2-thioepoxypropane, allyl thioglycidyl ether, 1,1-diphenyl-ethylene sulfide, thioglycidyl (meth) acrylate, thioglycidyl butyrate, iodomethyl thiirane, 4- (2,3-thioepoxypropyl) morpholine, thioglycidyl methyl ether, 2-phenyl-propylene sulfide, 2,3-thioepoxypropyl-furfuryl ether, 2,3,4,5,6-pentafluorostyrene Fido, ethyl-3-phenylthioglycidate, limonene sulfide, thioepoxysuccinic acid, 3-thioglycidoxypropyltrimethoxysilane, (3-thioglycidoxypropyl) pentamethyldisiloxane, 3-thioglycid Xylpropyl (methyl) dimethoxysilane, 3-thioglycidoxypropyl (methyl) diethoxysilane, 3-thioglycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyl (methyl) ) Dimethoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-thioepoxypropyl (methyl) dimethoxysilane, 2,3-thioepoxypropyl (phenyl) dimethoxysilane, 3 -Thioglycidoxypropyltrime Xysilane, 3-thioglycidoxypropyltriethoxysilane, 3-thioglycidoxypropyltributoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-thioepoxycyclohexyl) ) Ethyltriethoxysilane, 2,3-thioepoxypropyltrimethoxysilane, 2,3-thioepoxypropyltriethoxysilane, and the like.

Among the above, the viewpoint that the vapor pressure in the standard state is high, the handling is easy, the stability of the resin composition of the present embodiment tends to be further improved, and the side reaction at the time of polymerization tends to be further suppressed. Therefore, the monofunctional episulfide compound is preferably at least one compound selected from the following group.
That is, for example, ethylene sulfide, propylene sulfide, 1-butene sulfide, 2-butene sulfide, butadiene sulfide, butadiene dithioepoxide, cyclobutene sulfide, 1,3-cyclobutadiene dithioepoxide, 1-pentene sulfide, 2-pentene sulfide, 1,3-pentadiene dithioepoxide, 1,4-pentadiene dithioepoxide, 2-methyl-2-butene sulfide, 2-methyl-3-butene sulfide, cyclopentene sulfide, 1,3-cyclopentadiene dithioepoxide, 1-methyl- Cyclobutene sulfide, 3-methyl-1-cyclobutene sulfide, 1-hexene sulfide, 2-hexene sulfide, 3-hexene sulfide, 1,3-hexadiene dithioepoxide 1,4-hexadiene dithioepoxide, 1,5-hexadiene dithioepoxide, 1,3,5-hexatriene thioepoxide, cyclohexene sulfide, 1,3-cyclohexadiene dithioepoxide, 1,3,5-cyclohexatriene thioepoxide 1-methyl-cyclopentene sulfide, 3-methyl-cyclopentene sulfide, 1-methyl-1,3-cyclopentadiene dithioepoxide, 2-methyl-1,3-cyclopentadiene dithioepoxide, 5-methyl-1,3-cyclo Pentadiene dithioepoxide, 3,4-dimethyl-cyclobutene sulfide, 2,3-dimethyl-cyclobutene sulfide, 1,2-dimethyl-cyclobutene sulfide, 1,2-dimethyl-1,3-cyclobutadiene dithioe Xoxide, 2,3-dimethyl-1,3-cyclobutadienedithioepoxide, 3,3-dimethyl-1,2-thioepoxybutane, 1-heptene sulfide, 2-heptene sulfide, 3-heptene sulfide, 1 , 3-heptadiene dithioepoxide, 1,4-heptadiene dithioepoxide, 1,5-heptadiene dithioepoxide, 1,5-heptadiene dithioepoxide, 1,6-heptadiene dithioepoxide, 1,3,5- Heptatrienethioepoxide, 1,3,6-heptatrienethioepoxide, 1,4,6-heptatrienethioepoxide, cycloheptene sulfide, 1-methyl-cyclohexene sulfide, 3-methyl-cyclohexene sulfide, 4-methyl- Cyclohexene sulfide, 1-methyl- 1,3-cyclohexadiene dithioepoxide, 1-methyl-1,4-hexadiene dithioepoxide, 1-methyl-1,3,5-hexatrienethioepoxide, 1,2-thioepoxy-5-hexene, 1,2- Thioepoxy-4-vinylcyclohexene, dioctyl thioepoxyhexahydrophthalate, di-2-ethylhexyl thioepoxyhexahydrophthalate, stibene sulfide, phenylthioglycidyl ether, 3- (2,2,3,3-tetrafluoropropoxy ) -1,2-thioepoxypropane, pinene sulfide, isoprene monosulfide, 1,2-thioepoxyethylbenzene, naphthylthioglycidyl ether, 3- (2-biphenyloxy) -1,2-thioepoxypropane, allylthioglycidyl ether 1,1-diphenyl-ethylene sulfide oxide, thioglycidyl (meth) acrylate, thioglycidyl butyrate, iodomethyl thiirane, 4- (2,3-thioepoxypropyl) morpholine, thioglycidyl methyl ether, 2-phenyl-propylene Sulfide, 2,3-thioepoxypropyl-furfuryl ether, 2,3,4,5,6-pentafluorostyrene sulfide, ethyl-3-phenylthioglycidate, limonene sulfide, thioepoxysuccinic acid, 3-thioglycol Sidoxypropyltrimethoxysilane, (3-thioglycidoxypropyl) pentamethyldisiloxane, 3-thioglycidoxypropyl (methyl) dimethoxysilane, 3-thioglycidoxypropyl (methyl) diethoxysilane, 3- Thioguri Doxypropyl (methyl) dibutoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-thio Epoxypropyl (methyl) dimethoxysilane, 2,3-thioepoxypropyl (phenyl) dimethoxysilane, 3-thioglycidoxypropyltrimethoxysilane, 3-thioglycidoxypropyltriethoxysilane, 3-thioglycidoxypropyl Tributoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyltriethoxysilane, 2,3-thioepoxypropyltrimethoxysilane and 2,3 -Thioepoxy propi Lutriethoxysilane is preferred.

More preferably, the monofunctional episulfide compound includes at least one compound selected from the following group.
That is, propylene sulfide, 1-butene sulfide, 2-butene sulfide, butadiene sulfide, butadiene dithioepoxide, 1-pentene sulfide, 2-pentene sulfide, 1,3-pentadiene dithioepoxide, 1,4-pentadiene dithioepoxide, 2- Methyl-2-butene sulfide, 2-methyl-3-butene sulfide, cyclopentene sulfide, 1-methyl-cyclobutene sulfide, 3-methyl-1-cyclobutene sulfide, 1-hexene sulfide, 2-hexene sulfide, 3-hexene Sulfide, 1,3-hexadiene dithioepoxide, 1,4-hexadiene dithioepoxide, 1,5-hexadiene dithioepoxide, 1,3,5-hexatrienethioepoxide, cyclohexene Rufide, 1,3-cyclohexadiene dithioepoxide, 1-methyl-cyclopentene sulfide, 3-methyl-cyclopentene sulfide, 2-heptene sulfide, 3-heptene sulfide, 1,3-heptadiene dithioepoxide, 1,4- Heptadiene dithioepoxide, 1,5-heptadiene dithioepoxide, 1,5-heptadiene dithioepoxide, 1,6-heptadiene dithioepoxide, 1-methyl-cyclohexene sulfide, 3-methyl-cyclohexene sulfide, 4-methyl- Cyclohexene sulfide, 1,2-thioepoxy-5-hexene, 1,2-thioepoxy-4-vinylcyclohexene, stibene sulfide, phenylthioglycidyl ether, 3- (2,2,3,3-tetrafluoropropoxy -1,2-thioepoxypropane, pinene sulfide, isoprene monosulfide, 1,2-thioepoxyethylbenzene, naphthylthioglycidyl ether, 3- (2-biphenyloxy) -1,2-thioepoxypropane, allylthioglycidyl ether, 1,1-diphenyl-ethylene sulfide, thioglycidyl (meth) acrylate, thioglycidyl butyrate, iodomethyl thiirane, 4- (2,3-thioepoxypropyl) morpholine, thioglycidyl methyl ether, 2-phenyl-propylene sulfide 2,3-thioepoxypropyl-furfuryl ether, 2,3,4,5,6-pentafluorostyrene sulfide, ethyl-3-phenylthioglycidate, limonene sulfide, thioepoxysuccinic acid, 3-thio Glycidoxypropyltrimethoxysilane, (3-thioglycidoxypropyl) pentamethyldisiloxane, 3-thioglycidoxypropyl (methyl) dimethoxysilane, 3-thioglycidoxypropyl (methyl) diethoxysilane, 3 -Thioglycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-thioepoxypropyl (methyl) dimethoxysilane, 2,3-thioepoxypropyl (phenyl) dimethoxysilane, 3-thioglycidoxypropyltrimethoxysilane, 3-thioglycidoxypropyltriethoxysilane, 3- Thioglycidoxypropyl tribute Sisilane, 2- (3,4-thioepoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-thioepoxycyclohexyl) ethyltriethoxysilane, 2,3-thioepoxypropyltrimethoxysilane, and 2,3- An example is thioepoxypropyltriethoxysilane.

<Polyfunctional episulfide compound>
The polyfunctional episulfide compound is an episulfide having at least one thiirane ring in the molecule, two or more sums of thiirane rings and oxirane rings, and having a plurality of aromatic skeletons and alicyclic skeletons in the molecule. Compounds.
The group connecting the plurality of aromatic skeletons or alicyclic skeletons in the molecule is not limited to the following, but for example, a divalent acyclic saturated hydrocarbon group having 1 to 10 carbon atoms. , A C1-C10 divalent acyclic saturated hydrocarbon group substituted with a hydroxyl group, an ether bond, an ester bond, an amide bond, and a structure in which two to three of these are combined.
Among these, preferred examples include a structure represented by the following formula (III) such as a methylene group and a dimethylmethylene group.

Moreover, in the site | part which connects several aromatic frame | skeleton or alicyclic skeleton, carbon on one frame | skeleton and the carbon on the other frame | skeleton may be directly connected by the covalent bond.
Examples in which a plurality of aromatic skeletons and alicyclic skeletons are connected are shown in the following formulas (IV) and (V).

<Aromatic episulfide compounds such as polyphenol type episulfide compounds and novolak type episulfide compounds>
The aromatic episulfide compound is not particularly limited as long as it is a compound having an aromatic skeleton and having at least one thiirane ring. In addition to the thiirane ring, a compound having an oxirane ring is also included.
These may be used alone or in combination of two or more.
The type of the aromatic episulfide compound is not particularly limited, but is excellent in the physical properties of the cured product and easy to obtain the raw materials. Therefore, the polyphenol type episulfide compound, the novolak type episulfide compound, and the halogenated phenol described later are used. Episulfide compounds having a skeleton in the skeleton are preferred, and polyphenol type episulfide compounds are more preferred.

[(1) Polyphenol type episulfide compound]
The polyphenol type episulfide compound which is an example of the aromatic episulfide compound is a polyfunctional episulfide compound whose aromatic skeleton is a phenol skeleton or a polyphenol skeleton. The polyphenol type episulfide compound is not particularly limited, and a bisphenol type episulfide compound is preferable because it is easy to obtain raw materials.
Examples of the polyphenol type episulfide compound include, but are not limited to, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, and dimethyl. Bisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1 -Bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6- t-butylphenol), trishydroxy Phenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di (4-hydroxyphenyl) fluorene And thioglycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.
Among these, a thioglycidyl etherified product of a phenol having a bisphenol A skeleton or a bisphenol F skeleton is preferable from the viewpoint that the production is easy, the production cost of the resin composition of the present embodiment is suppressed, and the cost is excellent.
The repeating unit of the aromatic episulfide compound (n in the representative example of the following (VI)) is not particularly limited, but is preferably less than 50, more preferably 0.001 to 5, still more preferably 0.01 to 2.
When the repeating unit n is 0.001 or more, the reactivity in curing is good, and when it is less than 50, practically sufficient fluidity is obtained.
From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit n of the aromatic episulfide compound is more preferably 0.01 to 2.
A typical example of the polyphenol type episulfide compound is shown in the following (VI).

[(2) Novolac-type episulfide compounds]
The novolak-type episulfide compound is not particularly limited as long as it has a skeleton of a novolak compound and has at least one thiirane ring, and includes a compound having an oxirane ring in addition to the thiirane ring.
These may be used alone or in combination of two or more.
Examples of the novolak type episulfide compound include, but are not limited to, various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols. Thioglycidyl ethers of various novolac compounds such as novolak compounds, xylylene skeleton-containing phenol novolak compounds, dicyclopentadiene skeleton-containing phenol novolak compounds, biphenyl skeleton-containing phenol novolak compounds, and fluorene skeleton-containing phenol novolak compounds. Can be mentioned.
Among these, a thioglycidyl etherified product of a novolak compound using phenol or cresol as a raw material is preferable from the viewpoint of easy production, reduced production cost of the resin composition of the present embodiment, and excellent economic efficiency.
A typical example of the novolak type episulfide compound is shown in the following formula (VII).

[(3) Episulfide compounds having halogenated phenols in the skeleton]
The episulfide compound having a halogenated phenol as a skeleton is not particularly limited as long as it is a compound having a skeleton of a halogenated phenol and having at least one thiirane ring. For example, halogenated phenols And an episulfide compound obtained by thioglycidylation.
Specifically, halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A are thioglycidyl ethers. Episulfide compounds and the like.

<Nuclear hydride of aromatic episulfide compound>
The nuclear hydride of an aromatic episulfide compound is not particularly limited as long as it has an alicyclic skeleton and has at least one thiirane ring. In addition to a thiirane ring, a compound having an oxirane ring included.
These may be used alone or in combination of two or more.

A method for producing a nuclear hydride of an aromatic episulfide compound is not particularly limited, and examples thereof include a method for thialating a nuclear hydride of an aromatic epoxy compound, a method for nuclear hydrogenation of an aromatic episulfide compound, and the like. .
A preferred alicyclic skeleton of the nuclear hydride of an aromatic episulfide compound includes a skeleton obtained by nuclear hydrogenation of polyphenol.
Although not limited to the following, for example, phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols (phenol, cresols, ethylphenols, butylphenols, octylphenols) , Bisphenol A, bisphenol F, bisphenol S, naphthols, and the like) and those obtained by nuclear hydrogenation of novolak resins.
The nuclear hydride of the aromatic episulfide compound is not particularly limited. For example, a thioglycidyl etherified product of a phenol compound (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols ( Phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and the hydrogen of thioglycidyl etherified products of novolak compounds A compound.

The repeating unit of the nuclear hydride of the aromatic episulfide compound (n in the representative example of (VIII) below) is not particularly limited, but is preferably less than 50, more preferably 0.001 to 5, more preferably 0.01-2.
When the repeating unit is 0.001 or more, the reactivity in curing is good, and when it is less than 50, practically good fluidity is obtained.
From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit is more preferably 0.01 to 2.
A typical example of a nuclear hydride of an aromatic episulfide compound is shown below.

<Alicyclic episulfide compound>
The alicyclic episulfide compound is an episulfide compound having an alicyclic episulfide structure, and is not particularly limited as long as it is a compound having at least one thiirane ring, and has an oxirane ring in addition to the thiirane ring. Also included are compounds.
These may be used alone or in combination of two or more.
For example, an episulfide compound having a cyclohexene sulfide group, a tricyclodecene sulfide group, a cyclopentene sulfide group, or the like can be given.

Examples of the alicyclic episulfide compound include, but are not limited to, for example, 3,4-thioepoxycyclohexenylmethyl-3 ′, 4′-thioepoxycyclohexenecarboxylate, 3,4-thioepoxycyclohexylmethyl. -3,4-thioepoxycyclohexanecarboxylate, 3,4-thioepoxycyclohexyloctyl-3,4-thioepoxycyclohexanecarboxylate, 2- (3,4-thioepoxycyclohexyl-5,5-spiro-3,4 -Thioepoxy) cyclohexane-meta-dioxane, bis (3,4-thioepoxycyclohexylmethyl) adipate, vinylcyclohexene disulfide, bis (3,4-thioepoxy-6-methylcyclohexylmethyl) adipate, 3,4-thioepoxy- -Methylcyclohexyl-3,4-thioepoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-thioepoxycyclohexane), dicyclopentadiene dithioepoxide, ethylene glycol di (3,4-thioepoxycyclohexylmethyl) ether, ethylene Bis (3,4-thioepoxycyclohexanecarboxylate) and 1,2,8,9-dithioepoxy limonene. Other polyfunctional alicyclic episulfide compounds include 2,2-bis (hydroxymethyl) -1-butanol, 1,2-epoxy-4- (2-thiylyl) cyclohexene or 1,2-thioepoxy-4- ( 2-thiylyl) cyclohexene adduct and the like.
A typical example of the alicyclic episulfide compound is shown in the following formula (IX).

<Heterocyclic episulfide compound>
Examples of the heterocyclic episulfide compound include, but are not limited to, a heterocyclic episulfide compound having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

<Thioglycidyl ester-based episulfide compound>
Examples of thioglycidyl ester-based episulfide compounds include, but are not limited to, episulfide compounds derived from carboxylic acid compounds such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester. .

<Thioglycidylamine-based episulfide compound>
Examples of thioglycidylamine-based episulfide compounds include, but are not limited to, thioglycidylation of amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, and diaminomethylbenzene derivatives. Episulfide compounds.

<Episulfide compounds obtained by thioglycidylation of halogenated phenols>
The compounds obtained by thioglycidylating halogenated phenols are not limited to the following. For example, bromophenol, chlorophenol, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak. And episulfide compounds obtained by thioglycidyl etherification of halogenated phenols such as brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A.

<(Sulfur-containing) polyfunctional aliphatic episulfide compound>
Examples of (sulfur-containing) polyfunctional aliphatic episulfide compounds include, but are not limited to, 1,1-bis (epithioethyl) methane, 1- (epithioethyl) -1- (β-epithiopropyl), for example. Methane, 1,1-bis (β-epithiopropyl) methane, 1- (epithioethyl) -1- (β-epithiopropyl) ethane, 1,2-bis (β-epithiopropylethane), 1- (epithioethyl) ) -3- (β-epithiopropyl) butane, 1,3-bis (β-epithiopropyl) propane, 1- (epithioethyl) -4- (β-epithiopropyl) pentane, 1,4-bis ( β-epithiopropyl) butane, 1- (epithioethyl) -5- (β-epithiopropyl) hexane, 1- (epithioethyl) -2- (γ-epithiobutylthio) ethane, 1 (Epithioethyl) -2- [2- (γ-epithiobutylthio) ethylthio] ethane, tetrakis (β-epithiopropyl) methane, 1,1,1-tris (β-epithiopropyl) propane, 1,3 -Bis (β-epithiopropyl) -1- (β-epithiopropyl) -2-thiapropane, 1,5-bis (β-epithiopropyl) -2,4-bis (β-epithiopropyl)- 3-thiapentane, 1,3 or 1,4-bis (epithioethyl) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyl) cyclohexane, 2,5-bis (epithioethyl) -1,4-dithiane 2,5-bis (β-epithiopropyl) -1,4-dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 2,2-bis [4- (epithioethyl) cycl Cyclohexyl] propane, 2,2-bis [4- (β-epithiopropyl) cyclohexyl] propane, bis [4- (epithioethyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) cyclohexyl] sulfide, bis [4- (epithioethyl) cyclohexyl] sulfide, bis (β-epithiopropyl) ether, bis (β-epithiopropyloxy) methane, 1,2- Bis (β-epithiopropyloxy) ethane, 1,3-bis (β-epithiopropyloxy) propane, 1,2-bis (β-epithiopropyloxy) propane, 1- (β-epithiopropyloxy) ) -2- (β-epithiopropyloxymethyl) propane, 1,4-bis (β-epithiopropyloxy) Xyl) butane, 1,3-bis (β-epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β-epithiopropyloxymethyl) butane, 1,5-bis (β -Epithiopropyloxy) pentane, 1- (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) pentane, 1,6-bis (β-epithiopropyloxy) hexane, 1- ( β-epithiopropyloxy) -5- (β-epithiopropyloxymethyl) hexane, 1- (β-epithiopropyloxy) -2-[(2-β-epithiopropyloxyethyl) oxy] ethane, 1- (β-epithiopropyloxy) -2-[[2- (2-β-epithiopropyloxyethyl) oxyethyl] oxy] ethane, tetrakis (β-epithiopropyloxy) Cymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, 1,5-bis (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) -3- Thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4-bis (β-epithiopropyloxymethyl) -3-thiapentane; 1- (β-epithiopropyloxy) -2,2- Bis (β-epithiopropyloxymethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3-thiahexane, 1,8 -Bis (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,5- (Β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) -3,6- Dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyl) Oxy) -2,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropyloxy) -5- (β-epithiopropyloxymethyl)- 5-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropyloxy) -5,6-bis [(2-β-epithio (Lopyloxyethyl) oxy] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropyloxy) -4,8-bis (β-epithiopropyloxymethyl) -3,6,9 -Trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis ( β-epithiopropyloxy) -5,7-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) ) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,3 or 1,4-bis (β-epithiopropyloxy) cyclohexane, 1,3 or 1, 4-bis (β-epithiopropyloxymethyl) cyclohexane, bis [4- (β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyloxy) cyclohexyl] propane, Bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2,5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyloxyethyl) Oxymethyl) -1,4-dithiane, bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) Methane, bis (β-epithiopropyldithio) methane, bis (β-epithiopropyldithio) ethane, bis (β- Pthiopropyldithioethyl) sulfide, bis (β-epithiopropyldithioethyl) disulfide, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithiopropyl) Thio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β -Epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) he Sun, 1- (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) ) Thio] ethane, 1- (β-epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethanetetrakis (β-epithiopropylthiomethyl) methane, Tetrakis (β-epithiopropyldithiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,2,3-tris (β-epithiopropyldithio) propane, 1,5 -Bis (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β- Pthiopropylthiomethyl) -3-thiapentane, 1,6-bis (β-epithiopropyldithiomethyl) -2- (β-epithiopropyldithioethylthio) -4-thiahexane, 1- (β-epithio) Propylthio) -2,2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis ( β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithio Propylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2 -Β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3 , 6,9-Trithiaundeca 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epi Thiopropylthio) -5,7-[(2-β-epithiopropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4, 7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (Β-epithiopropylthio) acetylmethyl] propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) Acetylmethyl] Lopan, 1,3 or 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-epi Thiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl)- 1,4-dithiane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epi Thiopropylthio) cyclohexyl] sulfide, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) si Rohekishiru] sulfide, and the like.

Among these, since the production is easy, the production cost of the resin composition of the present embodiment can be suppressed, and the economy is excellent. Therefore, the (sulfur-containing) polyfunctional aliphatic episulfide compound is selected from the following group: Preferably, at least one compound is used.
That is, for example, bis (β-epithiopropyloxy) methane, 1,2-bis (β-epithiopropyloxy) ethane, 1,3-bis (β-epithiopropyloxy) propane, 1,2-bis (Β-epithiopropyloxy) propane, 1- (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) propane, 1,4-bis (β-epithiopropyloxy) butane, , 3-bis (β-epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β-epithiopropyloxymethyl) butane, 1,6-bis (β-epithiopropyloxy) ) Hexane, 1- (β-epithiopropyloxy) -5- (β-epithiopropyloxymethyl) hexane, 1- (β-epithiopropyloxy) -2-[(2-β-et Thiopropyloxyethyl) oxy] ethane, 1- (β-epithiopropyloxy) -2-[[2- (2-β-epithiopropyloxyethyl) oxyethyl] oxy] ethane, tetrakis (β-epithiopropyl) Oxymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, 1- (β-epithiopropyloxy) -2,2-bis (β-epithiopropyloxymethyl) -4 -Thiahexane, 1,5,6-tris (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (β-epithiopropyloxy) -4 -(Β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,5-bis (β-epithio) (Lopyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8 -Bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2, 5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,3 or 1,4-bis (β-epithiopropyloxy) cyclohexane, 1,3 or 1,4-bis (β- Epithiopropyloxymethyl) cyclohexane, bis [4- (β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyloxy) cyclohexane Syl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide, 2,5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epi Thiopropyloxyethyloxymethyl) -1,4-dithiane, bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, bis (β-epi Thiopropyldithio) methane, bis (β-epithiopropyldithio) ethane, bis (β-epithiopropyldithioethyl) sulfide, bis (β-epithiopropyldithioethyl) disulfide, 1,2-bis (β-epi Thiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropyl) Ruthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithiopropylthio) butane, 1,3-bis (β -Epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,6-bis (β-epithiopropylthio) hexane, 1- ( β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β-epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethanetetrakis (β-epithiopropylthiomethyl) methane, tetrakis (β- Pthiopropyldithiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,2,3-tris (β-epithiopropyldithio) propane, 1,6-bis (β -Epithiopropyldithiomethyl) -2- (β-epithiopropyldithioethylthio) -4-thiahexane, 1- (β-epithiopropylthio) -2,2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl)- , 6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Propylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bis (β-epi Thiopropylthiomethyl) -3,6-dithiaoctane, tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthio) acetylmethyl] Propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane, 1,3 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-epithiopropylthiomethyl)- 1,4-dithiane, 2,5-bis (β-epithiopropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane, Bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] Sulfide, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfur Is included.

<Silicone compound having thiirane ring in the molecule>
The silicone compound having a thiirane ring in the molecule is not particularly limited, and may be selected from, for example, compounds represented by the following formula (X).
(R ₁₀ R ₁₁ R ₁₂ SiO _1/2 ) _a (R ₁₃ R ₁₄ SiO _2/2 ) _b (R ₁₅ SiO _3/2 ) _c (SiO _4/2 ) _d (formula X)
In the formula (X), a, b, c and d are numerical values satisfying a + b + c + d = 1.0, and 0 ≦ a / (a + b + c + d) ≦ 1, 0 ≦ b / (a + b + c + d) ≦ 1, 0 ≦ c / (a + b + c + d) ≦ 1 and 0 ≦ d / (a + b + c + d) <1.
At least one of R ₁₀ to R ₁₅ represents a group containing a thiirane ring, other R ₁₀ to R ₁₅ represents a linear or branched hydrocarbon group or the hydrocarbon having 1 to 8 carbon atoms The group represents a fluorinated group. These may be the same as or different from each other.

<Hexogenous polymerizable functional group-containing episulfide compound>
The heteropolymerizable functional group-containing episulfide compound is not particularly limited, and may be selected from, for example, compounds represented by the following formula (XI).

In the above formula (XI), R _{20 to} R ₂₂ represent a substituted or unsubstituted chain, branched or cyclic aliphatic or aromatic hydrocarbon group which may be thiated.
m, n, o and p each independently represent a number of 1 or more.
X represents a thiirane ring or a substituent containing a thiirane ring portion.
When Y represents a single type of polymerizable functional group, a thiirane ring or a substituent containing a thiirane ring portion, a lactone structure, a cyclic carbonate structure, and a sulfur-containing analog structure thereof, a cyclic acetal structure, and a sulfur-containing analog structure thereof, Selected from the group consisting of cyclic amine structure, cyclic imino ether structure, lactam structure, cyclic thiourea structure, cyclic phosphinate structure, cyclic phosphonite structure, cyclic phosphite structure, vinyl structure, allyl structure, (meth) acrylic structure, cycloalkane structure The structure is shown.
When Y represents a plurality of polymerizable functional groups, it represents at least two structures selected from the above group.

((A) Method for producing compound having at least one thiirane ring)
The method for producing a compound having (A) at least one thiirane ring contained in the resin composition of the present embodiment is a method capable of synthesizing a target compound (A) having at least one thiirane ring. There is no particular limitation.

(A) A preferable method for producing a compound having at least one thiirane ring includes a method of converting an oxirane ring into a thiirane ring using a sulfide by a method known to those skilled in the art using an epoxy compound as a raw material.
In addition, at this time, the compound which does not have a thiirane ring which remained without converting a part of oxirane rings into a thiirane ring may be contained.
(A) When producing a compound having at least one thiirane ring, the epoxy compound used as a raw material is not particularly limited as long as it is a compound having at least one oxirane ring. The compound etc. which are illustrated for a compound can be used as a raw material.
The epoxy compound as the raw material may be used alone or in combination of two or more.

  (A) The compound having at least one thiirane ring is obtained by converting a part or all of the oxirane ring of the raw material epoxy compound into a thiirane ring, but as described above, does not have a thiirane ring, A compound having an oxirane ring may be contained.

The conversion rate of the oxirane ring to the thiirane ring (hereinafter also referred to as S conversion rate) is preferably 5% or more from the viewpoint of the curing rate of the resin composition of the present embodiment. The S conversion is preferably 10 to 100%, more preferably 30 to 100%, and still more preferably 50 to 100%.
The lower the S conversion rate, the higher the production efficiency.
However, when the resin composition of the present embodiment is used for an application requiring high refractive index, it is advantageous that the S conversion rate is high. In such a case, the preferable S conversion is 80 to 100%, more preferably 90 to 100%, still more preferably 95 to 100%, and still more preferably 98 to 100%.

The S conversion can be controlled by the reaction temperature, reaction time, blending amount of the thiating agent, and the like. The S conversion can also be adjusted by mixing a compound having a plurality of thiirane rings having a known S conversion.
The S conversion can be obtained by (A) NMR measurement of a compound having at least one thiirane ring. Specifically, it can be measured by the method described in [Example] described later.

As described above, in order to convert the oxirane ring of the epoxy compound into a thiirane ring, it is necessary to react the oxirane ring of the epoxy compound with a thialating agent to form a thiirane ring.
The thialating agent is not particularly limited as long as it is a compound that can react with an oxirane ring to form a thiirane ring.
Only one type of chelating agent may be used alone, or two or more types may be used in combination.
It is preferable that the thiarizing agent contains at least one compound selected from the group consisting of thioureas and thiocyanates. More preferably, the thiarizing agent is at least one compound selected from the group consisting of thiourea, sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and more preferably thiourea.
Since thioureas and thiocyanates are easily available, they tend to be economical.
Further, when thiurea, sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate are used, the reaction time tends to be short and the productivity tends to be high, and thiourea is even more preferable from the same viewpoint.

  Examples of the thiating agent include, but are not limited to, for example, lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, cesium thiocyanate, silver thiocyanate, cobaltous thiocyanate, and thiocyanate. Mercuric acid, thallium thiocyanate, cuprous thiocyanate, lead dithiocyanate, nickel dithiocyanate, barium dithiocyanate, ammonium thiocyanate, guanidine thiocyanate, thiourea, N, N'-dimethylthiourea N, N, N ′, N′-tetramethylthiourea, N, N′-diethylthiourea, propylthiourea, N, N′-diisopropylthiourea, N, N′-dibutylthiourea, N-methyl-N′- (2-Methyl-2-propenyl) thiourea, N-phenylthiourine N, N'-diphenylthiourea, 1-methyl-2-imidazolidinethione, 1-benzyl-2-thiourea, N- (3,5-dimethylphenyl) thiourea, N- (2,6- Dimethylphenyl) thiourea, N- (2,3-dimethylphenyl) thiourea, N- (2,4,6-trimethylphenyl) thiourea, N, N′-bis (2-methylphenyl) thiourea, N , N′-bis (3,5-dimethylphenyl) thiourea, N, N′-bis (2,6-dimethylphenyl) thiourea, N, N′-bis (2,4,6-trimethylphenyl) thio Urea, N- (2-chlorophenyl) thiourea, N- (3-chlorophenyl) thiourea, N- (4-chlorophenyl) thiourea, N- (3,4-dichlorophenyl) thiourea, N- (3,5 -Dichlorophenyl) thi Urea, N- (2,6-dichlorophenyl) thiourea, N- (2,4,6-trichlorophenyl) thiourea, N, N′-bis (2-chlorophenyl) thiourea, N, N′-bis ( 3,5-dichlorophenyl) thiourea, N, N′-bis (2,6-dichlorophenyl) thiourea, N- (2-fluorophenyl) thiourea, N- (3-fluorophenyl) thiourea, N- ( 4-fluorophenyl) thiourea, N- [2- (trifluoromethyl) phenyl] thiourea, N- [3- (trifluoromethyl) phenyl] thiourea, N- [4- (trifluoromethyl) phenyl] Thiourea, N- (2,6-difluorophenyl) thiourea, N- (2,4-difluorophenyl) thiourea, N- (2,3-difluorophenyl) thiourea, N- (2,4,6 − Trifluorophenyl) thiourea, N, N′-bis (2-fluorophenyl) thiourea, N, N′-bis (2,6-difluorophenyl) thiourea, N, N′-bis (2,4,4) 6-trifluorophenyl) thiourea, N- (2-cyanophenyl) thiourea, N- (3-cyanophenyl) thiourea, N- (4-cyanophenyl) thiourea, N- (3,5-dicyano Phenyl) thiourea, N, N′-bis (4-cyanophenyl) thiourea, N, N′-bis (3,5-dicyanophenyl) thiourea, N- (2-methoxyphenyl) thiourea, N— (3-methoxyphenyl) thiourea, N- (4-methoxyphenyl) thiourea, N- (2,6-dimethoxyphenyl) thiourea, N- (3,5-dimethoxyphenyl) thiourea, N- (2 , 4,6 trige Toxiphenyl) thiourea, N, N′-bis (4-methoxyphenyl) thiourea, N, N′-bis (2,6-dimethoxyphenyl) thiourea, N, N′-bis (2,4,6) Tridimethoxyphenyl) thiourea, N- (2-nitrophenyl) thiourea, N- (3-nitrophenyl) thiourea, N- (4-nitrophenyl) thiourea, N- (3,5-dinitrophenyl) Examples include thiourea and N, N′-bis (3,5-dinitrophenyl) thiourea.

The chelating agent may be used as a support supported on a predetermined carrier.
By using a support having a thiating agent supported on a carrier, the reaction time is shortened, and the production of a polymer between episulfide compounds and a reaction product of an episulfide compound and a thiarizing agent can be suppressed, and the yield is increased. Enhanced. Moreover, there is a tendency that the operation for separating the thiating agent is facilitated by separating the support after completion of the reaction.
Here, “supporting” refers to attaching a thiating agent on or inside the carrier, or exchanging anionic atoms or molecules contained in the carrier with a thioisocyanate anion.
As the carrier, any commonly used carrier can be used, and is not limited to the following. For example, silica (spherical, crushed, scaly, etc. may be used, and acidic, Neutral (which may be neutral), alumina (spherical, ring-shaped, pellet-shaped, etc., which may or may not be activated), ion exchange resin (for example, Amberlyst TM, Amberlite TM, AmberJet TM, Dowex TM, polyvinylamine, polyvinylpyridine, etc. manufactured by Dow Chemical Co.).

The chelating agent preferably has a lower impurity content.
Less impurities (for example, sulfate, chloride, sulfide, copper, lead, iron, iodine, sodium, etc.) contained in the chelating agent is advantageous from the viewpoint of further enhancing the effect of the present invention. Separation of impurities during separation and purification of episulfide compounds, unreacted epoxy compounds, compounds formed by replacing sulfur atoms of thiating agents with oxygen atoms, thiating agents, and polyhydric hydroxyl compounds after completion This is advantageous from the standpoint that a high-purity compound is obtained without the need for a process.
The content of the impurities of the chelating agent is preferably 5000 ppm or less, more preferably 2000 ppm or less, and even more preferably 500 ppm or less.

In the step of producing a compound having a thiirane ring, the mixing ratio in the reaction between the raw material epoxy compound and the thiating agent can be represented by a mixing index α calculated by the following formula (1). .
Mixing index α = αt / αe (1)
In the formula (1), αt represents a substance amount (mol) of a sulfur atom that can be used to form a thiirane ring contained in the thiarizing agent, and αe represents a substance amount (mol of the oxirane ring contained in the epoxy compound). ).
In the present embodiment, the mixing index α is preferably 1 to 5, and more preferably 1 to 2.
When the mixing index α is 1 or more, the reaction time between the epoxy compound and the thiarizing agent becomes shorter and the productivity tends to be improved. When the mixing index α is 5 or less, production of a reaction product of a compound having at least one thiirane ring and a thiarizing agent can be suppressed, and the yield tends to be increased.

The thialation reaction may be performed without a solvent or in a solvent.
When using a solvent, it is preferable to use a solvent in which either thiourea or thiocyanate, or an epoxy compound is soluble.
The solvent used in the thialation reaction is not limited to the following. , Hydroxy ethers such as ethyl cellosolve and butyl cellosolve ”,“ aromatic hydrocarbons such as benzene, toluene and xylene ”,“ halogenated hydrocarbons such as dichloroethane, chloroform and chlorobenzene ”and the like. These may be used alone or in combination of two or more.
Examples of the solvent combination include a combination of alcohols and water, ethers, hydroxy ethers, halogenated hydrocarbons, a combination of aromatic hydrocarbons and alcohols, and the like. Among these, from the viewpoint of the balance between reaction rate and yield, a combination of aromatic hydrocarbons and alcohols is preferable, and a combination of toluene and methanol is more preferable.
The composition ratio when combining the solvents is not particularly limited. For example, the ratio of aromatic hydrocarbons to alcohols is preferably aromatic hydrocarbons: alcohols = 90: 10 to 30:70. More preferably, it is 80: 20-40: 60, More preferably, it is 70: 30-50: 50 (mass ratio, 100 in total).

The ratio of the raw material epoxy compound and the solvent is not particularly limited, but preferably the raw material epoxy compound: solvent = 5: 95 to 50:50, more preferably 10:90 to 40:60, still more preferably. 15: 85-30: 70.
In addition, the said ratio shall be mass ratio and shall be 100 in total.
In the case of the said ratio, it becomes possible to maintain a reaction liquid at a suitable viscosity, and quality can be stabilized.

Moreover, adding an acid, an acid anhydride, or the like as a polymerization inhibitor to the reaction solution in the step of performing the thialation reaction is an effective means from the viewpoint of improving the reaction results.
Examples of acids and acid anhydrides that are polymerization inhibitors include, but are not limited to, nitric acid, hydrochloric acid, sulfuric acid, fuming sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, Thioacetic acid, succinic acid, tartaric acid, propionic acid, butyric acid, succinic acid, maleic acid, benzoic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, Examples include butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, silica gel, silica alumina, and aluminum chloride.
Among these, from the viewpoint of by-product suppression, it is preferable to use an acid anhydride, and from the viewpoint of availability, acetic anhydride, succinic anhydride, and maleic anhydride are more preferable, and acetic anhydride is more preferable.
These acids or acid anhydrides may be used alone or in combination.
The amount of the acid or acid anhydride added is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the total amount of the reaction solution.

The temperature in the step of performing the thialation reaction is not particularly limited, but is preferably 20 to 100 ° C, more preferably 30 to 80 ° C, and further preferably 40 to 65 ° C.
By making it 20 degreeC or more, practically sufficient productivity is obtained, and stable quality can be ensured by making it 100 degreeC or less.

  The reaction time in the thialation reaction step is not particularly limited as long as the reaction is completed under the various conditions described above, but is preferably 24 hours or less from the viewpoint of productivity.

  The atmosphere in the thialation reaction is not particularly limited, but the thialation reaction should be performed in an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon, or in the air. Can do. Among these gases, inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon is preferable from the viewpoint of safety and suppression of by-products, and nitrogen, helium, neon, argon , Krypton, xenon and carbon dioxide are more preferable, nitrogen and helium are more preferable, and nitrogen is particularly preferably used.

  The pressure in the thialation reaction can be carried out under the above gas atmosphere, under circulation, under reduced pressure, under pressure, or a combination thereof. The pressure need not be constant and may be changed during the reaction.

The reaction solution obtained by the above-mentioned thialation reaction (step A) may be used as it is, but it is preferable to remove by-products by carrying out a washing step (step B) for further washing the reaction solution.
The cleaning liquid is not particularly limited as long as it is water or a solvent that can be used for the above-mentioned thialation reaction. Only one type of cleaning liquid may be used alone, or two or more types may be used in combination.
Further, the number of times of cleaning is not particularly limited, and the type and ratio of the cleaning liquid may be changed for each number of times of cleaning.
Further, from the viewpoint of improving the stability of the obtained compound, it is possible to perform washing using an acidic aqueous solution.
The pH of the acidic aqueous solution is not particularly limited, but is preferably 6 or less, more preferably 3 or less, because a stabilizing effect is surely obtained.
Examples of the acid used in the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, succinic acid, tartaric acid, succinic acid, maleic acid, ascorbic acid and the like. Sulfuric acid is particularly preferred from the standpoint of availability and effect. These acids may be used alone or in combination of two or more.

When water, an organic solvent, etc. remain in the reaction liquid after the washing described above, a devolatilization step (Step C) for removal by a devolatilizer described later may be performed.
The devolatilization apparatus is not particularly limited. For example, a rotary evaporator, a vertical stirring tank equipped with a distillation tube, a surface renewal stirring tank, a thin film evaporator, a surface renewal biaxial kneader, two Horizontal axis stirrer, wet wall type reactor, free fall type perforated plate reactor, reactor that drops volatile components while dropping compounds along the support, freeze dryer, vacuum dryer, etc. Can be mentioned.
These devices may be used alone or in combination of two or more.
The devolatilization method is not particularly limited, but a method of distilling off water or an organic solvent under reduced pressure with a rotary evaporator or the like is preferable from the viewpoint of suppressing deterioration due to heating.
Distillation under reduced pressure is usually carried out at a pressure of 0.1 to 10,000 Pa at 10 to 100 ° C. The distillation time is not particularly limited, but is usually 24 hours or less.
Furthermore, in order to increase the purity of the obtained reaction solution or resin, purification may be carried out by distillation or filtration. Usually, distillation is performed at 0-100 degreeC under the reduced pressure of 0.1-10000Pa. Filtration is a filter having a pore size of about 0.05 to 10 micron, and filters impurities, polymers and the like at a freezing point to 50 ° C.

As described above, a preferred embodiment of the method for producing a compound having at least one thiirane ring according to this embodiment includes a production method through the following (Step A) to (Step C).
(Step A): A step of reacting the epoxy compound with thioureas or thiocyanate at 40 to 65 ° C. in the presence of alcohol and toluene.
(Step B): A step of washing the reaction solution obtained in Step A.
(Step C): A step of devolatilizing the cleaning liquid obtained in Step B.

((B) ester compound)
In the manufacturing method of the resin composition of this embodiment, it has the process (process 1) which mix | blends (B) ester (Hereinafter, it may be described as (B) component.) In the (A) component mentioned above. .
(B) As an ester compound, the ester compound of an oxo acid is preferable, and an inorganic acid ester compound is more preferable from a viewpoint of a storage stabilization effect and handleability.

Examples of inorganic acids include, but are not limited to, phosphoric acid, phosphorous acid, phosphonic acid, boric acid, silicic acid, silicone acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and the like. Furthermore, oligomers or polymer anhydrides thereof may be used.
Among the inorganic acid ester compounds, phosphoric acid esters, phosphite esters, and boric acid esters are preferable, phosphorous acid esters or boric acid esters are more preferable, and phosphorous acid esters from the viewpoint of easy availability and handling. Is more preferable.
(B) An ester compound may be used individually by 1 type, or may be used in combination of 2 or more types.

(B) Although the pH of ester compound is not specifically limited, Preferably it is 5.5-8.5, More preferably, it is 6-8, More preferably, it is 6.3-7.7, More preferably 6.5-7.5.
Since the curable resin composition of the present embodiment, which will be described later, may be cured by anionic polymerization or cationic polymerization, it is preferably close to neutral in order to maintain a stable curing reaction.

  (B) Although the compounding quantity of an ester compound is not specifically limited, 0.02-20 mass parts is preferable with respect to 100 mass parts of (A) compounds which have at least 1 thiirane ring, 0.05- 10 mass parts is more preferable, and 0.1-5 mass parts is further more preferable. By blending 0.02 parts by mass or more of component (B) with respect to 100 parts by mass of component (A), a storage stabilizing effect can be obtained. Adhesiveness with reinforcing fibers when obtaining fiber reinforced plastics can be obtained.

<Phosphate ester>
Examples of the phosphate ester include, but are not limited to, phosphate esters represented by the following formula (2).
Specifically, diethylbenzyl phosphate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) ₃ P═O [R = lauryl group, cetyl Group, stearyl group or oleyl group], tris (2-chloroethyl) phosphate, tris (2-dichloropropyl) phosphate, triphenylphosphate, butylpyrophosphate, tricresyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, cresyl Diphenyl phosphate, xylenyl diphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, ammonia Um ethyl acid phosphate, and 2-ethylhexyl acid phosphate salt.
Of these, diethylbenzyl phosphate is preferably used.

(In the formula (2), in R ^{1 to} R ³ , R ¹ is a hydrocarbon group having 1 to 30 carbon atoms; R ² and R ³ are each independently 1 to 30 carbon atoms. It is a hydrocarbon group or a hydrogen atom.)

<Phosphorous ester>
The structure of the phosphite ester is not particularly limited as long as it is an ester compound in which a phosphorus atom and an organic group are bonded via a P—O bond. For example, the following formulas (3) to ( The phosphite represented by 6) is mentioned.

(In the general formula (3), in R ^{1 to} R ³ , R ² is a hydrocarbon group having 1 to 30 carbon atoms; R ¹ and R ³ are each independently 1 to 30 carbon atoms. It is a hydrocarbon group or a hydrogen atom.)

(In the general formula (4), in R ^{4 to} R ⁵ , R ⁴ and R ⁵ are each independently a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom.)

(In the formula (5), in R ^{6 to} R ⁹ , R ^{6 to} R ⁹ are each independently a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom.)

From the viewpoints of compatibility in the resin composition of the present embodiment and storage stability, among the phosphites represented by the above formulas (3) and (4), an ester moiety (-PO- It is preferable that at least one of R) has a structure containing an aromatic ring such as a benzene ring.
When the aromatic ring has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and the substitution position is preferably a meta position or a para position.

  In addition, in the compounds represented by the formulas (3) and (4), those having a structure containing an alkyl group in the ester moiety (—P—O—R) are preferable from the viewpoints of storage stability and handleability. From the viewpoint of inhibiting hydrolysis, the alkyl group preferably has 4 or more carbon atoms, and from the viewpoint of heat resistance, the alkyl group preferably has 6 or more carbon atoms.

  The phosphite having a bisphenol skeleton as represented by the formula (5) and the phosphite having four or more aromatic rings as represented by the formula (6) are other components in the resin composition of the present embodiment. Excellent properties in terms of compatibility and low hydrolyzability.

  Examples of the phosphite ester include, but are not limited to, trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris (2-ethylhexyl) phosphite, triisooctyl phosphite, tri Decyl phosphite, triisodecyl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t- Butylphenyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isooctyl phosphite, diphenyl monodecyl phosphite, diph Nyl monoisodecyl phosphite, diphenyl mono (tridecyl) phosphite, bis (nonylphenyl) dinonyl phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, diisodecyl pentaerythritol diphos Phyto, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4, 4'-isopropylidene diphenyl phosphite, trilauryl trithiophosphite, dimethyl hydrogen phosphite, dibutyl alcohol Drodiene phosphite, di (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phos Phyto, diphenyl mono (tridecyl) phosphite, tetra (C12-C15 alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetraphenyl dipropylene glycol diphosphite and the like.

Among these, from the viewpoint that at least one of the ester moieties (—P—O—R) includes a structure containing an aromatic ring such as a benzene ring, for example, triphenyl phosphite, tricresyl phosphite, trisnonylphenyl phosphine. From the viewpoint of including a structure containing an alkyl group having 4 or more carbon atoms in the ester moiety (—P—O—R), triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite is more preferable. Phyto, trilauryl phosphite, tris (tridecyl) phosphite, and trioleyl phosphite are more preferable.
From the viewpoint that at least one of the ester moieties (—P—O—R) includes a structure including an aromatic ring such as a benzene ring and includes a structure including an alkyl group having 4 or more carbon atoms, diphenyl mono (2-Ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, tetra (C12-C15 alkyl) -4,4′-isopropylidene diphenyl diphosphite are more preferred.
Among these, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, and diphenyl mono (tridecyl) phosphite are particularly preferable from the viewpoint of balance between versatility and compatibility.

  Moreover, as a phosphite, it is also possible to use a commercial item, for example, Johoku Chemical Co., Ltd. make, JP-360, JP-351, JP-3CP, JP-302, JP-308E, JP-310, JP-312L, JP-333E, JP-318-O, JPM-308, JPM-311, JPM-313, JPS-312, JPP-100, JPP-613M, JA-805, JPP-88, Examples include JPE-10, JPE-13R, JP-318E, JP-2000PT, JP-650, JPH-3800, and HBP.

<Boric acid ester>
The borate ester compound is not particularly limited as long as it is an ester compound in which a boron atom and an organic group are bonded via a B—O bond. For example, the following formulas (7) and (8) The boric acid ester represented by these is mentioned.

(In General Formula (7), R ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms; R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom. is there.)

(In General Formula (8), R ¹⁴ is a hydrocarbon group having 1 to 30 carbon atoms; R ¹⁵ and R ¹⁶ are each independently a hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom. is there.)

From the viewpoints of compatibility with other components in the resin composition and storage stability, the ester moiety (-B-O-- It is preferable that at least one of R) has a structure containing an aromatic ring such as a benzene ring. When the aromatic ring has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and the substitution position is preferably a meta position or a para position.
In addition, in the compounds represented by the formulas (7) and (8), those having a structure containing an alkyl group in the ester moiety (—B—O—R) are preferable from the viewpoint of storage stability and handleability. Among these, from the viewpoint of inhibiting hydrolysis, the alkyl group preferably has 4 or more carbon atoms, and from the viewpoint of heat resistance, the alkyl group preferably has 6 or more carbon atoms.

  Examples of the borate ester include, but are not limited to, trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tri-t-butyl borate, boric acid Tripentyl, trihexyl borate, trioctyl borate, trihexadecyl borate, trioctadecyl borate, trihexadecyl borate, tris (2-methoxymethyl) borate, tricyclohexyl borate, triphenyl borate, tribenzyl borate, Tri (o-tolyl) borate, 2-ethoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-isopropoxy-4,4,5,5-tetramethyl-1, 3,2-dioxaborolane, 2-isopropoxy-4,4,6-trimethyl-1,3,2-dioxa Linane, trisubstituted borate compounds such as 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2,4,6-trimethoxyboroxine, diisopropoxymethylborane and Disubstituted borate compounds such as butyldiisopropoxyborane, monosubstituted borate compounds such as diethylmethoxyborane, 2,4,6-trimethoxyboroxine, 2,4,6-triphenylboroxine, methyl- 1,3,2-dioxaborinane, 2-butyl-1,3,2-dioxaborinane, triethanolamine borate, bis (neopentylglycolato) diboron, bis (pinacolato) boroxine and 4- (4,4,5,5 -Cyclic boric acid ester such as tetramethyl-1,3,2-dioxaborolan-2-yl) phenol Compound, otherwise, borate esters of triethylene glycol monoalkyl ethers, poly borate ester (oxyethylene-oxypropylene) glycol monoalkyl ether, tris (trimethylsilyl) borate, etc. catechol borane.

Among these, from the viewpoint that at least one of the ester moieties (—B—O—R) includes a structure containing an aromatic ring such as a benzene ring, for example, triphenyl borate, tribenzyl borate, triborate borate (o— Tolyl) is more preferred.
From the viewpoint of including a structure containing an alkyl group having 4 or more carbon atoms in the ester moiety (—P—O—R), tributyl borate, tri-t-butyl borate, tripentyl borate, trihexyl borate, boron Trioctyl acid, trihexadecyl borate, trioctadecyl borate, and trihexadecyl borate are more preferable.

(Epoxy compound)
In the method for producing a resin composition of the present embodiment, an epoxy compound may be further added in addition to the above-described components (A) and (B).
The epoxy compound refers to a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding the compound constituting the compound (A) having at least one thiirane ring, and satisfies the above-mentioned requirements. If it is a thing, it will not specifically limit.
Epoxy compounds may be used alone or in combination of two or more.

It is preferable that the epoxy equivalent (WPE) of an epoxy compound is 100-600 g / eq, More preferably, it is 100-500 g / eq, More preferably, it is 100-300 g / eq.
When the epoxy equivalent (WPE) is 100 g / eq or more, practically good storage stability is obtained in the resin composition of this embodiment, and when it is 600 g / eq or less, the physical properties of a practically good cured product are obtained. can get.

The epoxy compound is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, still more preferably 100 Pa · s or less, and even more preferably 50 Pa · s or less. is there.
When the viscosity of the epoxy compound at 25 ° C. is 1000 Pa · s or less, good fluidity as a liquid is obtained, and compatibility with the alkoxysilane compound described later is good.
In addition, when the viscosity at 25 ° C. is more than 500 Pa · s and 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. Since manufacturing conditions tend to be somewhat limited, it is preferably 500 Pa · s or less.

The type of the epoxy compound is not particularly limited and is not limited to the following. For example, a monofunctional epoxy compound, a polyfunctional epoxy compound that is a glycidyl etherified product of a polyphenol compound, an alicyclic epoxy compound, Polyfunctional epoxy compounds that are glycidyl ethers of various novolak compounds, nuclear hydrides of aromatic epoxy compounds, heterocyclic epoxy compounds, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, and halogenated phenols are glycidylated. Examples include epoxy compounds, sulfur-containing polyfunctional aliphatic epoxy compounds, silicone compounds having an epoxy group in the molecule, and heteropolymerizable substituent-containing epoxy compounds.
These may be used alone or in combination of two or more.

<Monofunctional epoxy compound>
The monofunctional epoxy compound is not limited to, for example, ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, butadiene oxide, butadiene diepoxide, cyclobutene oxide, 1,3-cyclobutadiene. Diepoxide, 1-pentene oxide, 2-pentene oxide, 1,3-pentadiene diepoxide, 1,4-pentadiene diepoxide, 2-methyl-2-butene oxide, 2-methyl-3-butene oxide, cyclopentene oxide, 1,3-cyclopentadiene diepoxide, 1-methyl-cyclobutene oxide, 3-methyl-1-cyclobutene oxide, 1-hexene oxide, 2-hexene oxide, 3-hexene oxide, 1,3-hexadiene diepoxide, 1,4- Xadiene diepoxide, 1,5-hexadiene diepoxide, 1,3,5-hexatriene epoxide, cyclohexene oxide, 1,3-cyclohexadiene diepoxide, 1,3,5-cyclohexatrient epoxide, 1-methyl -Cyclopentene oxide, 3-methyl-cyclopentene oxide, 1-methyl-1,3-cyclopentadiene diepoxide, 2-methyl-1,3-cyclopentadiene diepoxide, 5-methyl-1,3-cyclopentadiene diepoxide, 3,4-dimethyl-cyclobutene oxide, 2,3-dimethyl-cyclobutene oxide, 1,2-dimethyl-cyclobutene oxide, 1,2-dimethyl-1,3-cyclobutadiene diepoxide, 2,3-dimethyl -1,3-cyclobutadiene diepo Sid, 3,3-dimethyl-1,2-epoxybutane, 1-heptene oxide, 2-heptene oxide, 3-heptene oxide, 1,3-heptadiene diepoxide, 1,4-heptadiene diepoxide 1,5-heptadiene diepoxide, 1,5-heptadiene diepoxide, 1,6-heptadiene diepoxide, 1,3,5-heptatriene epoxide, 1,3,6-heptatrient epoxide, 1,4,6-heptatriene epoxide, cycloheptene oxide, 1-methyl-cyclohexene oxide, 3-methyl-cyclohexene oxide, 4-methyl-cyclohexene oxide, 1-methyl-1,3-cyclohexadiene diepoxide, 1-methyl-1,4-hexadiene diepoxide, 1-methyl-1,3,5-he Xatrient epoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-4-vinylcyclohexene, 2-norbornene oxide, 7-methyl-2-norbornene oxide, 7,7-dimethyl-2-norbornene oxide 2-methyl-2-norbornene oxide, 2,3-dimethyl-2-norbornene oxide, 2,7-dimethyl-2-norbornene oxide, 2,7,7-trimethyl-2-norbornene oxide, 2,3-epoxy -Bicyclo [2,2,2] octane, 2,3-epoxy-2-methyl-bicyclo [2,2,2] octane, 2,3-epoxy-2,3-dimethyl-bicyclo [2,2,2] ] Octane, 2,3-epoxy-2,5-dimethyl-bicyclo [2,2,2] octane, 2,3-epoxy-2,6-dimethyl Bicyclo [2,2,2] octane, 2,3-epoxy-2,3,5-trimethyl-bicyclo [2,2,2] octane, 2,3-epoxy-2,5,6-trimethyl-bicyclo [ 2,2,2] octane, 2,3-epoxy-2,3,5,6-tetramethyl-bicyclo [2,2,2] octane, dioctyl epoxyhexahydrophthalate, di-2 epoxyhexahydrophthalate -Ethylhexyl, stibene oxide, phenylglycidyl ether, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-epoxypropane, pinene oxide, isoprene monooxide, 1,2-epoxyethylbenzene, naphthylglycidyl Ether, 3- (2-biphenyloxy) -1,2-epoxypropane, allyl glycidyl ether, 1,1-diphe Ru-ethylene oxide, glycidyl (meth) acrylate, glycidyl butyrate, iodomethyloxirane, 4- (2,3-epoxypropyl) morpholine, glycidyl methyl ether, 2-phenyl-propylene oxide, 2,3-epoxypropyl-furfuri Ether, 2,3,4,5,6-pentafluorostyrene oxide, ethyl-3-phenylglycidate, fosmidomycin, limonene oxide, epoxysuccinic acid, 3-glycidoxypropyltrimethoxysilane, (3- Glycidoxypropyl) pentamethyldisiloxane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-D Poxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxypropyltriethoxysilane, and the like.

Among the above, since the vapor pressure in the standard state is high, the handling is easy, and there is a tendency to suppress the formation of a polymer and the reaction between the thiating agent and the thiirane ring. It is preferable that it is at least 1 type of compound chosen from these groups.
That is, for example, ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, butadiene oxide, butadiene diepoxide, cyclobutene oxide, 1,3-cyclobutadiene diepoxide, 1-pentene oxide, 2-pentene oxide, 1 , 3-pentadiene diepoxide, 1,4-pentadiene diepoxide, 2-methyl-2-butene oxide, 2-methyl-3-butene oxide, cyclopentene oxide, 1,3-cyclopentadiene diepoxide, 1-methyl-cyclo Butene oxide, 3-methyl-1-cyclobutene oxide, 1-hexene oxide, 2-hexene oxide, 3-hexene oxide, 1,3-hexadiene diepoxide, 1,4-hexadiene diepoxide, 1,5-hexadiene Epoxide, 1,3,5-hexatriene epoxide, cyclohexene oxide, 1,3-cyclohexadiene diepoxide, 1,3,5-cyclohexatriene epoxide, 1-methyl-cyclopentene oxide, 3-methyl-cyclopentene oxide, 1-methyl-1,3-cyclopentadiene diepoxide, 2-methyl-1,3-cyclopentadiene diepoxide, 5-methyl-1,3-cyclopentadiene diepoxide, 3,4-dimethyl-cyclobutene oxide, 2 , 3-dimethyl-cyclobutene oxide, 1,2-dimethyl-cyclobutene oxide, 1,2-dimethyl-1,3-cyclobutadiene diepoxide, 2,3-dimethyl-1,3-cyclobutadiene diepoxide, 3, , 3-Dimethyl-1,2-epoxybutane 1-heptene oxide, 2-heptene oxide, 3-heptene oxide, 1,3-heptadiene diepoxide, 1,4-heptadiene diepoxide, 1,5-heptadiene diepoxide, 1,5- Heptadiene diepoxide, 1,6-heptadiene diepoxide, 1,3,5-heptatriente epoxide, 1,3,6-heptatriente epoxide, 1,4,6-heptatriente epoxide, cycloheptene Oxide, 1-methyl-cyclohexene oxide, 3-methyl-cyclohexene oxide, 4-methyl-cyclohexene oxide, 1-methyl-1,3-cyclohexadiene diepoxide, 1-methyl-1,4-hexadiene diepoxide, 1- Methyl-1,3,5-hexatrientepoxide, 1,2-epoxy 5-hexene, 1,2-epoxy-4-vinylcyclohexene, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, stibene oxide, phenylglycidyl ether, 3- (2,2,3, 3-tetrafluoropropoxy) -1,2-epoxypropane, pinene oxide, isoprene monooxide, 1,2-epoxyethylbenzene, naphthyl glycidyl ether, 3- (2-biphenyloxy) -1,2-epoxypropane, allyl glycidyl ether 1,1-diphenyl-ethylene oxide, glycidyl (meth) acrylate, glycidyl butyrate, iodomethyloxirane, 4- (2,3-epoxypropyl) morpholine, glycidyl methyl ether, 2-phenyl-propylene ester Sid, 2,3-epoxypropyl-furfuryl ether, 2,3,4,5,6-pentafluorostyrene oxide, ethyl-3-phenylglycidate, fosmidomycin, limonene oxide, epoxysuccinic acid, 3-glycol Sidoxypropyltrimethoxysilane, (3-Gucylidoxypropyl) pentamethyldisiloxane, 3-Glycidoxypropyl (methyl) dimethoxysilane, 3-Glycidoxypropyl (methyl) diethoxysilane, 3-Glycidoxy Propyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl ( Methyl) dimethoxysilane, 2,3-epoxy Lopyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, and 2,3-epoxypropyltriethoxysilane are preferred.

More preferably, the monofunctional epoxy compound includes at least one compound selected from the following group.
That is, for example, propylene oxide, 1-butene oxide, 2-butene oxide, butadiene oxide, butadiene diepoxide, 1-pentene oxide, 2-pentene oxide, 1,3-pentadiene diepoxide, 1,4-pentadiene diepoxide, 2-methyl-2-butene oxide, 2-methyl-3-butene oxide, cyclopentene oxide, 1-methyl-cyclobutene oxide, 3-methyl-1-cyclobutene oxide, 1-hexene oxide, 2-hexene oxide, 3 -Hexene oxide, 1,3-hexadiene diepoxide, 1,4-hexadiene diepoxide, 1,5-hexadiene diepoxide, 1,3,5-hexatriene epoxide, cyclohexene oxide, 1,3-cyclohexadiene diepoxide 1-methyl-cyclopentene oxide, 3-methyl-cyclopentene oxide, 2-heptene oxide, 3-heptene oxide, 1,3-heptadiene diepoxide, 1,4-heptadiene diepoxide, 1,5-heptadi Enddiepoxide, 1,5-heptadiene diepoxide, 1,6-heptadiene diepoxide, 1-methyl-cyclohexene oxide, 3-methyl-cyclohexene oxide, 4-methyl-cyclohexene oxide, 1,2-epoxy-5 Hexene, 1,2-epoxy-4-vinylcyclohexene, stibene oxide, phenylglycidyl ether, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-epoxypropane, pinene oxide, isoprene monooxide 1,2-epoxyethylbenzene, Butyl glycidyl ether, 3- (2-biphenyloxy) -1,2-epoxypropane, allyl glycidyl ether, 1,1-diphenyl-ethylene oxide, glycidyl (meth) acrylate, glycidyl butyrate, iodomethyloxirane, 4- (2 , 3-epoxypropyl) morpholine, glycidyl methyl ether, 2-phenyl-propylene oxide, 2,3-epoxypropyl-furfuryl ether, 2,3,4,5,6-pentafluorostyrene oxide, ethyl-3-phenyl Glycidate, fosmidomycin, limonene oxide, epoxysuccinic acid, 3-glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl) pentamethyldisiloxane, 3-glycidoxypropyl (methyl) dimethoxysilane 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3- Epoxypropyltrimethoxysilane, and , 3-epoxypropyl triethoxysilane, and the like as preferred.

<Polyfunctional epoxy compound>
Examples of the polyfunctional epoxy compound that is a glycidyl etherified product of the polyphenol compound include, but are not limited to, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6- -Butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, and glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.
Among them, glycidyl ethers of phenols having a bisphenol A skeleton or a bisphenol F skeleton because they can be obtained at low cost and tend to suppress the formation of a polymer of an episulfide compound and the reaction of a thiating agent with an episulfide compound. The polyfunctional epoxy compound which is a compound is preferable.

The repeating unit in the case of using a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound as the epoxy compound is not particularly limited, but is preferably less than 50, more preferably 0.001 to 5, more preferably Is 0.01-2.
When the repeating unit is 0.001 or more, good reactivity is obtained, and when it is 50 or less, practically sufficient fluidity is obtained. From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit is particularly preferably from 0.01 to 2.

<Alicyclic epoxy compound>
The alicyclic epoxy compound may be an epoxy compound having an alicyclic epoxy group, and is not limited to the following, but includes, for example, a cyclohexene oxide group, a tricyclodecene oxide group, or a cyclopentene oxide group. An epoxy compound is mentioned.
Examples of the alicyclic epoxy compound include, but are not limited to, for example, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta- Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4- Epoxy-6-me Cyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), and 1 2,8,9-diepoxy limonene.
Examples of other polyfunctional alicyclic epoxy compounds include, but are not limited to, 1,2-epoxy-4- (2-oxiranyl) of 2,2-bis (hydroxymethyl) -1-butanol. ) Cyclohexene adduct and the like.
Although it does not limit to the following as a commercial item of a polyfunctional alicyclic epoxy compound, For example, Epolide GT401 (Daicel Chemical Industries Ltd.), EHPE3150 (made by Daicel Chemical Industries Ltd.), etc. are mentioned.

<Polyfunctional epoxy compound which is glycidyl etherified product of novolak compound>
The polyfunctional epoxy compound that is a glycidyl etherified product of a novolak compound is not limited to the following, but examples include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, and bisphenol S. And novolak compounds made from various phenols such as naphthols, xylylene skeleton-containing phenol novolak compounds, dicyclopentadiene skeleton-containing phenol novolak compounds, biphenyl skeleton-containing phenol novolac compounds, and fluorene skeleton-containing phenol novolak compounds. Examples thereof include glycidyl etherified compounds.
Among these, from the viewpoint of easy availability, a novolak compound using phenol or cresols as a raw material is preferable.

<Nuclear hydride of aromatic epoxy compound>
Examples of the nuclear hydride of the aromatic epoxy compound include, but are not limited to, glycidyl etherified products of phenolic compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) Nuclear hydrogenated aromatic rings of phenol (phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and nuclei of glycidyl etherified products of novolak compounds A hydride etc. are mentioned.

<Heterocyclic epoxy compound>
Examples of the heterocyclic epoxy compound include, but are not limited to, a heterocyclic epoxy compound having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

<Glycidyl ester epoxy compound>
Examples of the glycidyl ester-based epoxy compound include, but are not limited to, epoxy compounds derived from carboxylic acid compounds such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester. .

<Glycidylamine epoxy compound>
Examples of the glycidylamine epoxy compound include, but are not limited to, for example, epoxy obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Compounds and the like.

<Epoxy compound obtained by glycidylation of halogenated phenols>
Examples of epoxy compounds obtained by glycidylation of halogenated phenols include, but are not limited to, for example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, Examples thereof include epoxy compounds obtained by glycidyl etherification of halogenated phenols such as chlorinated bisphenol S and chlorinated bisphenol A.

<Sulfur-containing polyfunctional aliphatic epoxy compound>
Examples of the sulfur-containing polyfunctional aliphatic epoxy compound include, but are not limited to, 1,1-bis (epoxyethyl) methane and 1- (epoxyethyl) -1- (β-epoxypropyl) methane. 1,1-bis (β-epoxypropyl) methane, 1- (epoxyethyl) -1- (β-epoxypropyl) ethane, 1,2-bis (β-epoxypropylethane), 1- (epoxyethyl)- 3- (β-epoxypropyl) butane, 1,3-bis (β-epoxypropyl) propane, 1- (epoxyethyl) -4- (β-epoxypropyl) pentane, 1,4-bis (β-epoxypropyl) ) Butane, 1- (epoxyethyl) -5- (β-epoxypropyl) hexane, 1- (epoxyethyl) -2- (γ-epoxybutylthio) ethane, 1- (epoxy) Cyethyl) -2- [2- (γ-epoxybutylthio) ethylthio] ethane, tetrakis (β-epoxypropyl) methane, 1,1,1-tris (β-epoxypropyl) propane, 1,3-bis (β -Epoxypropyl) -1- (β-epoxypropyl) -2-thiapropane, 1,5-bis (β-epoxypropyl) -2,4-bis (β-epoxypropyl) -3-thiapentane, 1,3 or 1,4-bis (epoxyethyl) cyclohexane, 1,3 or 1,4-bis (β-epoxypropyl) cyclohexane, 2,5-bis (epoxyethyl) -1,4-dithiane, 2,5-bis ( β-epoxypropyl) -1,4-dithiane, 4-epoxy-1,2-cyclohexene oxide, 2,2-bis [4- (epoxyethyl) cyclohexyl] propyl Bread, 2,2-bis [4- (β-epoxypropyl) cyclohexyl] propane, bis [4- (epoxyethyl) cyclohexyl] methane, bis [4- (β-epoxypropyl) cyclohexyl] methane, bis [4- (Β-epoxypropyl) cyclohexyl] sulfide, bis [4- (epoxyethyl) cyclohexyl] sulfide, bis (β-epoxypropyl) ether, bis (β-epoxypropyloxy) methane, 1,2-bis (β-epoxy Propyloxy) ethane, 1,3-bis (β-epoxypropyloxy) propane, 1,2-bis (β-epoxypropyloxy) propane, 1- (β-epoxypropyloxy) -2- (β-epoxypropyl) Oxymethyl) propane, 1,4-bis (β-epoxypropyloxy) butane, , 3-bis (β-epoxypropyloxy) butane, 1- (β-epoxypropyloxy) -3- (β-epoxypropyloxymethyl) butane, 1,5-bis (β-epoxypropyloxy) pentane, -(Β-epoxypropyloxy) -4- (β-epoxypropyloxymethyl) pentane, 1,6-bis (β-epoxypropyloxy) hexane, 1- (β-epoxypropyloxy) -5- (β- Epoxypropyloxymethyl) hexane, 1- (β-epoxypropyloxy) -2-[(2-β-epoxypropyloxyethyl) oxy] ethane, 1- (β-epoxypropyloxy) -2-[[2- (2-β-epoxypropyloxyethyl) oxyethyl] oxy] ethane, tetrakis (β-epoxypropyloxymethyl) meta 1,1,1-tris (β-epoxypropyloxymethyl) propane, 1,5-bis (β-epoxypropyloxy) -2- (β-epoxypropyloxymethyl) -3-thiapentane, 1,5- Bis (β-epoxypropyloxy) -2,4-bis (β-epoxypropyloxymethyl) -3-thiapentane, 1- (β-epoxypropyloxy) -2,2-bis (β-epoxypropyloxymethyl) -4-thiahexane, 1,5,6-tris (β-epoxypropyloxy) -4- (β-epoxypropyloxymethyl) -3-thiahexane, 1,8-bis (β-epoxypropyloxy) -4- (Β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropyloxy) -4,5-bis (β-epoxy) Cypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropyloxy) -4,4-bis (β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (Β-epoxypropyloxy) -2,4,5-tris (β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropyloxy) -2,5-bis (β -Epoxypropyloxymethyl) -3,6-dithiaoctane, 1,9-bis (β-epoxypropyloxy) -5- (β-epoxypropyloxymethyl) -5-[(2-β-epoxypropyloxyethyl) Oxymethyl] -3,7-dithianonane, 1,10-bis (β-epoxypropyloxy) -5,6-bis [(2-β-epoxypropyloxye) Til) oxy] -3,6,9-trithiadecane, 1,11-bis (β-epoxypropyloxy) -4,8-bis (β-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropyloxy) -5,7-bis (β-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropyloxy)- 5,7-[(2-β-epoxypropyloxyethyl) oxymethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropyloxy) -4,7-bis (β- Epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,3 or 1,4-bis (β-epoxypropyloxy) cyclohexane, 1,3 or 1,4-bis (β- Poxypropyloxymethyl) cyclohexane, bis [4- (β-epoxypropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epoxypropyloxy) cyclohexyl] propane, bis [4- (β-epoxypropyl) Oxy) cyclohexyl] sulfide, 2,5-bis (β-epoxypropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epoxypropyloxyethyloxymethyl) -1,4-dithiane, bis ( β-epoxypropyl) sulfide, bis (β-epoxypropyl) disulfide, bis (β-epoxypropyl) trisulfide, bis (β-epoxypropylthio) methane, bis (β-epoxypropyldithio) methane, bis (β- Epoxypropyldithio) ethane, bis (β-epoxypropipropyl) Dithioethyl) sulfide, bis (β-epoxypropyldithioethyl) disulfide, 1,2-bis (β-epoxypropylthio) ethane, 1,3-bis (β-epoxypropylthio) propane, 1,2-bis (β -Epoxypropylthio) propane, 1- (β-epoxypropylthio) -2- (β-epoxypropylthiomethyl) propane, 1,4-bis (β-epoxypropylthio) butane, 1,3-bis (β -Epoxypropylthio) butane, 1- (β-epoxypropylthio) -3- (β-epoxypropylthiomethyl) butane, 1,5-bis (β-epoxypropylthio) pentane, 1- (β-epoxypropyl) Thio) -4- (β-epoxypropylthiomethyl) pentane, 1,6-bis (β-epoxypropylthio) hexane, 1- (β -Epoxypropylthio) -5- (β-epoxypropylthiomethyl) hexane, 1- (β-epoxypropylthio) -2-[(2-β-epoxypropylthioethyl) thio] ethane, 1- (β- Epoxypropylthio) -2-[[2- (2-β-epoxypropylthioethyl) thioethyl] thio] ethanetetrakis (β-epoxypropylthiomethyl) methane, tetrakis (β-epoxypropyldithiomethyl) methane, 1, 1,1-tris (β-epoxypropylthiomethyl) propane, 1,2,3-tris (β-epoxypropyldithio) propane, 1,5-bis (β-epoxypropylthio) -2- (β-epoxy Propylthiomethyl) -3-thiapentane, 1,5-bis (β-epoxypropylthio) -2,4-bis (β-epoxypropipropyl) Thiomethyl) -3-thiapentane, 1,6-bis (β-epoxypropyldithiomethyl) -2- (β-epoxypropyldithioethylthio) -4-thiahexane, 1- (β-epoxypropylthio) -2,2 -Bis (β-epoxypropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (Β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,5-bis (β-epoxypropylthiomethyl) ) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,4-bis (β-epoxypropylthiomethyl) -3,6-dithi Aoctane, 1,8-bis (β-epoxypropylthio) -2,4,5-tris (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio)- 2,5-bis (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epoxypropylthio) -5- (β-epoxypropylthiomethyl) -5-[(2- β-epoxypropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epoxypropylthio) -5,6-bis [(2-β-epoxypropylthioethyl) thio] -3, 6,9-trithiadecane, 1,11-bis (β-epoxypropylthio) -4,8-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11- Bis (β-epoxypropylthio) -5,7-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -5,7- [(2-β-epoxypropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -4,7-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, tetra [2- (β-epoxypropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epoxypropylthio) acetylmethyl] propane, tetra [2- (β-epoxypropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epoxypropylthiomethyl) acetylmethyl] propane, 1, Or 1,4-bis (β-epoxypropylthio) cyclohexane, 1,3 or 1,4-bis (β-epoxypropylthiomethyl) cyclohexane, 2,5-bis (β-epoxypropylthiomethyl) -1, 4-dithiane, 2,5-bis (β-epoxypropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epoxypropylthioethylthiomethyl) -1,4-dithiane, bis [4- (Β-epoxypropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxypropylthio) cyclohexyl] sulfide, 2,2-bis [4- (β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxypropylthio) cyclohexyl] And sulfides.

Among the above, since the production is easy, the cost of the obtained episulfide compound can be suppressed, and since it is excellent in economic efficiency, the sulfur-containing polyfunctional aliphatic epoxy compound is selected from the following group, at least one kind Compounds are preferred.
That is, although not limited to the following, for example, bis (β-epoxypropyloxy) methane, 1,2-bis (β-epoxypropyloxy) ethane, 1,3-bis (β-epoxypropyloxy) Propane, 1,2-bis (β-epoxypropyloxy) propane, 1- (β-epoxypropyloxy) -2- (β-epoxypropyloxymethyl) propane, 1,4-bis (β-epoxypropyloxy) Butane, 1,3-bis (β-epoxypropyloxy) butane, 1- (β-epoxypropyloxy) -3- (β-epoxypropyloxymethyl) butane, 1,6-bis (β-epoxypropyloxy) Hexane, 1- (β-epoxypropyloxy) -5- (β-epoxypropyloxymethyl) hexane, 1- (β-epoxypropyl) Pyroxy) -2-[(2-β-epoxypropyloxyethyl) oxy] ethane, 1- (β-epoxypropyloxy) -2-[[2- (2-β-epoxypropyloxyethyl) oxyethyl] oxy] Ethane, tetrakis (β-epoxypropyloxymethyl) methane, 1,1,1-tris (β-epoxypropyloxymethyl) propane, 1- (β-epoxypropyloxy) -2,2-bis (β-epoxypropyl) Oxymethyl) -4-thiahexane, 1,5,6-tris (β-epoxypropyloxy) -4- (β-epoxypropyloxymethyl) -3-thiahexane, 1,8-bis (β-epoxypropyloxy) -4- (β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropyloxy) C) -4,5-bis (β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropyloxy) -4,4-bis (β-epoxypropyloxymethyl)- 3,6-dithiaoctane, 1,8-bis (β-epoxypropyloxy) -2,4,5-tris (β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxy) Propyloxy) -2,5-bis (β-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,3 or 1,4-bis (β-epoxypropyloxy) cyclohexane, 1,3 or 1,4- Bis (β-epoxypropyloxymethyl) cyclohexane, bis [4- (β-epoxypropyloxy) cyclohexyl] methane, 2,2-bis [4- (β- Epoxypropyloxy) cyclohexyl] propane, bis [4- (β-epoxypropyloxy) cyclohexyl] sulfide, 2,5-bis (β-epoxypropyloxymethyl) -1,4-dithiane, 2,5-bis (β -Epoxypropyloxyethyloxymethyl) -1,4-dithiane, bis (β-epoxypropyl) sulfide, bis (β-epoxypropyl) disulfide, bis (β-epoxypropylthio) methane, bis (β-epoxypropyldithio) ) Methane, bis (β-epoxypropyldithio) ethane, bis (β-epoxypropyldithioethyl) sulfide, bis (β-epoxypropyldithioethyl) disulfide, 1,2-bis (β-epoxypropylthio) ethane, 1 , 3-Bis (β-epoxypropylthio) propane 1,2-bis (β-epoxypropylthio) propane, 1- (β-epoxypropylthio) -2- (β-epoxypropylthiomethyl) propane, 1,4-bis (β-epoxypropylthio) butane, 1,3-bis (β-epoxypropylthio) butane, 1- (β-epoxypropylthio) -3- (β-epoxypropylthiomethyl) butane, 1,6-bis (β-epoxypropylthio) hexane, 1- (β-epoxypropylthio) -5- (β-epoxypropylthiomethyl) hexane, 1- (β-epoxypropylthio) -2-[(2-β-epoxypropylthioethyl) thio] ethane, 1 -(Β-epoxypropylthio) -2-[[2- (2-β-epoxypropylthioethyl) thioethyl] thio] ethanetetrakis (β-epoxypropylthio Methyl) methane, tetrakis (β-epoxypropyldithiomethyl) methane, 1,1,1-tris (β-epoxypropylthiomethyl) propane, 1,2,3-tris (β-epoxypropyldithio) propane, 1, 6-bis (β-epoxypropyldithiomethyl) -2- (β-epoxypropyldithioethylthio) -4-thiahexane, 1- (β-epoxypropylthio) -2,2-bis (β-epoxypropylthiomethyl) ) -4-thiahexane, 1,5,6-tris (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (β-epoxypropylthio) -4 -(Β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,5-bis (β Epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,4-bis (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (Β-epoxypropylthio) -2,4,5-tris (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2,5-bis (β -Epoxypropylthiomethyl) -3,6-dithiaoctane, tetra [2- (β-epoxypropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epoxypropylthio) acetylmethyl] propane , Tetra [2- (β-epoxypropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epoxypropylthiomethyl) a Tilmethyl] propane, 1,3 or 1,4-bis (β-epoxypropylthio) cyclohexane, 1,3 or 1,4-bis (β-epoxypropylthiomethyl) cyclohexane, 2,5-bis (β-epoxy Propylthiomethyl) -1,4-dithiane, 2,5-bis (β-epoxypropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epoxypropylthioethylthiomethyl) -1,4 -Dithiane, bis [4- (β-epoxypropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxypropylthio) cyclohexyl] Sulfide, 2,2-bis [4- (β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxy group) (Lopylthio) cyclohexyl] sulfide and the like are preferable.

<Silicone compound having an epoxy group in the molecule>
Although it does not specifically limit as a silicone compound which has an epoxy group in a molecule | numerator, For example, it may be chosen from the compound represented by a following formula (XII).
(R ₂₁ R ₂₂ R ₂₃ SiO _1/2 ) _a (R ₂₄ R ₂₅ SiO _2/2 ) _b (R ₂₆ SiO _3/2 ) _c (SiO _4/2 ) _d (XII)
In the formula (XII), a, b, c, and d are numerical values satisfying a + b + c + d = 1.0, and 0 ≦ a / (a + b + c + d) ≦ 1, 0 ≦ b / (a + b + c + d) ≦ 1, 0 ≦ c / (a + b + c + d) ≦ 1 and 0 ≦ d / (a + b + c + d) <1. At least one of R ₂₁ to R ₂₆ represents a group containing an epoxy group, other R ₂₁ to R ₂₆ represents a linear or branched hydrocarbon group or the hydrocarbon having 1 to 8 carbon atoms The group represents a fluorinated group, which may be the same or different from each other.

<Hexogenous polymerizable substituent-containing epoxy compound>
The heteropolymerizable substituent-containing epoxy compound is not particularly limited, and examples thereof include a compound represented by the following formula (XIII).

In the formula (XIII), R _{30 to} R ₃₂ represent a substituted or unsubstituted chain, branched, or cyclic aliphatic or aromatic hydrocarbon group.
m, n, o, and p are one or more real numbers.
X represents an epoxy group.
When Y represents a single type of polymerizable substituent, a cyclic ether structure, a lactone structure, a cyclic carbonate structure, and a sulfur-containing analog structure thereof, a cyclic acetal structure, and a sulfur-containing analog structure thereof, a cyclic amine structure, and a cyclic imino ether Selected from the group consisting of a structure, a lactam structure, a cyclic thiourea structure, a cyclic phosphinate structure, a cyclic phosphonite structure, a cyclic phosphite structure, a vinyl structure, an allyl structure, a (meth) acrylic structure, and a cycloalkane structure. In the case of showing a group, at least two kinds of structures selected from the above group are shown.

  It is preferable from the viewpoint of further enhancing the effect of the present invention that the impurities (for example, raw materials for producing the epoxy compound, chloride, heavy metal, sodium, etc.) contained in the epoxy compound are small. After completion of the reaction for forming a thiirane ring, the episulfide compound, the unreacted epoxy compound, the compound formed by replacing the sulfur atom of the thiating agent with an oxygen atom, the thiating agent, and the polyvalent hydroxyl compound are separated and separated. When purifying, impurities need not be separated, which is preferable from the viewpoint of obtaining the high-purity compound.

As content of the impurity of an epoxy compound, 5000 ppm or less is preferable, More preferably, it is 2000 ppm or less, More preferably, it is 500 ppm or less.
It is preferable that the epoxy equivalent (WPE) of an epoxy compound is 100-600 g / eq, More preferably, it is 100-500 g / eq, More preferably, it is 100-300 g / eq.
Depending on the composition of the resin composition of the present embodiment, when the epoxy equivalent (WPE) of the epoxy compound is 100 g / eq or more, good storage stability is obtained in the fiber-reinforced resin composition of the present embodiment, and 600 g When it is / eq or less, the cured product has good physical properties.

The epoxy compound is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa · s or less.
When the viscosity at 25 ° C. is 1000 Pa · s or less, fluidity as a good liquid is obtained, and (A) the compatibility with the compound having at least one thiirane ring tends to be good.
In addition, when the viscosity at 25 ° C. is more than 500 Pa · s and 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. Since manufacturing conditions tend to be somewhat limited, it is preferably 500 Pa · s or less.

The content of the epoxy compound in the resin composition of the present embodiment is preferably 0 to 80 parts by mass, more preferably 10 to 100 parts by mass of “(A) a compound having at least one thiirane ring”. It is -70 mass parts, More preferably, it is 20-60 mass parts.
When the content of the epoxy compound is 10 parts by mass or more, an effect of cost reduction is obtained, and when it is 80 parts by mass or less, an effect of maintaining high-speed curability is obtained.

The manufacturing method of the resin composition of the present embodiment is characterized by going through the following (Step 1) and (Step 2).
(Step 1): (A) A step of blending (B) an ester compound with a compound having at least one thiirane ring.
(Process 2): The process of heat-processing after the said (process 1).

In the (step 1), the above-described component (A) and component (B) are blended. Moreover, you may mix | blend the epoxy compound mentioned above in the said (process 1) further.
The blending method is not particularly limited, but it is preferable to mix uniformly. Although the apparatus used for mixing is not limited to the following, for example, a magnetic stirrer, a propeller stirring blade, an evaporator, a rotation / revolution mixer (Sinky Corporation), a line mixer, a KRC kneader (Kurimoto Iron Works Co., Ltd.) , Polylab system (manufactured by HAKKE), "labo plast mill, nanocon mixer (manufactured by Toyo Seiki Seisakusho)", "Nauter mixer bus co kneader, extruder (manufactured by Buss)", TEM type extrusion Machine (Toshiba Machine Co., Ltd.), TEX twin-screw kneader (Japan Steel Works), PCM kneader (Ikegai Co., Ltd.), "Three roll mill, mixing roll mill, planetary mixer, kneader (Inoue Manufacturing Co., Ltd.) Made) ", Kneedex (Mitsui Mining Co., Ltd.)," MS type pressure kneader, kneader ruder (Manufactured by Moriyama Co., Ltd.) ", a Banbury mixer (manufactured by Kobe Steel, Ltd.), and the like.

The heat treatment temperature in (Step 2) is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. to 150 ° C., still more preferably 80 to 120 ° C., and even more preferably 90 to 110 ° C.
The heat treatment time in (Step 2) is not particularly limited, but is preferably 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, and further preferably 30 minutes to 2 hours.
When the heat treatment time is 10 minutes or more, the variation in the storage stabilization effect is reduced, and when the heat treatment time is 4 hours or less, the side reaction tends to be suppressed.
The apparatus used for the heat treatment is not limited to the following. And can be arbitrarily selected from these.

In (Step 1) or (Step 2), or after (Step 1) or (Step 2), a devolatilization treatment (defoaming treatment) may be further performed.
The apparatus used for the devolatilization process (defoaming process) is not particularly limited. For example, an evaporator, a glass tube oven, a thin film distillation apparatus, a rotation / revolution mixer (Sinky Corporation), a vacuum dryer, etc. Can be mentioned.

(Resin composition)
As described above, the resin composition obtained by the method for producing a resin composition of the present embodiment described above includes (A) a compound having at least one thiirane ring, and (B) an ester compound. An epoxy compound may be included.

  The alcohol content contained in the resin composition of the present embodiment is not particularly limited, but is preferably 500 ppm or less, more preferably less than 100 ppm, and even more preferably 50 ppm or less from the viewpoint of improving storage stability. .

The viscosity at 25 ° C. of the resin composition of the present embodiment is not particularly limited, but is preferably 1000 Pa · s or less, more preferably 500 Pa · s or less, still more preferably 100 Pa · s or less, Even more preferably, it is 50 Pa · s or less, and still more preferably 20 Pa · s or less.
When the viscosity at 25 ° C. is 1000 Pa · s or less, good fluidity is obtained, and compatibility with other raw materials becomes good.

The storage stability index of the resin composition of the present embodiment is not particularly limited, but the resin composition has fluidity, that is, the viscosity is 1000 Pa · s or less, and the storage stability index β Is preferably 5 or less, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1.5 or less.
Here, the “storage stability index β” can be measured by the method described in Examples described later, and specifically, is determined by the following formula.
Storage stability index β = (storage viscosity) / (starting viscosity)
In the above formula, “starting viscosity” refers to the viscosity at 25 ° C. of the resin composition immediately after production.
In the above formula, “storage viscosity” means the viscosity at 25 ° C. after the container containing the resin composition is sealed and stored at 25 ° C. for 30 days.
If the storage stability index β is 5 or less, it can be determined that the stored resin composition is excellent in handleability.

The haze that is an index of transparency of the resin composition of the present embodiment is not particularly limited, but is preferably 50% or less, more preferably 30% or less, still more preferably 10% or less, and even more preferably. 5% or less. When the haze is 50% or less, the light transmission is excellent and the photocuring reaction proceeds promptly.
Specifically, the haze after storage at 25 ° C. for 30 days is preferably 50% or less, more preferably 30% or less, still more preferably 10% or less, and even more preferably 5% or less.
The haze after storage at 60 ° C. for 7 days is preferably 50% or less, more preferably 30% or less, still more preferably 10% or less, and even more preferably 5% or less.

[Curable resin composition]
The curable resin composition of the present embodiment contains the above-described resin composition of the present embodiment and (C) a curing agent.

((C) Curing agent)
(C) The curing agent acts on (A) a compound which reacts with a compound having at least one thiirane ring to form a crosslinked structure, or (A) acts on a compound having at least one thiirane ring to accelerate the polymerization reaction. There is no particular limitation as long as it is a compound.
(C) As a hardening | curing agent, a conventionally well-known thing can be used as a hardening | curing agent of an epoxy compound, for example.
(C) The curing agent is not limited to the following, but, for example, an amine curing agent, a polyamide resin curing agent, an imidazole curing agent, a phosphorus curing agent, a polymercaptan curing agent, and an acid anhydride curing agent. , Photocuring agents, and other conventionally known curing agents.
Moreover, it is more preferable that the said (C) hardening | curing agent is a latent hardening agent mentioned later from a viewpoint of pot life maintenance.
(C) A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

<Amine-based curing agent>
Examples of the amine curing agent include aliphatic amines, aromatic amines, and modified amines.
Examples of the aliphatic amine include, but are not limited to, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, and BAMIL Ramilon C-260. Araldit HY-964 manufactured by CIBA, Mensendiamine, Isophoronediamine, Wandamin HM manufactured by Nippon Nippon Chemical Co., Ltd., Wandamin CHE-20P manufactured by Nippon Nippon Chemical Co., Ltd., 1,3-bis (aminomethyl) cyclohexane, piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0 ) Undecene-7 and its salts (for example, U-CAT SA-1, SA-102, SA-506, SA-603, SA-810, SA-831, SA-841, SA-851, SA manufactured by Sun Apro Co., Ltd.) -881), U-CAT 18X, 12XD manufactured by San Apro Co., Ltd., and the like.
Examples of the aromatic amine include, but are not limited to, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylenediamine, xylenediamine trimer, and various xylenediamine derivatives.
Examples of the modified amine include, but are not limited to, for example, a complex of polyamine and an epoxy resin (for example, Three Bond 2102, 2131B manufactured by Three Bond Co., Ltd.), the above aliphatic amine and ketones such as methyl ethyl ketone and isobutyl ketone. And ketoimine compounds obtained from the compounds.

<Polyamide resin curing agent>
Examples of the polyamide resin curing agent include, but are not limited to, polyamide amines containing primary and secondary amines (for example, Three Bond 2105, 2105C, 2105F, and 2107 manufactured by Three Bond Co., Ltd.). .

<Imidazole-based curing agent>
Examples of the imidazole curing agent include, but are not limited to, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, bisphenol A glycidyl ether. And a complex of imidazole and the like.

<Phosphoric curing agent>
Examples of the phosphorus-based curing agent include, but are not limited to, triphenylphosphine, triphenyl phosphite, and tetraphenylphosphine bromide.

<Polymercaptan curing agent>
Examples of polymercaptan curing agents include, but are not limited to, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3 -Mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, diethylene glycol bis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1, 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), liquid poly Mercaptans (for example, Three Corporation) Manufactured command, ThRee Bond 2086B), polysulfide resin (e.g. Three Bond Co., Ltd. made include THREE Bond 2104), and the like.

<Acid anhydride curing agent>
Examples of the acid anhydride curing agent include, but are not limited to, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitic acid. Tate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic acid anhydride, polyazeline acid anhydride, polyadipic acid anhydride, polysebacic acid anhydride, poly (phenylhexadecanedioic acid) anhydride , Poly (ethyloctadecandioic acid) anhydride, cyclohexene dicarboxylic acid anhydride, hexahydro-4,7-methano-2-benzofuran-1,3-dione, methylhexahydro-4,7-methano-2-benzofuran-1 , 3-dione, methyl hymic anhydride and the like.
In using these acid anhydride curing agents, it is desirable to use an amine curing agent, an imidazole curing agent, a phosphorus curing agent, a Lewis acid curing agent, or the like as a curing accelerator, if necessary.

<Photocuring agent>
The photo-curing agent refers to a curing agent that generates active species such as cations and anions by light irradiation.
Examples of the photocuring agent include, but are not limited to, the following compounds.
These may be used alone or in combination of two or more compounds.
[(1) Photoacid generator (curing agent that generates cations by light irradiation)]
Examples of the photoacid generator include, but are not limited to, various onium salts, and sulfonium salts having BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ as a counter anion, Examples include iodonium salts.
Examples of the sulfonium salt include triphenylsulfonium salt, dimethylphenylsulfonium salt, diphenylbenzylsulfonium salt, tolylylsulfonium salt, 4-butoxyphenyldiphenylsulfonium salt, tris (4-phenoxyphenyl) sulfonium salt, 4-acetoxy-phenyl. Examples thereof include diphenylsulfonium salt, tris (4-thiomethoxyphenyl) sulfonium salt, di (methoxynaphthyl) methylsulfonium salt, dimethylnaphthylsulfonium salt, and phenylmethylbenzylsulfonium salt.
Examples of the iodonium salt include diphenyliodonium salt, phenyl-2-thienyliodonium salt, di (2,4-methoxyphenyl) iodonium salt, di (3-methoxycarbonylphenyl) iodonium salt, di (4-acetamidophenyl) iodonium. Salt, (4-octyloxyphenyl) phenyliodonium salt, and the like.
Further, an iron-allene compound that generates a Lewis acid can also be used.
[(2) Photobase generator (curing agent that generates anion by light irradiation)]
Examples of the photobase generator include, but are not limited to, ammonium salts of phenylglyoxylic acid, o-nitrobenzoyl carbamate, α, α-dimethyl-3,5-dimethoxybenzyloxycarbamate, cobalt (III) alkylamine complex, zinc hydroxide + guanidine picolinate, nitrobenzyl alcohol, “benzyl alcohol-urethane compound obtained by reaction of dinitrobenzyl alcohol and isocyanate”, “nitro-1-phenylethyl alcohol or dinitro-1” -Phenyl alcohol-urethane compound obtained by reaction of phenylethyl alcohol and isocyanate "," Propanol-urethane compound obtained by reaction of dimethoxy-2-phenyl-2-propanol and isocyanate ", etc. That.
Further, JP-A-10-77264, JP-A-2005-264156, JP-A-2003-212856, JP-A-2003-20339, “UV / EB Curing Technology III (1997, CMC Publishing, P .7) "may be used.
Even when a photo-curing agent is used, an appropriate heat treatment may be performed after the light irradiation.

<Other curing agents>
Examples of other curing agents include, but are not limited to, Lewis acids, dicyandiamides, organic acid hydrazide compounds, sulfonium salts having hydrocarbon groups (for example, ADEKA OPTON CP-66, 77 manufactured by ADEKA Corporation), Examples include allene-ion complexes, aluminum chelate compounds, sulfonate esters, and imide sulfonates.

  The compounding amount of (C) the curing agent, excluding the latent curing agent described later, is not particularly limited, but is 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin composition of the present embodiment. It is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. If the said compounding quantity is 0.01 mass part or more, hardening by crosslinking reaction will advance favorably, and if it is 20 mass parts or less, since the influence of coloring etc. of hardened | cured material tends to be small, it is preferable.

<Latent curing agent>
In this embodiment, it is preferable to use a latent curing agent as the (C) curing agent.
A latent curing agent does not react with a functional group when it is normally stored (room temperature, under visible light, etc.) even if it is mixed with the main resin. A curing agent exhibiting reactive activity.
A conventionally well-known thing can be used as a latent hardening agent, It does not specifically limit.
Only one latent curing agent may be used alone, or two or more latent curing agents may be used in combination.
In this embodiment, as a latent hardener, the latent hardener activated at 70-125 degreeC, the below-mentioned photo-acid generator, a photobase generator, etc. can also be used, for example.
The latent method is not particularly limited. For example, a method of adducting by reacting an active component such as an imidazole compound or a tertiary amine with any compound capable of reacting with those compounds, Examples include a method of inclusion with dextrin and the like, and a method of microencapsulation as described later.

[Latent curing agent activated at 70 to 125 ° C.]
The latent curing agent activated at 70 to 125 ° C. is not particularly limited as long as it has such an activation temperature. For example, an anionic curing latent curing agent, an amine adduct latent curing agent, a micro Capsule type latent curing agents, amine imides, blocked isocyanates, compounds made by reacting carbamic acid esters with epoxy groups to form oxazolidinone rings, vinyl ether block carboxylic acids, salts of imidazoles and carboxylic acids, amine carbamine salts, onium salts, etc. It is done.

  Here, the anionic curing type latent curing agent does not react with the functional group under normal storage conditions, that is, at room temperature, under visible light, etc., and reacts with the functional group by heat or light. It refers to a curing agent that generates anionic species (imidazole compounds, tertiary amines, etc.) to be exhibited and advances anionic polymerization.

  Examples of the anionic curable latent curing agent are not limited to the following, but examples include “TBG-01, TBG-02 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)”, “Cureduct P-0505, L -07N (manufactured by Shikoku Kasei Kogyo Co., Ltd.) "," Novacure (manufactured by Asahi Kasei E-Materials Co., Ltd.) "," WPBG-140 (manufactured by Wako Pure Chemical Industries, Ltd.) "

Here, the amine adduct type latent curing agent is to react an active ingredient such as a compound having a primary, secondary or tertiary amino group or various imidazole compounds with any compound capable of reacting with those compounds. Refers to those having a high molecular weight and insolubilized at storage temperature.
Examples of the amine adduct type latent curing agent include, but are not limited to, for example, “Amicure PN-23, MY-24 (manufactured by Ajinomoto Fine Techno Co., Ltd.)”, “Adeka Hardener EH-3293S, EH— 3615S, EH-4070S (Asahi Denka Kogyo Co., Ltd.), “Fujicure FXE1000, FXR-1020 (Fuji Kasei Kogyo Co., Ltd.) and the like.

Moreover, when a specific hardening | curing agent is combined with the said latent hardening | curing agent, hardening of the resin composition of this embodiment may be further accelerated | stimulated.
For example, a curing agent system in which an organic acid dihydrazide such as bazine dihydrazide is combined with a latent curing agent such as “Amicure PN-23”, or a curing agent system in which a curing accelerator such as DCMU is combined with a latent curing agent. Can be mentioned.

The latent curing agent is preferably a microcapsule type latent curing agent from the viewpoint of storage stability.
A microcapsule-type latent curing agent refers to a curing agent having at least a structure in which the surface of a core containing a curing agent is covered with a shell containing an inorganic oxide or a synthetic resin.
From the viewpoint of stability of the shell, ease of destruction during heating, and uniformity of physical properties of the resulting cured product, it is preferable to have a structure in which the surface of the core is covered with a shell made of a synthetic resin.
It does not specifically limit as a hardening | curing agent used for a microcapsule-type latent hardening | curing agent, A well-known thing can be used including the epoxy resin hardening | curing agent mentioned above.
From the viewpoint of storage stability, the latent curing agent is preferably a latent curing agent having an average particle size of 10 μm or less that is solid at normal temperature.
Here, the average particle diameter means an average particle diameter measured by a laser diffraction particle size distribution measuring method.

As a method for obtaining a microcapsule type latent curing agent having an average particle diameter of 10 μm or less, for example, a commonly used epoxy resin curing agent is pulverized from a lump state into particles of a desired size using a pulverizer, and thereafter And a method of forming a shell film on the surface by a method described later and adjusting to a desired average particle diameter.
The inorganic oxide used for the shell is not limited to the following, and examples thereof include boron compounds such as boron oxide and boric acid ester, silicon dioxide, and calcium oxide. Among these, boron oxide is preferable from the viewpoints of shell stability and ease of destruction during heating.

The synthetic resin used for the shell is not limited to the following, and examples thereof include an epoxy resin, a polyester resin, a polyethylene resin, a nylon resin, a polystyrene resin, and a urethane resin.
Among these, urethane resins that are addition products of mono- or polyhydric alcohols and mono- or polyisocyanates, reaction products of amine curing agents and epoxy resins, and phenol resins are preferable. Among these, from the viewpoint of shell stability and ease of destruction during heating, a reaction product of a polyvalent isocyanate and a compound having active hydrogen (active hydrogen compound), and / or an epoxy resin and an epoxy resin curing agent The reaction product with

The polyvalent isocyanate used for the production of the synthetic resin contained in the shell may be a compound having one or more isocyanate groups in one molecule, but a compound having two or more isocyanate groups in one molecule. Is preferred. Examples of such isocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, low molecular triisocyanates, polyisocyanates, and the like.
Examples of the aliphatic diisocyanate include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
Examples of the alicyclic diisocyanate include, but are not limited to, isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanate). Natomethyl) -cyclohexane, 1,3-bis (2-isocyanatopropyl-2-yl) -cyclohexane and the like.
Examples of the aromatic diisocyanate include, but are not limited to, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate.
Examples of the low-molecular triisocyanate include, but are not limited to, for example, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene. Triisocyanate, aliphatic triisocyanate compounds such as 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl, 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl, tricyclohexylmethane triisocyanate And alicyclic triisocyanate compounds such as bicycloheptane triisocyanate, and aromatic triisocyanate compounds such as triphenylmethane triisocyanate and tris (isocyanatephenyl) thiophosphate.
Examples of the polyisocyanate include, but are not limited to, polyisocyanates derived from polymethylene polyphenyl polyisocyanate, the above diisocyanates, and low molecular triisocyanates.

Examples of the polyisocyanate derived from the above diisocyanate and low molecular triisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate and the like.
These isocyanate compounds may be used individually by 1 type, and may use 2 or more types together.

The active hydrogen compound used to produce the synthetic resin contained in the shell is not limited to the following, but includes, for example, water, one or more primary and / or secondary amino groups in one molecule. Compounds having one or more hydroxyl groups in one molecule.
These may be used alone or in combination of two or more.
Among these, water and a compound having one or more hydroxyl groups in one molecule are preferable.

The compound having one or more primary and / or secondary amino groups in one molecule is not limited to the following, but, for example, an aliphatic amine, an alicyclic amine, or an aromatic amine is used. Can do.
Examples of aliphatic amines include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine, and alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine. And polyalkylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.
Examples of alicyclic amines include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.
Examples of the aromatic amine include, but are not limited to, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.

  Examples of the compound having one or more hydroxyl groups in one molecule used as the active hydrogen compound include alcohol compounds and phenol compounds.

  Examples of the alcohol compound include, but are not limited to, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, and lauryl. Alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monoalcohols such as monoethyl ether and diethylene glycol monobutyl, ethylene glycol Polyhydric alcohols such as coal, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Can be mentioned. A secondary compound obtained by a reaction between a compound having one or more epoxy groups in one molecule and a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. Compounds having two or more hydroxyl groups in one molecule are also exemplified as polyhydric alcohols. As these alcohol compounds, any of primary, secondary, or tertiary alcohols can be used.

  Examples of the phenol compound include, but are not limited to, monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, And polyphenols such as phloroglucin.

  As the compound having one or more hydroxyl groups in one molecule, polyhydric alcohols and polyhydric phenols are preferable, and polyhydric alcohols are more preferable.

As a method for forming a shell on the surface of the core containing the curing agent, a conventionally known method can be used and is not particularly limited. For example, in a dispersion medium in which the shell component is dissolved and the curing agent is dispersed, the shell component is lowered in solubility and the shell is deposited on the surface of the curing agent, in the dispersion medium in which the epoxy resin curing agent is dispersed. Examples include a method of forming a shell by performing a shell formation reaction to deposit the shell on the surface of the epoxy resin curing agent, or using the surface of the curing agent as a reaction field.
Among these, the latter method is preferable from the viewpoint that reaction and coating can be performed simultaneously.

Examples of the dispersion medium include, but are not limited to, solvents, plasticizers, and resins.
Moreover, an epoxy resin can also be used as a dispersion medium.
Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, Examples include esters such as acetic acid-n-butyl and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and water.
Examples of the plasticizer include, but are not limited to, phthalic acid diester plasticizers such as dibutyl phthalate and di (2-ethylhexyl) phthalate, and fats such as di (2-ethylhexyl) adipate. Group dibasic acid ester plasticizers, phosphate triester plasticizers such as tricresyl phosphate, glycol ester plasticizers such as polyethylene glycol esters, and the like.
Examples of the resins include, but are not limited to, silicone resins, epoxy resins, phenol resins, and the like.

  In the method of coating the curing agent with the shell component, the epoxy resin that can be used as a dispersion medium is not limited to the following, but examples thereof include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, Bisphenol-type epoxy resins obtained by glycidylating bisphenols such as tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A; biphenol, dihydroxynaphthalene, dihydroxybenzene, Epoxy resin obtained by glycidylation of other dihydric phenols such as 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris Epoxy resin obtained by glycidylation of trisphenols such as 4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol; 1 , 1,2,2, -tetrakis (4-hydroxyphenyl) ethane and other glycidylated epoxy resins; phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak Novolak epoxy resins obtained by glycidylation of novolaks; epoxy resins obtained by glycidylation of polyhydric phenols, aliphatic ether type epoxy resins obtained by glycidylation of polyhydric alcohols such as glycerin and polyethylene glycol; p-oxy Ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as benzoic acid and β-oxynaphthoic acid; Ester type epoxy resin obtained by glycidylation of polycarboxylic acid such as phthalic acid and terephthalic acid; 4,4-diaminodiphenylmethane And glycidyl compounds of amine compounds such as m-aminophenol, glycidyl type epoxy resins such as amine type epoxy resins such as triglycidyl isocyanurate, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate And alicyclic epoxides. Among these, from the viewpoint of increasing the storage stability of the resin composition, a glycidyl type epoxy resin is preferable, and from the viewpoint of excellent electrical reliability of the cured product, an epoxy resin obtained by glycidylating polyhydric phenols is more preferable. Bisphenol type epoxy resins are more preferred, epoxy resins obtained by glycidylating bisphenol A and epoxy resins obtained by glycidylating bisphenol F are more preferred, and epoxy resins obtained by glycidylating bisphenol A are even more preferred.

In the method in which the surface of the curing agent is used as a reaction field and the shell is formed there, the reaction when the isocyanate compound and the active hydrogen compound are used as the shell forming material is usually in the temperature range of −10 ° C. to 150 ° C. It is carried out with a reaction time of min to 12 hours.
The ratio of the isocyanate compound and the active hydrogen compound is not particularly limited. Usually, the equivalent ratio of the isocyanate group in the isocyanate compound to the active hydrogen in the active hydrogen compound is used in the range of 1: 0.1 to 1: 1000. It is done.

As the shell of the microcapsule type latent curing agent in the present embodiment, the reaction in the case of using a shell composed of a reaction product of a curing agent and an epoxy resin is usually 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C. The reaction is carried out in the temperature range for a reaction time of 1 to 168 hours, preferably 2 to 72 hours, and can be carried out in a dispersion medium.
As the dispersion medium, a solvent, a plasticizer, or the like can be used. Moreover, epoxy resin itself can also be used as a dispersion medium.
Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, Examples include esters such as acetic acid-n-butyl and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and water.
Examples of the plasticizer include, but are not limited to, for example, phthalic acid diesters such as dibutyl phthalate and di (2-ethylhexyl) phthalate, and aliphatic diesters such as di (2-ethylhexyl) adipate. Examples thereof include basic acid ester systems, phosphate triester systems such as tricresyl phosphate, and glycol ester systems such as polyethylene glycol esters. Examples of the resins include silicone resins, epoxy resins, phenol resins and the like.
As a method of coating the core with a shell made of a reaction product of a curing agent and an epoxy resin, for example, the shell component is dissolved and the solubility of the shell component is lowered in a dispersion medium in which the curing agent is dispersed. A method of depositing a shell on the surface of a curing agent; a method of depositing a shell on the surface of a curing agent by carrying out a shell formation reaction in a dispersion medium in which the curing agent is dispersed; Therefore, there is a method for generating a shell.
Among these, the latter two methods are preferable from the viewpoint that reaction and coating can be performed simultaneously.
In the latter case, the curing agent of this embodiment may be added separately.

The thickness of the shell is not particularly limited, but an average layer thickness of 5 to 1000 nm is preferable.
When the average layer thickness is 5 nm or more, excellent storage stability is obtained, and when it is 1000 nm or less, practical curability is obtained.
The thickness of a layer here is measured with a transmission electron microscope. A particularly preferable shell thickness is 50 to 700 nm as an average layer thickness.

  Among the microcapsule-type latent curing agents, from the viewpoints of storage stability and low temperature / short-time properties, those containing an imidazole compound that are amine adduct curing agents having a core and a shell are more preferable. Furthermore, a capsule-type imidazole, 2-methylimidazole-modified, or 2-phenylimidazole-modified amine adduct curing agent is even more preferable.

In the resin composition of the present embodiment, the ratio of the latent curing agent used is (C) latent curing with respect to 1 equivalent of the total amount of thiirane and oxirane rings in the compound having at least one thiirane ring. The functional group having active hydrogen in the agent is preferably in the range of 0.001 to 10 equivalents, more preferably in the range of 0.01 to 5 equivalents, and still more preferably in the range of 0.005 to 1 equivalents. is there.
When the functional group having active hydrogen in the latent curing agent is 0.001 equivalent or more, an effect that the curing reaction proceeds stably is obtained, and when it is 10 equivalent or less, appropriate cured physical properties are obtained. .

  The microcapsule-type latent curing agent is not limited to the following, for example, “Novacure HX-3088, HX-3613, HX-3721, HX-3722, HX-3741, HX-3742, HX- 3748, HXA3792 and the like (manufactured by Asahi Kasei E-Materials Co., Ltd.) "and the like.

[Photoacid generator]
Among the photoacid generators described above, the photoacid generator that is a latent curing agent includes a compound that generates an acid upon irradiation with active energy rays such as visible light and ultraviolet light, and is not particularly limited. However, a compound sensitive to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm is preferred.
In addition, a photoacid generator that does not directly respond to an active energy ray having a wavelength of 300 nm or more can be used as long as it is a compound that generates an acid by reacting with an active ray having a wavelength of 300 nm or more when used in combination with a sensitizer. It can be preferably used in combination.
Photoacid generators that are latent curing agents include, but are not limited to, for example, trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonates. Examples thereof include compounds, oxime sulfonate compounds, compounds disclosed in JP2011-221494A and JP2014-96563A.

[Photobase generator]
Among the photobase generators described above, the photobase generator that is a latent curing agent includes a compound that generates a base by irradiation with active energy rays such as visible light and ultraviolet rays, and is not particularly limited. Examples of the base to be generated include compounds that generate amine compounds, imidazole compounds, and phosphine compounds.
Examples of the photobase generator include, but are not limited to, N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, and N- (4-nitrobenzyl). Oxycarbonyl) imidazole, N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4,5-dimethyl-2-nitrobenzyl) Imidazole derivatives such as oxycarbonyl) imidazole, N- (2-methyl-2-phenylpropionyloxy) -N-cyclohexylamine, compounds disclosed in JP 2012-1453 A, and Table 2005/14696 be able to.
As a method for producing these photobase generators, known methods can be used. For example, the photobase generator can be synthesized by reacting a nitrobenzyl alcohol derivative with carbonyldiimidazole as a raw material.
The proportion of the photobase generator used is not particularly limited as long as the curable composition is cured well and a satisfactory cured product is obtained. Preferably, (A) at least one thiirane is used. The photobase generator is 0.03 to 0.2 equivalent with respect to 1 equivalent of the total amount of thiirane ring and oxirane ring in the compound having a ring. When the photobase generator is 0.03 equivalent or more, curing tends to proceed rapidly, and when it is 0.2 equivalent or less, generation of components other than the base generated by photolysis tends to be suppressed. is there.

The curable resin composition of this embodiment preferably has a pot life viscosity of 100 Pa · s or less.
The pot life viscosity is a viscosity at 25 ° C. after storage for 1 hour under a temperature condition of 25 ° C. The pot life viscosity can be measured by the method described in [Example] described later.
The pot life viscosity is not particularly limited, but is preferably 100 Pa · s or less, more preferably, from the viewpoint of handleability when producing a cured product using the curable resin composition of the present embodiment. 80 Pa · s or less, more preferably 50 Pa · s or less, and even more preferably 30 Pa · s or less.
As described above, since the pot life viscosity is 100 Pa · s or less, the resin composition has good characteristics in maintaining fluidity, and is constant when considering a manufacturing process using a large facility in industrialization. The ability of the resin composition to maintain fluidity over time is very advantageous from the viewpoint of productivity.

The curable resin composition of the present embodiment has a gel time at 100 ° C. of preferably 15 minutes or less, more preferably 10 minutes or less, still more preferably 300 seconds or less, and even more preferably 180 seconds or less, from the viewpoint of fast curing. More preferably, it is 60 seconds or less.
Similarly, the gel time at 150 ° C. is not particularly limited, but is preferably 180 seconds or less, more preferably 120 seconds or less, still more preferably 60 seconds or less, and even more preferably 30 seconds or less.
Here, the gel time is the time for the sample to lose its fluidity and gel under the temperature setting condition of 100 ° C. or 150 ° C. according to the hot plate method of JIS C2105: 2006 (Test method for solvent-free liquid resin for electrical insulation). It can measure by the method described in the Example mentioned later.

Although the curable resin composition of this embodiment is not specifically limited, It is preferable that it is a thermosetting resin composition or an energy-beam curable composition. Among the energy ray curable compositions, a photocurable resin composition is particularly preferable.
In order to make the resin composition of this embodiment into a thermosetting resin composition, a thermosetting resin component is selected as (A) component.
Since the resin composition of the present embodiment is a thermosetting resin composition, it is possible to cure opaque resin compositions and materials that are opaque to light. It can also be applied to the manufacture of FRP.
In order to make the resin composition of this embodiment into a photocurable resin composition, a photocurable resin component is selected as (A) component. In the case of a photocurable resin composition, transparency is important.

(Curing accelerator)
The curable resin composition of this embodiment may further contain a curing accelerator.
Here, the curing accelerator refers to a substance having an effect of lowering the curing temperature or a substance having an effect of increasing the curing reaction rate.
Examples of the curing accelerator include, but are not limited to, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol. , Tertiary amines such as tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine Organic phosphines such as triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpho Tetraphenyl boron salts such as down-tetraphenylborate and the like.
Although the compounding quantity of a hardening accelerator is not specifically limited, When the compound which has (A) at least 1 thiirane ring is 100 mass parts, Preferably it is 0.001-10 mass parts, More preferably, it is 0.01. -5 parts by mass.

(Curable compound)
The curable resin composition of this embodiment may further contain (A) a curable compound capable of reacting with a compound having at least one thiirane ring.
As a curable compound, a polyfunctional epoxy compound, a polyfunctional vinyl compound, an acid anhydride, a sulfur containing compound etc. are mentioned, for example.
These curable compounds can be used alone or in combination of two or more.

  Examples of the polyfunctional epoxy compound include, but are not limited to, dicyclopentadiene dioxide, limonene dioxide, di (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexanecarboxylic acid 2 , 3-epoxypropyl, 3,4-epoxy-6-methylcyclohexanecarboxylic acid 2,3-epoxypropyl, 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclohexyl) methyl, 3,4-epoxy-6 -Methylcyclohexanecarboxylic acid (3,4-epoxy-6-methylcyclohexyl) methyl, ethylene-1,2-di (3,4-epoxycyclohexanecarboxylate), bicyclohexa-3,3'-diene dioxide, etc. Epoxy compound having cycloaliphatic skeleton, grease Epoxidized acrylates and methacrylates such as dil methacrylate, 2-methyl-glycidyl methacrylate, 3,4-epoxyisoprenyl methacrylate, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine- Trifunctional epoxy compounds such as 2,4,6 (1H, 3H, 5H) -trione, diglycidyl ethers of various bisphenols, glycidyl ethers of hydrogenated bisphenols, glycidyl ethers of novolac type phenol resins, polycyclic aromatic Examples thereof include glycidyl ether and a silicone compound having an epoxy group.

  Examples of the polyfunctional vinyl compound include, but are not limited to, dicyclopentadiene, limonene, di (3-cyclohexenyl) adipate, (3-cyclohexenyl) methyl-3-cyclohexene carboxylate, (6 Cycloaliphatic skeletons such as -methyl-3-cyclohexenyl) methyl-6-methyl-3-cyclohexenecarboxylate, ethylene-1,2-di (3-cyclohexenecarboxylate), bicyclohexa-3,3'-diene Vinyl compounds, vinyl methacrylate, allyl methacrylate, vinylated acrylates and methacrylates such as 2-methyl-vinyl methacrylate, 2-methyl-allyl methacrylate, 1,3,5-triallyl-1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -G Trifunctional vinyl compounds such as ON, vinyl and allyl ethers of various bisphenols, vinyl and allyl ethers of hydrogenated aromatic bisphenols, vinyl and allyl ethers of novolac type phenol resins, polycyclic aromatic vinyls and allyl ethers, vinyl groups And a silicone compound having an allyl group.

  Examples of acid anhydrides include, but are not limited to, polyazeline acid anhydride, polyadipic acid anhydride, dodecenyl succinic anhydride, polysebacic acid anhydride, poly (phenylhexadecanedioic acid) anhydride, poly (Ethyloctadecanedioic acid) and other aliphatic carboxylic acid anhydrides and carboxylic acids, cyclohexene dicarboxylic acid anhydrides, methylcyclohexene dicarboxylic acid anhydrides, hexahydro-4,7-methano-2-benzofuran-1,3- Dione, methylhexahydro-4,7-methano-2-benzofuran-1,3-dione, trialkyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, methylhexahydrophthalic anhydride Alicyclics such as acid and methylhexahydrophthalic anhydride Carboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, aromatic carboxylic acid anhydrides such as glycerol tristrimellitate and the like.

  Examples of the sulfur-containing compound include, but are not limited to, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3- Mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, diethylene glycol bis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3 , 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), liquid polypercaptan ( For example, ThreeBond Co., Ltd. , ThRee Bond 2086B), polysulfide resin (e.g. Three Bond Co., Ltd. made include THREE Bond 2104), and the like.

(Photo radical initiator)
The curable resin composition of this embodiment may further contain a photo radical initiator.
The photo-radical initiator may be any compound that generates radicals upon irradiation with active energy rays such as visible light and ultraviolet rays, irradiation with actinic rays or radiation, and is not limited to the following. For example, acetophenones Benzoins, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, oxime esters, etc. Is used. Specific examples of the photo radical initiator include 2,2′-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxydimethylphenyl ketone, 2-methyl-4′-methylthio-2. -Morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 1,2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane Acetophenones such as -1-one, α-hydroxyacetophenone, α-aminoacetophenone; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethylletal; benzophenone, 2,4′- Dichlorobenzophenone, 4,4'-dic Benzophenones such as lobenzophenone and p-chlorobenzophenone; 1,2-octanedione-1- [4- (phenylthio) -2- (0-pentoyloxime)], ethanone-1- [9-ethyl-6- ( Examples include oxime esters such as 2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0 monoacetyloxime).

(Chain transfer agent)
The curable resin composition of this embodiment may further contain a chain transfer agent.
By using a chain transfer agent in combination, the obtained cured product or FRP has a reduced volatile content when held for a long time at a high temperature, and generation of voids during molding by melt processing, or in the vicinity of the polymer or cured product In some cases, contamination or corrosion of a metal member can be further suppressed.
As the chain transfer agent, those generally used can be used, and are not limited to the following, but for example, at least selected from the group consisting of a cyclic ester compound, a cyclic carbonate compound, a cyclic siloxane compound, and a hydroxyl group-containing compound. One type of compound is preferable.
These may be used alone or in combination of two or more.
The chain transfer agent is preferably at least one compound selected from the group consisting of a cyclic ester compound, a cyclic carbonate compound and a hydroxyl group-containing compound from the viewpoint of easy availability, and is a hydroxyl group-containing compound. It is more preferable.

The cyclic ester compound as the chain transfer agent may be a compound having an ester group in the cyclic structure, and is not limited to the following. For example, ethano-2-lactone, propano-2-lactone, propano -3-lactone, butano-2-lactone, butano-3-lactone, butano-4-lactone, 3-methyl-butano-4-lactone, pentano-2-lactone, pentano-3-lactone, pentano-4-lactone , Pentano-5-lactone, 4-methyl-pentano-4-lactone, hexano-2-lactone, hexano-3-lactone, hexano-4-lactone, hexano-5-lactone, hexano-6-lactone, heptano-2 -Lactone, heptano-3-lactone, heptano-4-lactone, heptano-5-lactone, heptano-6 Kuton, heptano-7-lactone, octano-2-lactone, octano-3-lactone, octano-4-lactone, octano-5-lactone, octano-6-lactone, octano-7-lactone, octano-8-lactone, Nonano-2-lactone, Nonano-3-lactone, Nonano-4-lactone, Nonano-5-lactone, Nonano-6-lactone, Nonano-7-lactone, Nonano-8-lactone, Nonano-9-lactone, Decano- 2-lactone, decano-3-lactone, decano-4-lactone, decano-5-lactone, decano-6-lactone, decano-7-lactone, decano-8-lactone, decano-9-lactone, decano-10- Lactone, undecano-2-lactone, undecano-3-lactone, undecano-4-lactone, undecano 5-lactone, undecano-6-lactone, undecano-7-lactone, undecano-8-lactone, undecano-9-lactone, undecano-10-lactone, undecano-11-lactone, dodecano-2-lactone, dodecano-3-lactone Lactone, dodecano-4-lactone, dodecano-5-lactone, dodecano-6-lactone, dodecano-7-lactone, dodecano-8-lactone, dodecano-9-lactone, dodecano-10-lactone, dodecano-11-lactone, Dodecano-12-lactone, tridecano-2-lactone, tridecano-3-lactone, tridecano-4-lactone, tridecano-5-lactone, tridecano-6-lactone, tridecano-7-lactone, tridecano-8-lactone, tridecano- 9-lactone, tridecano-1 0-lactone, tridecano-11-lactone, tridecano-12-lactone, tridecano-13-lactone, tetradecano-2-lactone, tetradecano-3-lactone, tetradecano-4-lactone, tetradecano-5-lactone, tetradecano-6 Lactone, tetradecano-7-lactone, tetradecano-8-lactone, tetradecano-9-lactone, tetradecano-10-lactone, tetradecano-11-lactone, tetradecano-12-lactone, tetradecano-13-lactone, tetradecano-14-lactone, Pentadecano-2-lactone, pentadecano-3-lactone, pentadecano-4-lactone, pentadecano-5-lactone, pentadecano-6-lactone, pentadecano-7-lactone, pentadecano-8-lactone Pentadecano-9-lactone, pentadecano-10-lactone, pentadecano-11-lactone, pentadecano-12-lactone, pentadecano-13-lactone, pentadecano-14-lactone, pentadecano-15-lactone, hexadecano-2-lactone, hexadecano- 3-lactone, hexadecano-4-lactone, hexadecano-5-lactone, hexadecano-6-lactone, hexadecano-7-lactone, hexadecano-8-lactone, hexadecano-9-lactone, hexadecano-10-lactone, hexadecano-11 Examples include lactone, hexadecano-12-lactone, hexadecano-13-lactone, hexadecano-14-lactone, hexadecano-15-lactone, hexadecano-16-lactone, and the like.
Among these, since it tends to be suppressed from remaining in a cured product or FRP, butano-4-lactone, pentano-4-lactone, pentano-5-lactone, hexano-4-lactone, hexano-6-lactone, heptano More preferred are -4-lactone, heptano-7-lactone, octano-4-lactone, octano-8-lactone, decano-10-lactone, dodecano-12-lactone, tetradecano-14-lactone, hexadecano-16-lactone, Butano-4-lactone, pentano-4-lactone, and hexano-4-lactone are preferred.

The cyclic carbonate compound as the chain transfer agent may be a compound having a carbonate group in the cyclic structure, and is not limited to the following. For example, ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, Hexylene carbonate, heptylene carbonate, octylene carbonate, nonylene carbonate, decylene carbonate, undecylene carbonate, dodecylene carbonate, tridecylene carbonate, tetradecylene carbonate, pentadecylene carbonate, hexadecylene carbonate, propyl- 1,3-dioxolan-2-one, butyl-1,3-dioxolan-2-one, pentyl-1,3-dioxolan-2-one, hexyl-1,3-dioxolane- -One, cyclohexyl-1,3-dioxolan-2-one, 1,3-dioxane-2-one, methyl-1,3-dioxan-2-one, dimethyl-1,3-dioxan-2-one, ethyl -1,3-dioxan-2-one, propyl-1,3-dioxan-2-one, butyl-1,3-dioxan-2-one, pentyl-1,3-dioxan-2-one, hexyl-1 , 3-dioxan-2-one, cyclohexyl-1,3-dioxan-2-one, and the like.
In particular, since it tends to be suppressed in the cured product and FRP, ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate, propyl-1,3-dioxolan-2-one, butyl- 1,3-dioxolan-2-one, 1,3-dioxan-2-one, dimethyl-1,3-dioxan-2-one, ethyl-1,3-dioxan-2-one, propyl-1,3- Dioxane-2-one and butyl-1,3-dioxan-2-one are more preferred, and ethylene carbonate, propylene carbonate, butylene carbonate, 1,3-dioxane-2-one, dimethyl-1,3-dioxane-2- Preferred is ON.

The cyclic siloxane compound as the chain transfer agent may be a compound in which the cyclic structure is formed by a siloxane bond, and is not limited to the following, for example, trimethylcyclotrisiloxane, triethylcyclotrisiloxane, tripropyl Cyclotrisiloxane, tributylcyclotrisiloxane, tripentylcyclotrisiloxane, trihexylcyclotrisiloxane, triheptylcyclotrisiloxane, trioctylcyclotrisiloxane, trinonylcyclotrisiloxane, tridecylcyclotrisiloxane, triphenylcyclotrisiloxane, Hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexapropylcyclotrisiloxane, hexabutylcyclotrisiloxane, hexapentyl Trisiloxane, hexahexylcyclotrisiloxane, hexaheptylcyclotrisiloxane, hexaoctylcyclotrisiloxane, hexanonylcyclotrisiloxane, hexadecylcyclotrisiloxane, hexaphenylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, tetramethylcyclotetra Siloxane, tetraethylcyclotetrasiloxane, tetrapropylcyclotetrasiloxane, tetrabutylcyclotetrasiloxane, tetrapentylcyclotetrasiloxane, tetrahexylcyclotetrasiloxane, tetraheptylcyclotetrasiloxane, tetraoctylcyclotetrasiloxane, tetranonylcyclotetrasiloxane, tetra Decylcyclotetrasiloxane, tetraphenylcyclote Lasiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octapropylcyclotetrasiloxane, octabutylcyclotetrasiloxane, octapentylcyclotetrasiloxane, octahexylcyclotetrasiloxane, octaheptylcyclotetrasiloxane, octaoctylcyclotetrasiloxane , Octanonylcyclotetrasiloxane, octadecylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, pentamethylcyclopentasiloxane, pentaethylcyclopentasiloxane, pentapropylcyclopentasiloxane, pentabutylcyclopentasiloxane, Pentapentylcyclopentasiloxane, pentahex Silcyclopentasiloxane, pentaheptylcyclopentasiloxane, pentaoctylcyclopentasiloxane, pentanonylcyclopentasiloxane, pentadecylcyclopentasiloxane, pentaphenylcyclopentasiloxane, decamethylcyclopentasiloxane, decaethylcyclopentasiloxane, decapropylcyclo Pentasiloxane, decabutylcyclopentasiloxane, decapentylcyclopentasiloxane, decahexylcyclopentasiloxane, decaheptylcyclopentasiloxane, decaoctylcyclopentasiloxane, decanonylcyclopentasiloxane, decadecylcyclopentasiloxane, decaphenylcyclopentasiloxane And pentamethylpentaphenylcyclopentasiloxane.
In particular, since it tends to be suppressed from remaining in a cured product or FRP, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexapropylcyclotrisiloxane, hexabutylcyclotrisiloxane, hexapentylcyclotrisiloxane, hexa Hexylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octapropylcyclotetrasiloxane, octabutylcyclotetrasiloxane, octapentylcyclotetrasiloxane, octahexylcyclotetrasiloxane, tetramethyl Tetraphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, decaethylcyclopentasiloxane, decapropyl Clopentasiloxane, decabutylcyclopentasiloxane, decapentylcyclopentasiloxane, decahexylcyclopentasiloxane, and pentamethylpentaphenylcyclopentasiloxane are more preferred, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane Are preferred.

The hydroxyl group-containing compound as the chain transfer agent is not particularly limited as long as it is a compound having a hydroxyl group in the structure.
However, the hydroxyl group-containing compound, as a chain transfer agent, has the effect of improving the curing rate, but depending on the substance, it may promote the opening of a thiirane ring as a proton donor, and may reduce storage stability. Depending on the storage environment and application, it is preferable to limit the content in the fiber-reinforced resin composition.
In particular, since the tendency is remarkable with alcohol, when using a hydroxyl-containing compound as a chain transfer agent, the content of alcohol is preferably 100 ppm or less, more preferably 50 ppm or less in the resin composition.
Examples of the hydroxyl group-containing compound include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, cyclopropanol, methylcyclopropanol, dimethylcyclopropanol, ethylcyclopropanol, propylcyclopropanol, and butyl. Cyclopropanol, 1-butanol, 2-butanol, tert-butanol, cyclobutanol, methylcyclobutanol, dimethylcyclobutanol, ethylcyclobutanol, propylcyclobutanol, butylcyclobutanol, 1-pentanol, 2-pentanol, 3- Pentanol, cyclopentanol, methylcyclopentanol, dimethylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, butylsilane Lopentanol, methyl-1-butanol, methyl-2-butanol, dimethyl-1-butanol, dimethyl-2-butanol, ethyl-1-butanol, ethyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, Cyclohexanol, methylcyclohexanol, dimethylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, methyl-1-pentanol, methyl-2-pentanol, methyl-3-pentanol, dimethyl-1-pentanol Dimethyl-2-pentanol, dimethyl-3-pentanol, ethyl-1-pentanol, ethyl-2-pentanol, ethyl-3-pentanol, 1-heptanol, 2-heptanol, 3-heptanol Cycloheptanol, methylcycloheptanol, dimethylcycloheptanol, ethylcycloheptanol, methyl-1-hexanol, methyl-2-hexanol, methyl-3-hexanol, dimethyl-1-hexanol, dimethyl-2-hexanol, ethyl -1-hexanol, ethyl-2-hexanol, ethyl-3-hexanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, cyclooctanol, methylcyclooctanol, dimethylcyclooctanol, ethylcyclooctanol, nonanol, Cyclononanol, decanol, cyclodecanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, ethylene glycol, 1 , 2-propanediol, 1,3-propanediol, methylpropanediol, dimethylpropanediol, cyclopropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, methylbutanediol, dimethylbutanediol, cyclobutanediol, methylcyclobutanediol, dimethylcyclobutanediol, ethylcyclobutanediol, propylcyclobutanediol, butylcyclobutanediol, 1,2-pentanediol, 1,3-pentanediol, 1, 4-pentanediol, 1,5-pentanediol, methylpentanediol, dimethylpentanediol, cyclopentanediol, methylcyclopentanediol, dimethylcyclopentanedio , Ethylcyclopentanediol, propylcyclopentanediol, butylcyclopentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexane Diol, methylhexanediol, dimethylhexanediol, cyclohexanediol, methylcyclohexanediol, dimethylcyclohexanediol, ethylcyclohexanediol, propylcyclohexanediol, butylcyclohexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4 -Heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, cycloheptanediol, methylcycloheptanediol, Methylcycloheptanediol, 1,2-octanediol, 1,3-octanediol, 1,4-octanediol, 1,5-octanediol, 1,6-octanediol, 1,7-octanediol, 1,8 -Octanediol, cyclooctanediol, methylcyclooctanediol, dimethylcyclooctanediol, nonanediol, cyclononanediol, decanediol, cyclodecanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanediol, hexadecanediol Glycerol, erythritol, xylitol, mannitol, boremitol, glucose, sucrose, diethylene glycol, triethylene glycol, tetraethylene glycol, Pentaethylene glycol, hexaethylene glycol, octaethylene glycol, dodecaethylene glycol, methylal, PEG200, PEG300, PEG400, PEG600, PEG1000, PEG1500, PEG1540, PEG4000, PEG6000, polycarbonate diol, polyester-8-hydroxy-1-acetylene bis- MPA dendron generation 3 (product name, manufactured by Aldrich), polyester-16-hydroxy-1-acetylene bis-MPA dendron generation 4 (product name, manufactured by Aldrich), polyester-32-hydroxy-1-acetylene bis-MPA dendron Generation 5 (product name, manufactured by Aldrich), polyester-8-hydroxy 1-carboxyl bis-MPA dendron generation 3 (product name, manufactured by Aldrich), polyester-16-hydroxy-1-carboxyl bis-MPA dendron generation 4 (product name, manufactured by Aldrich), polyester-32-hydroxy-1- Carboxyl bis-MPA dendron generation 5 (product name, manufactured by Aldrich), hyperbranched bis-MPA polyester-16-hydroxyl, generation 2 (product name, manufactured by Aldrich), hyperbranched bis-MPA polyester-32-hydroxyl , Generation 3 (product name, manufactured by Aldrich) and the like.
In particular, from the viewpoint of easy availability, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, 1- Hexanol, 2-hexanol, 3-hexanol, cyclohexanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, cyclopentanediol, 1,2-hexanediol, 1,3 -Hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6- Xanthdiol, cyclohexanediol, glycerol and methylal are preferred, and 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, cyclopentanol, 2-hexanol, 3-hexanol, cyclohexanol, ethylene glycol, 1, Preferable examples include 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and methylal.

(Antioxidant)
The resin composition or the curable resin composition of this embodiment may further contain an antioxidant.
Although antioxidant is not limited to the following, for example, it mentions later (1) phenolic antioxidant, (2) phosphorus antioxidant, (3) sulfur antioxidant, and (4) An amine antioxidant is mentioned.
Only one type of antioxidant may be used alone, or two or more types may be used in combination.

<(1) Phenolic antioxidant>
Examples of the phenol-based antioxidant include, but are not limited to, for example, the following alkylphenols, hydroquinones, thioalkyl or thioaryls, bisphenols, benzyl compounds, triazines, β- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionic acid and monovalent or polyhydric ester, β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and monovalent or polyvalent Esters with alcohol, β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and monovalent or polyhydric alcohol, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monovalent Or an ester with a polyhydric alcohol, β- (3,5-di-tert-butyl-4-hydro Shifeniru) -propionic acid, and vitamins are exemplified.

[(1-1) Alkylphenols]
Examples of the alkylphenols include, but are not limited to, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-diphenol. -Tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4- Methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl -4-methoxymethylphenol, nonylphenols having a linear or branched side chain (for example, 2,6-di-no- 4-methylphenol), 2,4-dimethyl-6- (1′-methylundec-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadeca-1′-yl) Phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof, 4-hydroxylauranilide, 4-hydroxystearanilide, and octyl N- (3,5-di- -Tert-butyl-4-hydroxyphenyl) carbamate and the like.

[(1-2) Hydroquinones]
Examples of hydroquinones include, but are not limited to, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert. -Amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- Examples thereof include butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[(1-3) thioalkyl or thioaryls]
Examples of thioalkyl or thioaryls include, but are not limited to, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4- Dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4 -Octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3 , 6-Di-sec-amylphenol) and 4,4′-bis (2,6-dimethyl-4-hydroxyphenyl) disulfi. Etc. The.

[(1-4) Bisphenols]
Examples of the bisphenols include, but are not limited to, 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4), for example. -Ethylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2, 2′-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4 -Nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'- Methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5) -Methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl) -4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl- '-Hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-) Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert- Butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane and 1,1,5,5-tetra (5 -Tert-butyl-4-hydroxy-2-methylphenyl) pentane and the like.

[(1-5) benzyl compounds]
Examples of benzyl compounds include, but are not limited to, 3,5,3 ′, 5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert -Butyl-4-hydroxybenzyl mercaptoacetate, dioctadecyl-2,2-bis (3 5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di- tert-butyl-4-hydroxybenzyl) malonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis ( 3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-tert Butyl-4-hydroxybenzyl) phenol, and the like.

[(1-6) Triazines]
The triazines are not limited to the following, but include, for example, 2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3. , 5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6- Bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3) -Hide Xyl-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3, 5-Tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine and 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) And isocyanurates.

[(1-7) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and ester of monohydric or polyhydric alcohol]
The ester of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and a monohydric or polyhydric alcohol is not limited to the following, for example, β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol , 3-thiapentadecanol, Esters such as mono- or polyhydric alcohols selected from methylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane, and the like Can be mentioned.

[(1-8) β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and ester of mono- or polyhydric alcohol]
The ester of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and a monohydric or polyhydric alcohol is not limited to the following, but for example, β- (5- tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol , 3-thiapentadecano , Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and 3,9-bis [2- {3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like Or ester with a polyhydric alcohol etc. are mentioned.

[(1-9) β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and ester of mono- or polyhydric alcohol]
The ester of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and a monohydric or polyhydric alcohol is not limited to the following. For example, β- (3,5-dicyclohexyl- 4-hydroxyphenyl) propionic acid, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oximide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trime Trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] esters with mono- or polyhydric alcohols selected from octane.

[Ester of (1-10) 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monohydric or polyhydric alcohol]
Examples of esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monohydric or polyhydric alcohols are not limited to the following. For example, 3,5-di-tert-butyl- 4-hydroxyphenylacetic acid, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, Triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, as well as Examples thereof include esters with monohydric or polyhydric alcohols selected from 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

[Amide of (1-11) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid]
Examples of amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid include, but are not limited to, for example, N, N′-bis (3,5-di- tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N′-bis (3 5-Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide and N, N′-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide Etc.

[(1-12) Vitamins]
Examples of vitamins include, but are not limited to, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof, tocotrienol, and ascorbic acid.

<(2) Phosphorous antioxidant>
(2) Examples of phosphorus antioxidants include the following phosphonates, phosphites and oxaphosphaphenanthrenes.

[(2-1) Phosphonates]
Examples of phosphonates include, but are not limited to, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4- Hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, tetrakis (2,4 -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonate and calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[(2-2) Phosphites]
Examples of phosphites include, but are not limited to, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, tris (2,4-di-tert-butyl). Phenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl) -5-tert-butyl-4-hydroxyphenyl) butanediphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, tetra (tridecyl) -4,4'-butylidenebis ( 3-methyl-6-tert- Tilphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono- and di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol poly Phosphite, bis (octylphenyl) -bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4′-isopropylidenedi Phenol-pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Tris [4,4′-isopropylidenebis (2- ert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-stearoyloxyisopropyl) phosphite, and 4,4′-isopropylidenebis ( 2-tert-butylphenol) -di (nonylphenyl) phosphite and the like.

[(2-3) Oxaphosphaphenanthrenes]
Examples of oxaphosphaphenanthrenes include, but are not limited to, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-chloro-9, And 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide It is done.

<(3) Sulfur-based antioxidant>
(3) As the sulfur-based antioxidant, the following dialkylthiopropionates, esters of octylthiopropionic acid and polyhydric alcohol, esters of laurylthiopropionic acid and polyhydric alcohol, and stearylthiopropionic acid and Examples include esters with polyhydric alcohols.

[(3-1) Dialkylthiopropionates]
Examples of dialkylthiopropionates include, but are not limited to, dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.

[(3-2) Esters of Octylthiopropionic Acid and Polyhydric Alcohol]
Examples of the ester of octylthiopropionic acid and polyhydric alcohol include, but are not limited to, for example, octylthiopropionic acid, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate. And esters with a polyhydric alcohol selected from the above.

[Ester of (3-3) Laurylthiopropionic Acid and Polyhydric Alcohol]
The ester of lauryl thiopropionic acid and polyhydric alcohol is not limited to the following, but examples include lauryl thiopropionic acid and glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, and trishydroxyethyl isocyanate. Examples include esters with nurate.

[Ester of (3-4) stearylthiopropionic acid and polyhydric alcohol]
Examples of esters of stearyl thiopropionic acid and polyhydric alcohols include, but are not limited to, stearyl thiopropionic acid, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, and trishydroxyethyl isocyanurate. And esters with a polyhydric alcohol selected from the above.

<(4) Amine-based antioxidant>
(4) The amine-based antioxidant is not limited to the following. For example, N, N′-di-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p- Phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'- Bis (1-methylheptyl) -p-phenylenediamine, N, N′-dicyclohexyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N, N′-bis (2-naphthyl) -p -Phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-mes Tilheptyl) -N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N′-dimethyl-N, N ′ -Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamine (eg, p, p′-di-tert-octyldiphenylamine), 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodeca Noylaminophenol, 4- Kutadecanoylaminophenol, bis (4-methoxyphenyl) -amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N , N, N ′, N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o- Tolyl) biguanide, bis [4- (1 ′, 3′-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mono- and di-alkylated tert-butyl- / tert-octyldiphenylamine A mixture of mono- and di-alkylated nonyldiphenylamine, mono- and di-alkyl A mixture of dodecyldiphenylamine, a mixture of mono- and di-alkylated isopropyl / isohexyldiphenylamine, a mixture of mono- and di-alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl) hexamethylenediamine, bis (2,2 , 6,6-tetramethylpiperidi-4-yl) sebacate, 2,2,6 6-tetramethyl-4-one, and, 2,2,6,6-tetramethyl-4-ol, and the like.

(Light stabilizer)
The resin composition or curable resin composition of this embodiment may further contain a light stabilizer.
The light stabilizer is not particularly limited, and examples thereof include UV absorbers such as triazole, benzophenone, ester, acrylate, nickel, triazine, and oxamide, and hindered amine light stabilizers. .
These may be used alone or in combination of two or more.
Specific examples of the light stabilizer include the following (1) to (8).

[(1) Triazoles]
Examples of triazoles include, but are not limited to, 2- (2′-hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (2 '-Hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2 -(3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2' -Hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydride Xyl-5 ′-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3′-tert-butyl-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl) benzotriazole, 2- (3′-dodecyl-2′-hydroxy-5′-methyl) Phenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2′-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], 2- [3′-tert-butyl- Transesterification product of '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300, triazole compound represented by the following formula (18), and 2- [2' -Hydroxy-3 '-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2'-hydroxy-3 '-(1, 1,3,3-tetramethylbutyl) -5 ′-(α, α-dimethylbenzyl) phenyl] benzotriazole and the like.

[(2) Benzophenone series]
Examples of benzophenone-based compounds include, but are not limited to, 4-decyloxy, 4-benzyloxy, 4,2 ′, 4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives. Etc.

[(3) Esters]
Examples of the ester system include, but are not limited to, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl Resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3, Examples include 5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[(4) Acrylate system]
Examples of the acrylate system include, but are not limited to, ethyl-α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbohydrate. Methoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N -(Β-carbomethoxy-β-cyanovinyl) -2-methylindoline and the like.

[(5) Nickel-based]
Nickel systems include, but are not limited to, 1: 1 or 1: 2 complexes with or without additional ligands such as n-butylamine, triethanolamine and N-cyclohexyldiethanolamine, for example. (For example, nickel complex of 2,2′-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol]), nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert- Nickel salts of monoalkyl esters of butylbenzyl phosphate (eg, methyl or ethyl esters), nickel complexes of ketoximes (eg, nickel complexes of 2-hydroxy-4-methylphenylundecyl ketoxime), and additional ligands 1-Phenyl-4-lauroyl-5-hydroxypyr with or without Examples thereof include a nickel complex of sol.

[(6) Triazine series]
The triazine series is not limited to the following, and examples thereof include 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2,4 -Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4 -Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, 6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4 -Dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1 , 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2- Hydroxypropo Cis) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine and 2- {2-hydroxy- 4- [3- (2-Ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like can be mentioned.

[(7) Oxamide type]
The oxamide type is not limited to the following, but for example, 4,4′-dioctyloxy oxanilide, 2,2′-diethoxy oxanilide, 2,2′-dioctyloxy-5,5 '-Di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethyl) Aminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p- And a mixture of methoxy-disubstituted oxanilide and a mixture of o- and p-ethoxy-disubstituted oxanilide.

[(8) Hindered amine system]
Examples of the hindered amine system include, but are not limited to, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4). -Piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2 , 6,6-Tetramethyl-4-hydroxypiperidine and succinic acid, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenedia A linear or cyclic condensate of min and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotri Acetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) -bis (3 , 3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1 , 2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7, 9,9-tetra Methyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy- 2,2,6,6-tetramethylpiperidyl) succinate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro- Linear or cyclic condensate with 1,3,5-triazine; 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3 , 5-triazine and 1,2-bis (3-aminopropylamino) ethane condensate, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6) -Pentamethylpiperidyl) -1,3,5 A condensate of triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4. 5] Decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2 , 2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 5- (2-ethylhexanoyl) -oxymethyl-3,3,5-trimethyl-2-morpholinone, 1- (2 -Hydroxy-2-methylpropyl) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1,3,5-tris (N-cyclohexyl-N- (2,2,6,6-) Tetramethylpiperazine 3-one-4-yl) amino) -s-triazine, 1,3,5-tris (N-cyclohexyl-N- (1,2,2,6,6-pentamethylpiperazin-3-one-4-one) Yl) amino) -s-triazine, 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine and N, N Reaction product with '-bis (3-aminopropyl) ethylenediamine), a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; N, N'-bis ( 2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine condensate, 1,2-bis (3- Aminopropy (Luamino) ethane and 2,4,6-trichloro-1,3,5-triazine, in addition to a condensate of 4-butylamino-2,2,6,6-tetramethylpiperidine, 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, and condensate of N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine, N- (2 , 2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7 , 7,9,9-Tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane; 5- (2-ethylhexanoyl) oxymethyl-3,3,5- Trimethyl-2- Ruphorinone, reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N′-bis-formyl-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methyl Propyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, and maleic anhydride α-olefin copolymer and 2,2,6,6-tetra Reaction products of the chill-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine and the like.

[Cured product]
The cured product of the present embodiment contains the curable resin composition of the present embodiment.
Although it does not specifically limit as a manufacturing method of the hardened | cured material of this embodiment, For example, it is arbitrary to the curable resin composition of this embodiment, or the said curable resin composition by thermosetting or energy ray hardening. And a method of curing a composition containing the material.
Here, the thermosetting is not particularly limited as long as it is a method for obtaining a cured product by generating a three-dimensional cross-linking bond between molecules by a chemical reaction by heat.
Although a thermosetting temperature is not specifically limited, From a viewpoint of productivity and quality, Preferably it is 20-200 degreeC, More preferably, it is 60-180 degreeC, More preferably, it is 100-150 degreeC.
The apparatus used for thermosetting is not particularly limited as long as it can be heated. For example, an oven, a dryer, a vacuum dryer, a block heating apparatus, a hot plate, an autoclave, a heat press apparatus, a vacuum, and the like. Heat press, in-line heating device (Versat cure heating device, transfer feed heating device, conveyor heating device, etc.), multi-stage heating device, dielectric heating device, reflow heating device, drying heating device, thermosetting An injection molding machine etc. are mentioned.
The energy ray curing is a method for obtaining a cured product by irradiating energy rays (light such as ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, electron beams, etc.).
The type of energy rays is not particularly limited, but is preferably light, more preferably ultraviolet rays.
The source of energy rays is not particularly limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a UV lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, Examples of the light source include argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, excimer laser, light emitting diode, CRT light source, plasma light source, and electron beam irradiator.
The method of energy beam curing is not particularly limited, and usually follows a process in which a polymerization initiator is generated by decomposition of a polymerization initiator by energy beam stimulation, and a polymerizable functional group of a target substance is polymerized. .
In the curing step, only one of the above-described curing methods may be used, or a plurality of curing methods may be combined. For example, after UV curing, heat treatment may be further performed to heat cure.

[Prepreg]
The prepreg of this embodiment contains the curable resin composition of this embodiment mentioned above and the reinforced fiber mentioned later.
The prepreg of this embodiment can be produced by a known method using the curable resin composition of this embodiment and reinforcing fibers.
The production method is not particularly limited, and examples thereof include a method of impregnating and applying a curable resin composition to reinforcing fibers.
Typical production methods include, for example, a method of impregnating a curable resin composition with reinforcing fibers, a method of laminating a plurality of reinforcing fibers impregnated with a curable resin composition, and the like.
The form of the reinforcing fiber is not particularly limited, and examples thereof include those that are aligned in one direction, woven fabric, and non-crimp fabric.
The method for impregnating the fiber with the curable resin composition is not particularly limited, and examples thereof include a wet method using a solvent and a hot melt method using no solvent.
When manufacturing a prepreg by a wet method, it is preferable to make it impregnate, after dissolving a curable resin composition in a solvent and preparing a varnish.
Examples of the solvent used for preparing the varnish include, but are not limited to, “alcohols such as methanol, ethanol, and propanol” and “ketones such as methyl ethyl ketone (MEK)”.
Although the usage-amount of a solvent is not specifically limited, From a viewpoint of shortening of drying time, about 1-2 times is preferable by mass with respect to curable resin composition.
The content of the curable resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 70% by mass in the prepreg, more preferably from the viewpoint of workability and mechanical properties. It is 35-60 mass%, Most preferably, it is 40-50 mass%.
The method of using the prepreg of the present embodiment is not particularly limited, and for example, a method of curing the prepreg as it is, a method of semi-curing and further curing the fiber reinforced prepreg, and the like can be appropriately employed.
Moreover, it is also possible to produce the FRP described later by laminating the prepreg and another member (for example, a honeycomb core). Specific examples include a honeycomb sandwich panel.
The prepreg of this embodiment preferably has a fiber volume content of reinforcing fibers in the range of 45 to 70%, more preferably in the range of 50 to 65%, and even more preferably in the range of 55 to 60%. It is preferable to be within the range.
When the fiber volume content is 45% or more, a prepreg having a higher elastic modulus and an excellent lightening effect can be obtained. A prepreg having excellent characteristics can be obtained.

[Fiber reinforced plastic]
The fiber reinforced plastic of this embodiment contains the curable resin composition of this embodiment mentioned above and the reinforced fiber mentioned later, and the hardening process is performed.
A preferred method for producing the fiber reinforced plastic (FRP) of the present embodiment is not particularly limited, but the liquid curable resin composition of the present embodiment described above is impregnated into a predetermined reinforcing fiber and cured. To obtain a fiber reinforced composite material, a method of blending reinforced fibers in the liquid curable resin composition of the present embodiment and curing to obtain a fiber reinforced composite material, specifically, an autoclave molding method Resin transfer molding method (RTM method), filament winding method, pultrusion method and the like.
Among these, from the viewpoint of physical properties of FRP, it is preferable to use an autoclave molding method or an RTM method.
The autoclave molding method is not particularly limited as long as it is a molding method using an autoclave. For example, the prepreg is laminated on a molding die and covered with a bag material as necessary, and the autoclave is then autoclaveed. In this method, FRP is formed by heating and pressurizing. This method is preferably used for molding aircraft members and the like because an extremely reliable FRP can be obtained by using a prepreg with few voids.
The RTM method is a method of obtaining FRP by impregnating a liquid fiber composition into a reinforcing fiber base disposed in a mold and curing it. This method has the advantage of excellent productivity.
Furthermore, as a method for producing a derivative form of the RTM method, for example, a vacuum injection molding method (VaRTM method), a SCRIMP (Seeman's Composite Resin Infusion Molding Process) method, and a CAPRI (Controlled Atmospheric Pressure) described in JP-T-2005-527410. (Infusion) method or the like can also be suitably used.
The mold used for the RTM method may be a closed mold made of a rigid material, or an open mold of a rigid material and a flexible film (bag). In the latter case, the reinforcing fiber substrate can be placed between an open mold of rigid material and a flexible film. As the rigid material, various existing materials such as metals such as steel and aluminum, fiber reinforced plastic (FRP), wood, and plaster are used. As the flexible film material, polyamide, polyimide, polyester, fluororesin, silicone resin, or the like is used.
In the RTM method, when a closed mold of a rigid material is used, it is common to pressurize and clamp and inject the curable resin composition under pressure. At this time, a suction port may be provided separately from the injection port and connected to a vacuum pump for suction. Moreover, it is also possible to inject | pour curable resin composition only by atmospheric pressure, without performing a suction and using a special pressurization means. In this method, a large member can be manufactured by providing a plurality of suction ports.
In the RTM method, when an open mold of a rigid material and a flexible film are used, the curable resin composition is usually injected only at atmospheric pressure without sucking and using a special pressurizing means. It is effective to use a resin diffusion medium for impregnation by injection at atmospheric pressure. Furthermore, it is preferable to apply a gel coat to the surface of the rigid material prior to installation of a fiber base material or preform made of reinforcing fibers.
When a rigid material closed mold is used as the mold, the inside of the mold means a cavity formed by the closed mold, and when a rigid material open mold and a flexible film are used, The term “in the space surrounded by the open mold and the flexible film” means.

(Other materials)
According to the purpose, the resin composition, curable resin composition, prepreg, and FRP of the present embodiment include various organic resins, inorganic fillers, colorants, leveling agents, lubricants, surfactants, silicone compounds, A reactive diluent, a non-reactive diluent, etc. can be included as appropriate.
In addition, generally used as additives for plastics (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, crosslinking agents, etc.) Substances to be made may be blended.

Examples of organic resins include, but are not limited to, for example, polyamide resins, “polymethacrylate resins including poly (methyl methacrylate) (pMMA)”, “polyethylene terephthalate (PET), poly Polyester resins including butylene terephthalate (PBT), unsaturated polyester resins, polyphenylene sulfide resins (PPS), polyimide resins, urethane resins, polyolefin resins including polyethylene (PE) and polypropylene (PP) , Polystyrene (pSt), polyacrylonitrile (PAN), “ABS resins including ABS resin, α-methylstyrene-based ABS resin, phenylmaleimide-based ABS resin”, ASA resin (AAS resin), ACS resin, Polychlorinated Sulfonyl resin, nylon, fluorine resin, polycarbonate (PC) ", a phenol resin, a melamine resin, polylactic acid, polyacrylic acid and salts thereof.
Among these, from the viewpoint of the physical properties of the cured product and FRP, a polyamide resin, a polyimide resin, and an unsaturated polyester resin are preferable, and a polyamide resin and a polyimide resin are more preferable.
These organic resins may be copolymerized or compounded with other compositions.
Moreover, organic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of inorganic fillers include, but are not limited to, silicas (fused crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.), silicon carbide, silicon nitride, and the like. Boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium silicate Examples include aluminum, zirconium silicate, barium titanate, glass fiber, carbon fiber, and molybdenum disulfide.
Among these, silicas, calcium carbonate, aluminum oxide, zirconium oxide, titanium oxide, aluminum hydroxide, calcium silicate, and barium titanate are preferable, and silicas are more preferable in view of physical properties of the cured product.
These inorganic fillers may be used alone or in combination of two or more.

The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. Various organic pigments, and inorganic pigments such as titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermilion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide and cobalt green Can be.
These colorants may be used alone or in combination of two or more.

The leveling agent is not limited to the following, but for example, an oligomer having a molecular weight of 4000 to 12000, an epoxidized soybean fatty acid, an epoxidized abiethyl formed from an acrylate such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate Examples include alcohol, hydrogenated castor oil, and titanium coupling agents.
These leveling agents may be used alone or in combination of two or more.

The lubricant is not limited to the following, for example, hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, and higher grades such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. Fatty acid lubricants, higher fatty acid amide lubricants such as stearylamide, palmitylamide, oleylamide, methylenebisstearamide and ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate and pentaerythritol (mono -, Di-, tri-, or tetra-) stearate and other higher fatty acid ester lubricants, cetyl alcohol, stearyl alcohol, polyethylene glycol and polyglycerol alcohol lubricants such as lauric acid, myristic acid, Metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc and lead such as luminitic acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid and naphthenic acid, and carnauba wax, candelilla wax, beeswax and montan wax Examples include natural wax.
These lubricants may be used alone or in combination of two or more.

A surfactant refers to an amphiphilic substance having a hydrophobic group having no affinity for a solvent in a molecule and a philic group (usually a hydrophilic group) having an affinity for a solvent.
The type of the surfactant is not particularly limited, and examples thereof include silicone surfactants and fluorine surfactants.
Only one surfactant may be used alone, or two or more surfactants may be used in combination.

Examples of silicone compounds include, but are not limited to, silicone resins, silicone condensates, silicone partial condensates, silicone oils, silane coupling agents, silicone oils, and polysiloxanes.
The silicone compound may be modified by introducing an organic group at both ends, one end, or side chains.
The method for modifying the silicone compound is not particularly limited, and is not limited to the following. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification. , Carboxyl modification, phenol modification, silanol modification, polyether modification, polyether / methoxy modification, and diol modification.

  The reactive diluent is not limited to the following, for example, alkyl glycidyl ether, monoglycidyl ether of alkylphenol, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, Examples thereof include ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether.

  Non-reactive diluents are not limited to the following, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol and propylene glycol monomethyl ether.

[Use]
The uses of the resin composition, curable resin composition, cured product, prepreg and FRP of the present embodiment are not particularly limited, but examples of those containing reinforcing fibers include "motorcycle frame, cowl, fender". Motorcycle parts such as, door, bonnet, tailgate, side fender, side panel, fender, energy absorbing member, trunk lid, hardp, side mirror cover, spoiler, diffuser, ski carrier, engine cylinder cover, engine hood, chassis , Automobile parts such as air spoilers, propeller shafts, etc., `` railway vehicle parts such as leading car noses, roofs, side panels, doors, bogie covers, side skirts, luggage racks, seats '', `` interior, Wing in on wing truck -Aero parts such as panels, outer panels, roofs, floors, aero parts such as side skirts, etc., window frames, luggage racks, seats, floor panels, wings, propellers, fuselage, etc., bicycle parts, "Cases for notebook computers, mobile phones, etc.", displays for transparent substrates, etc., "construction materials for construction and civil engineering repair sheets, structural materials", "medical applications for X-ray cassettes, top boards, etc.""Sound product applications such as flat speaker panels and speaker cones", "Applications for sports equipment such as golf clubs, faceplates, snowboards, surfboards, protectors, tennis rackets and fishing rods", "Hydrogen tanks, gas tanks, leaf springs, windmill blades, elevators" (General industrial use such as (panel, door), suitcase, furniture " .

Other uses of the resin composition and the cured product of the present embodiment are not limited to the following, for example, paint, printing ink, photosensitive material, structural adhesive, civil engineering adhesive, organic EL And LED sealing sealant and adhesive, polarizing plate adhesive, color filter, organic EL light extraction layer and light extraction film, display substrate, flexible display substrate, flexible display film, semiconductor device, electronic component, Examples include interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, holograms, optical members, or building material components, and these include printed materials, transparent sealants, color filters, and display substrates. , Flexible display substrates, flexible display films, semiconductor devices, electronic components, interlayer insulation films, wiring Kutsugaemaku, optical circuit, an optical circuit component, the anti-reflection film, hologram, connecting material, anisotropic conductive film (ACF), an optical member, building components and the like are provided.
In addition, the pattern formed as a cured product is not limited to the following, for example, transparent sealing agent, color filter, display substrate, flexible display substrate, film for flexible display, electronic component, semiconductor device, It can be advantageously used as an interlayer insulating film, wiring coating film, optical circuit, optical circuit component, antireflection film, other optical member or electronic member.

Hereinafter, the present invention will be described in detail with specific examples, but the present invention is not limited to the following examples.
The physical property evaluation methods applied to the examples and comparative examples are as follows.

〔Evaluation method〕
(Epoxy equivalent (WPE))
The epoxy equivalent of the raw material epoxy compound was measured according to “JIS K7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.

(Sodium and calcium content)
The raw material epoxy compound is used as a measurement sample, and the measurement sample is thermally decomposed in the presence of an acid, and then the contents of sodium (Na) and calcium (Ca) are measured by an inductively coupled plasma mass spectrometer (ICP-MS). did.

(S conversion rate of a compound having at least one thiirane ring)
The measurement of the S conversion rate of the “compound having at least one thiirane ring” was performed by the following procedures (1) to (4) by H-NMR measurement.
(1) A 10 mg sample was placed in a sample bottle, and chloroform-d (manufactured by Wako Pure Chemical Industries, Ltd.) was added to prepare a 1 g solution.
(2) The solution of (1) was transferred to an NMR tube having a diameter of 5 mmφ, and H-NMR was measured under the following conditions.
Fourier transform nuclear magnetic resonance apparatus used for measurement: “Spectrospin 400 type” manufactured by Bruker
Frequency: 400MHz
Nuclide: H
Integration number: 200 times (3) The integrated value (X) of the peak derived from the oxirane ring and the integrated value (Y) of the peak derived from the thiirane ring were determined.
The peaks derived from the oxirane ring and thiirane ring were selected so as not to overlap with peaks derived from other structures.
(4) The integrated value read in (3) above was substituted into the following equation to calculate the S conversion rate (%).
S conversion rate (%) = Y / (X + Y) × 100

(Viscosity of compound having at least one thiirane ring and resin composition)
The viscosity was measured under the following conditions.
・ Rotary E-type viscometer used: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
・ Measurement temperature: 25 ℃
・ Sample volume: 0.4mL

(Ester compound pH)
The pH of the ester compound was measured with a pH test paper (manufactured by Toyo Roshi Kaisha, Ltd.).

(Calculation of storage stability index β of resin composition and evaluation of storage stability of resin composition)
The storage stability in the resin composition was evaluated by the storage stability index β of the resin composition containing a compound having at least one thiirane ring represented by the following general formula (9).
Storage stability index β = (storage viscosity) / (starting viscosity) (9)
The viscosity at 25 ° C. of a resin composition containing a compound having at least one thiirane ring immediately after production was measured, and this was defined as “starting viscosity”.
Further, as a measurement sample, the container containing the resin composition was sealed and stored at 25 ° C. for 30 days. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.
When the measurement sample has fluidity (viscosity is 1000 Pa · s or less) and the storage stability index β is 5 or less, the resin composition was judged to have good storage stability.

(Alcohol content of resin composition)
The alcohol content of the resin composition was measured under the following conditions.
The resin composition immediately after production was diluted with tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter also referred to as THF), and measured with a gas chromatograph (GC).
Measuring device: “GC-14B type” manufactured by Shimadzu Corporation
Detector: FID
Carrier gas: helium Injection temperature: 230 ° C
Detector temperature: 280 ° C
Column: “TC-1” manufactured by GL Science Co., Ltd., inner diameter 0.25 mm × length 30 m, film thickness 0.25 μm
Column temperature: 40 ° C. × 2 minutes → Temperature increase 20 ° C./min→300° C. × 2 minutes If the alcohol content was 500 ppm or less, it was evaluated that it was an appropriate alcohol content.

(Haze of resin composition)
Measurement was performed under the following conditions.
Two TAC films (manufactured by Fuji Film Co., Ltd., thickness 60 μm, haze = 0.5%, haze when two sheets are stacked = 0.8%) were prepared.
A predetermined amount of “resin composition after storage at 25 ° C. × 30 days” or “resin composition after storage at 60 ° C. × 7 days” is placed on one TAC film, and another TAC film. Was pressed with a press machine until the thickness of the layer of the resin composition sandwiched between the TAC films became 0.5 mm to prepare a sample.
Using the haze meter (“NDH 5000W” manufactured by Nippon Denshoku Industries Co., Ltd.), the above sample was measured for haze according to “JIS K7105: Test method for optical properties of plastic”.

(Gel time of curable resin composition)
The gel time of the curable resin composition was measured under the following conditions according to the hot plate method of “JIS C2105: 2006 (Test method for solvent-free liquid resin for electrical insulation)”.
Measurement temperature: 150 ° C and 100 ° C
Measurement time: set to the above temperature, and the gelation time (seconds) was recorded. However, if it did not gel after 30 minutes, it was determined that it would not cure.
When the gel time at 150 ° C. was within 180 seconds, the curability was judged to be good (acceptable range).

(Evaluation of cured product of curable resin composition)
(Manufacture of cured product)
First, a cured product for evaluating physical properties was produced by the following procedures (1) to (5).
(1) The curable resin composition was degassed with a rotation / revolution mixer (Sinky Corporation, “Awatori Nertaro”).
(2) A U-shaped silicon rubber having a desired thickness (example: 2 mm) was sandwiched between two stainless steel plates coated with a release agent to prepare a molding jig.
(3) The degassed curable resin composition was poured into this molding jig, and further deaerated with a vacuum dryer as necessary (at this time, in order to ensure the fluidity of the curable resin composition). And warmed as needed.)
(4) The molding jig was placed in an oven and subjected to heat treatment for a predetermined time to produce a cured product.
(5) After the oven internal temperature fell to 30 ° C. or lower, the cured product was taken out and processed into a predetermined shape to obtain a sample for evaluating physical properties.
The evaluation method of hardened | cured material is shown below.

(Tackiness of cured product)
Wearing latex gloves, the tackiness of the surface of the obtained cured product was evaluated.
The case where there was no stickiness was regarded as acceptable, and the case where there was stickiness was regarded as unacceptable.

(Glass transition temperature (Tg) of cured product)
Using a dynamic viscoelasticity measuring apparatus (DMA), the glass transition temperature of the cured product was measured by the following procedures (1) to (3).
(1) The cured product was cut into a width of about 8 mm, a length of 30 to 50 mm, and a thickness of about 2 mm, and the accurate dimensions were measured and recorded.
(2) The sample was set in a dynamic viscoelasticity measuring device (DMA), and the storage elastic modulus (G ′) and loss elastic modulus (G ″) were measured under the following conditions.
-Equipment: Anton Paar, "Physica MCR 301"
・ Measurement mode: Solid torsion measurement ・ Strain: Swing angle γ = 0.005 to 0.05%
・ Frequency f = 1Hz
Normal force: FN = -0.2N
・ Temperature: 30 to 200 ° C. (temperature increase: 2 ° C./min)
(3) From the obtained storage elastic modulus (G ′) and loss elastic modulus (G ″), loss tangent (tan δ) = G ″ / G ′ is calculated, and the peak top temperature of tan δ is set to the glass of the cured product. The transition temperature (Tg) was obtained.

(Hardness of cured product (durometer hardness: Shore D))
The hardness (Shore D) of the cured product is determined according to “JIS K6253-3: 2012 (vulcanized rubber and thermoplastic rubber—How to obtain hardness—Part 3: Durometer hardness)”. Manufactured by Asker Rubber Hardness Tester, Type D).

(Bending test of cured product)
The bending test of the cured product was performed under the following conditions in accordance with ASTM D790, and the maximum stress and elastic modulus were obtained.
・ Equipment: Shimadzu Corporation, Autograph "AG-5000D type"
Measurement temperature (relative humidity): 24 ° C. (RH = 50%)
Test piece: The cured product was cut into a width of about 12 mm, a length of about 120 mm, and a thickness of about 2 to 3 mm, and the accurate dimensions were measured and recorded.
-Between spans: 50mm
・ Bending speed: 1.3 mm / min

(Cross section observation of cured product)
The cross section of the cured product was observed visually and with a digital microscope (manufactured by Keyence Corporation, “VH-Z100R type”) to observe the presence or absence of bubbles.
A case where no abnormality such as bubbles was observed was accepted, and a case where abnormality was found was regarded as unacceptable.
When the storage stability of the resin composition produced by the examples described later is better than the resin composition to be compared, the storage stability is good (A), and the storage stability is bad (B). Judged.
Moreover, the case where the gel time in 150 degreeC of the curable resin composition of an Example and a comparative example is 180 second or less was determined to be a pass (A), and the case where it does not gel in 180 seconds was determined to be a rejection (B).
When the determination of the above-mentioned resin composition is a pass (A) and the determination of the curable resin composition is also a pass (A), the comprehensive determination is determined to be a pass (A).
Of the determination of the resin composition and the determination of the curable resin composition, if any one is rejected (B), or both are rejected (B), the comprehensive determination is rejected (B). It was determined that

〔raw materials〕
About the raw material used by the Example and the comparative example, it shows to the following (1)-(4).
((1) Epoxy compound)
(1-1) Bisphenol A type epoxy compound (hereinafter referred to as “BisA-O”, “BisA type epoxy”)
・ Product name: “AER250”, manufactured by Asahi Kasei Epoxy Corporation
Epoxy equivalent (WPE): 186 g / eq
Viscosity (25 ° C.): 9.4 Pa · s
・ Sodium content: Less than the lower limit of detection (<0.25 ppm)
・ Calcium content: 0.8ppm
(1-2) Bisphenol F-type epoxy compound (hereinafter referred to as “BisF-O” and “BisF-type epoxy”)
・ Product name: “jER 806” manufactured by Mitsubishi Chemical Corporation
Epoxy equivalent (WPE): 164 g / eq
Viscosity (25 ° C.): 2.1 Pa · s
・ Sodium content: Less than the lower limit of detection (<0.25 ppm)
・ Calcium content: Less than the lower limit of detection (<0.25 ppm)
(1-3) Hydrogenated bisphenol A type epoxy resin (hereinafter referred to as “hydrogenated BisA-O” and “hydrogenated BisA type epoxy”)
・ Product name: “jER YX8000”, manufactured by Mitsubishi Chemical Corporation
Epoxy equivalent (WPE): 203 g / eq
Viscosity (25 ° C.): 2.0 Pa · s

((2) Curing agent)
(2-1) Latent curing agent: “Novacure HX-3722” (hereinafter, referred to as “Novacure”) manufactured by Asahi Kasei E-Materials Co., Ltd.

((3) Ester compound)
(3-1) Tributyl borate: manufactured by Tokyo Chemical Industry Co., Ltd. pH: 6-7
(3-2) Diphenylisodecyl phosphite: Johoku Chemical Industry Co., Ltd., "JPM-311" (hereinafter referred to as "DIDP")
・ PH: 6-7

((4) solvent)
(4-1) Methanol: Wako Pure Chemical Industries, Ltd. (hereinafter referred to as “MeOH”)
(4-2) Toluene: Wako Pure Chemical Industries, Ltd. (hereinafter referred to as “Tol”)
(4-3) Chloroform-d: manufactured by Aldrich (4-4) tetrahydrofuran: manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free type (hereinafter referred to as “THF”)

[Production example of compound having at least one thiirane ring]
(Production Example 1)
Compound V having at least one thiirane ring was produced according to the procedures of (1) to (8) below according to the formulation shown in Table 1 below.
The evaluation results of Compound V having the at least one thiirane ring are shown in Table 2 below.
(1) A stirrer is placed in a flask equipped with a thermometer and a nitrogen introduction tube, and 17.7 parts by mass of bisphenol F-type epoxy resin (BisF-type epoxy resin) and 45.8 parts by mass of toluene in accordance with the composition shown in Table 1 Then, 24.7 parts by mass of methanol was introduced and dissolved by stirring at 25 ° C.
(2) Under a nitrogen atmosphere, 11.8 parts by mass of thiourea was further added little by little, and a thialation reaction was carried out for 360 minutes while maintaining at 45 ° C.
(3) The reaction solution was cooled to 25 ° C., and 50 parts by mass of toluene and 50 parts by mass of ion-exchanged water were added to a separatory funnel with respect to 100 parts by mass of the reaction solution, and the lower layer was discarded. First wash).
(4) To the above separatory funnel, 25 parts by mass of toluene and 50 parts by mass of ion-exchanged water were added, stirred and allowed to stand, and the lower layer was discarded (second wash).
(5) To the above separatory funnel, 50 parts by mass of ion-exchanged water was added, stirred and allowed to stand, and the lower layer was discarded (3rd washing).
(6) To the above separatory funnel, 50 parts by mass of ion-exchanged water was added, stirred and allowed to stand, and the lower layer was discarded (4th washing).
(7) The obtained upper layer was distilled off under reduced pressure at 60 ° C. using a rotary evaporator. The pressure was gradually reduced from atmospheric pressure and distilled off at 500 Pa for 30 minutes to obtain a compound having at least one thiirane ring.
In the step of producing a compound having a thiirane ring, the mixing ratio at the time of the reaction between the raw material epoxy compound and the thiating agent was represented by a mixing index α calculated by the following formula (1).
Mixing index α = αt / αe (1)
In the formula (1), αt represents a substance amount (mol) of a sulfur atom that can be used to form a thiirane ring contained in the thiarizing agent, and αe represents a substance amount (mol of the oxirane ring contained in the epoxy compound). ).
(8) S conversion was 99.0%, and the viscosity at 25 ° C. was 5.2 Pa · s.

[Production Example 2]
Compound W having at least one thiirane ring was produced according to the formulation in Table 1 below.
It was produced in the same manner as in [Preparation Example 1] except that the thialation reaction time was 10 minutes.
Table 2 below shows the evaluation results of the compounds having at least one thiirane ring.

[Production Example 3]
Compound X having at least one thiirane ring was prepared according to the formulation in Table 1 below.
It was produced in the same manner as in [Preparation Example 1] except that the thialation reaction time was 78 minutes.
Table 2 below shows the evaluation results of the compounds having at least one thiirane ring.

[Production Example 4]
Compound Y having at least one thiirane ring was produced according to the formulation in Table 1 below.
The product was produced in the same manner as in [Production Example 1] except that the thialation reaction time was 30 minutes.
Table 2 below shows the evaluation results of the compounds having at least one thiirane ring.

[Production Example 5]
Compound Z having at least one thiirane ring was prepared according to the formulation in Table 1 below.
The product was produced in the same manner as in [Production Example 1] except that the thialation reaction time was 320 minutes.
Table 2 below shows the evaluation results of the compounds having at least one thiirane ring.

[Production of resin composition, curable resin composition, and cured product]
[Example 1]
In accordance with the formulation shown in Table 3 below, 0.25 part by mass of boric acid ester is added to Compound V (100 parts by mass) having at least one thiirane ring of [Production Example 1], and a rotating / revolving mixer (Co., Ltd.) Using a “Shinky”, “Awatori Nertaro”), the mixture was processed by mixing at a stirring mode of 2000 rpm for 3 minutes and further by a degassing mode of 2200 rpm for 3 minutes to obtain a composition.
The composition was placed in a glass sample bottle, covered, placed in a safety oven, and heat-treated at 100 ° C. for 1 hour to obtain a resin composition A.
The evaluation results of the resin composition A are shown in Table 4.
The alcohol content of the obtained resin composition A was less than the detection limit (less than 50 ppm).
The “starting viscosity” was measured and found to be 5.3 Pa · s.
Furthermore, as a measurement sample, the container containing the resin composition A was sealed and stored at 25 ° C. for 30 days. The sample for measurement after storage had fluidity, and the viscosity at 25 ° C. was 10.2 Pa · s, which was defined as the “storage viscosity”. The storage stability index β determined from the above starting viscosity and storage viscosity was 1.9, which was 5 or less. The resin composition a of [Comparative Example 1], which will be described later, and the resin composition n of [Comparative Example 14], which will be described later, have lost fluidity after being stored at 25 ° C. for 30 days. Could not be measured.
Furthermore, when the haze of the resin composition A stored for 30 days at 25 days was measured, the haze of the resin composition A stored for 7 days at 60 ° C. was 1.2%, which will be described later [Comparative Example 1) and resin composition n of [Comparative Example 14] to be described later had good transparency.
From the above, it is determined that the resin composition A of [Example 1] has good storage stability with respect to the resin composition a of [Comparative Example 1] and the resin composition n of [Comparative Example 14]. did.
Next, according to the mixing | blending of Table 5, 3 mass parts of NOVACURE was mix | blended with the said resin composition A (100 mass parts), and it mixed sufficiently, and the curable resin composition A was manufactured.
Table 6 shows the evaluation results of the curable resin composition A.
The gel time at 150 ° C. of the curable resin composition was 25 seconds, and the curable resin composition A of Example 1 was in an acceptable range.
Furthermore, using the said curable resin composition, according to the procedure mentioned above, after heating at 100 degreeC for 1 hour, it heated at 150 degreeC for 1 hour, and manufactured hardened | cured material. The evaluation results of this cured product are shown in Table 6 below. It was found that the surface of the obtained cured product had no tackiness and was normally cured.
Moreover, Tg of hardened | cured material was 133 degreeC and hardness (Shore D) was 88. According to the bending test, the maximum stress was 126 MPa, and the elastic modulus was 3230 MPa, which had sufficient hardness. Also, no abnormalities such as bubbles were observed in the cross section of the cured product.

[Comparative Example 1]
A resin composition a was produced in the same manner as in [Example 1] except that the heat treatment was not performed. The evaluation results are shown in Table 4 below.
The “starting viscosity” of the resin composition was measured and found to be 5.2 Pa · s. Further, as a measurement sample, the container containing the resin composition a was sealed and stored at 25 ° C. for 30 days. It was found that the sample for measurement after storage lost fluidity and could not measure “storage viscosity”, and the viscosity was severer compared with the resin composition A of [Example 1].
Further, the haze of the resin composition a stored for 30 days at 25 days was 97.5%, and the haze of the resin composition α stored for 7 days at 60 ° C. was 96.7%, and the resin composition of [Example 1] It was found that the transparency was inferior compared to the product A.
From these, it was judged that the resin composition a was poor in storage stability with respect to the resin composition A of [Example 1].

[Example 2]
In accordance with the composition shown in Table 3 below, the heat treatment was performed at 100 ° C. for 30 minutes. The resin composition B was prepared in the same manner as in [Example 1] under the other conditions. The evaluation results are shown in Table 4 below.
It turned out that the resin composition B is excellent in storage stability with respect to the resin composition b of [Comparative Example 2] described later and the resin composition n of [Comparative Example 14].
Further, Table 6 shows the results of preparing and evaluating the curable resin composition B in the same manner as in [Example 1] according to the formulation in Table 5. The curability of the curable resin composition B was within an acceptable range.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 2]
Resin composition b was produced in the same manner as in [Example 2] except that the heat treatment was not performed in accordance with the formulation shown in Table 3 below. Table 4 shows the evaluation results.
The resin composition b was judged to have poor storage stability compared to the resin composition B of [Example 2].

Example 3
Resin composition C was prepared in the same manner as in [Example 1] according to the formulation shown in Table 3 below. The evaluation results are shown in Table 4 below.
It turned out that the resin composition C is excellent in storage stability with respect to the resin composition c of [Comparative Example 3] described later and the resin composition n of [Comparative Example 14].
Furthermore, according to the composition of Table 5, a curable resin composition C was prepared in the same manner as in [Example 1]. The evaluation results are shown in Table 6. The curability of the curable resin composition C was practically acceptable.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 3]
Resin composition c was produced in the same manner as in [Example 3] except that the heat treatment was not performed according to the formulation shown in Table 3 below. Table 4 shows the evaluation results.
From these, it was judged that the resin composition c had poor storage stability compared to the resin composition C of [Example 3].

Example 4
According to the composition shown in Table 3 below, a resin composition D was prepared in the same manner as in [Example 1]. The evaluation results are shown in Table 4 below.
It turned out that the resin composition D is excellent in storage stability with respect to the resin composition d of [Comparative Example 4] mentioned later and the resin composition n of [Comparative Example 14].
Further, Table 6 shows the results of preparing and evaluating the curable resin composition D in the same manner as in [Example 1] according to the formulation in Table 5. The curability of the curable resin composition D was within an acceptable range.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 4]
A resin composition d was produced in the same manner as in [Example 4] except that the heat treatment was not performed according to the formulation shown in Table 3 below. Table 4 shows the evaluation results.
From these, it was judged that the resin composition d was poor in storage stability with respect to the resin composition D of [Example 4].

Example 5
The compound having at least one thiirane ring produced in (1) to (7) of [Preparation Example 1] is dropped from the rotary evaporator, and according to the composition of Table 3, the eggplant flask containing the above compound is added with toluene. Diluted phosphite was added and mixed well.
The eggplant flask was set again on the rotary evaporator, and the pressure was gradually reduced from atmospheric pressure to 500 Pa at 50 ° C., followed by evaporation under reduced pressure.
Furthermore, it distilled for 1 hour at 100 degreeC and 500 Pa, and produced the resin composition E. FIG.
The evaluation results are shown in Table 4 below.
It turned out that the resin composition E is excellent in storage stability with respect to the resin composition e of [Comparative Example 5] mentioned later and the resin composition n of [Comparative Example 14].
Furthermore, according to the composition of Table 5, a curable resin composition E was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 6. The curability of the curable resin composition E was within an acceptable range.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 5]
According to the composition shown in Table 3 below, the resin composition e was prepared in the same manner as in [Example 5] except that the rotary evaporator was used to distill off at 100 ° C. and 500 Pa for 1 hour and the heat treatment was omitted. Manufactured. Table 4 shows the evaluation results.
From these, it was judged that the resin composition e was poor in storage stability with respect to the resin composition E of [Example 5].

Example 6
According to the composition shown in Table 3 below, a resin composition F was prepared in the same manner as in [Example 1]. The evaluation results are shown in Table 4 below.
It turned out that the resin composition F is excellent in storage stability with respect to the resin composition f of [Comparative Example 6] mentioned later and the resin composition n of [Comparative Example 14] mentioned later.
Furthermore, according to the composition of Table 5, a curable resin composition F was produced in the same manner as in [Example 1]. Table 6 shows the evaluation results. The curability of the curable resin composition F was within an acceptable range.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 6]
Resin composition f was produced in the same manner as in [Example 6] except that the heat treatment was not performed according to the formulation shown in Table 3 below. Table 4 shows the evaluation results.
From these, it was judged that the resin composition f had poor storage stability with respect to the resin composition F of [Example 6].

Example 7
Resin composition G was produced in the same manner as in [Example 1] according to the formulation shown in Table 3 below. The evaluation results are shown in Table 4 below.
It turned out that the resin composition G is excellent in storage stability with respect to the resin composition g of [Comparative Example 7] described later and the resin composition n of [Comparative Example 14].
Furthermore, according to the composition of Table 5, curable resin composition G was produced in the same manner as in [Example 1]. Table 6 shows the evaluation results. The curability of the curable resin composition G was within an acceptable range.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 7]
Resin composition g was produced in the same manner as in [Example 7] except that the heat treatment was not performed in accordance with the formulation shown in Table 3 below. Table 4 shows the evaluation results.
From these, it was judged that the resin composition g had poor storage stability with respect to the resin composition G of [Example 7].

Example 8
According to the composition of the following Table 3, except that the compound Z having at least one thiirane ring of [Preparation Example 5] was used instead of the compound V having at least one thiirane ring of [Preparation Example 1]. Resin composition H was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 4 below.
It turned out that the resin composition H is excellent in storage stability with respect to the resin composition h of [Comparative Example 8] mentioned later and the resin composition n of [Comparative Example 14].
Furthermore, according to the composition of Table 5, curable resin composition H was produced in the same manner as in [Example 1]. Table 6 shows the evaluation results. The curability of the curable resin composition H was within an acceptable range.
In addition, a cured product was produced in the same manner as in [Example 1] except that the curing condition was changed to heating at 100 ° C. × 1 hour and then further heating to 150 ° C. × 3 hours, and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 8]
Resin composition h was produced in the same manner as in [Example 8] except that the heat treatment was not performed in accordance with the formulation shown in Table 3 below. Table 4 shows the evaluation results.
From these, it was judged that the resin composition h had poor storage stability with respect to the resin composition H of [Example 8].

Example 9
According to the composition of the following Table 3, except that the compound W having at least one thiirane ring of [Preparation Example 2] was used instead of the compound V having at least one thiirane ring of [Preparation Example 1]. Resin Composition I was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 4 below.
It turned out that the resin composition I is excellent in storage stability with respect to the resin composition i of [Comparative Example 9] described later.
Furthermore, according to the composition of Table 5, a curable resin composition J was produced in the same manner as in [Example 1]. Table 6 shows the evaluation results. The curability of the curable resin composition I was within an acceptable range.
A cured product was produced in the same manner as in [Example 1] except that the curing conditions were changed to 150 ° C. × 6 hours, and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 9]
Resin composition i was produced in the same manner as in [Example 9] except that the heat treatment was not performed in accordance with the formulation shown in Table 3 below. Table 4 shows the evaluation results.
From these, it was judged that the resin composition i had poor storage stability with respect to the resin composition I of [Example 9].

Example 10
According to the composition of the following Table 3, except that the compound X having at least one thiirane ring of [Preparation Example 3] was used instead of the compound V having at least one thiirane ring of [Preparation Example 1]. Resin composition J was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 4 below.
It turned out that the resin composition J is excellent in storage stability with respect to the resin composition j of [Comparative Example 10] mentioned later.
Furthermore, according to the composition of Table 5, a curable resin composition J was produced in the same manner as in [Example 1]. Table 6 shows the evaluation results. The curability of the curable resin composition J was within an acceptable range.
A cured product was produced in the same manner as in [Example 1] except that the curing condition was changed to 150 ° C. for 4 hours, and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 10]
In accordance with the composition shown in Table 3 below, the compound having at least one thiirane ring of [Preparation Example 3] is used in place of the compound having at least one thiirane ring of [Preparation Example 1] and subjected to heat treatment. A resin composition j was produced in the same manner as in [Example 10] except that the composition was not present. Table 4 shows the evaluation results.
From these, it was judged that the resin composition j had poor storage stability with respect to the resin composition J of [Example 10].

Example 11
According to the composition shown in Table 3 below, Example 1 was used except that Compound Y having at least one thiirane ring in Production Example 4 was used instead of Compound V having at least one thiirane ring in Production Example 1. In the same manner as in 1], a resin composition K was produced. The evaluation results are shown in Table 4.
It turned out that the resin composition K is excellent in storage stability with respect to the resin composition k of [Comparative Example 11] mentioned later.
Furthermore, according to the composition of Table 3, a curable resin composition K was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 4. The curability of the curable resin composition K was within an acceptable range.
Moreover, when the curable resin composition k of [Comparative Example 11] described later was used, a normal cured product could not be produced. That is, it was found that [Example 11] is superior also in handling during production of the cured product.
A cured product was produced in the same manner as in [Example 1] except that the curing condition was changed to 150 ° C. × 4 hours, and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 11]
Resin composition k was produced in the same manner as in [Example 11], except that the heat treatment was not performed according to the formulation shown in Table 3 below. The evaluation results are shown in Table 4.
After storage at 25 ° C. for 30 days, the resin composition k was clouded and the storage viscosity could not be measured.
From these, it was judged that the resin composition k had poor storage stability compared to the resin composition K of [Example 11].
Furthermore, according to the composition of Table 5, the curable resin composition k was produced in the same manner as in the above [Example 1], and a cured product was produced, but cured at the stage of mixing and deaeration treatment before curing. The resin composition k rapidly thickened and crystallized, and a normal cured product could not be obtained.
It turned out that the curable resin composition k of [Comparative Example 11] is inferior to the curable resin composition K of [Example 11] in handling at the time of producing a cured product.

Example 12
According to the composition of Table 3, the compound V having at least one thiirane ring of [Production Example 1], bisphenol F type epoxy, and phosphite were added and mixed. Further, a heat treatment was performed in the same manner as in [Example 1] to produce a resin composition L. The evaluation results are shown in Table 4.
It turned out that the resin composition L is excellent in storage stability with respect to the resin composition 1 of [comparative example 12] mentioned later.
Furthermore, according to the composition of Table 5, curable resin composition L was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 6. The curability of the curable resin composition L was within an acceptable range.
A cured product was produced in the same manner as in [Example 1] except that the curing condition was changed to 150 ° C. for 4 hours, and tackiness was evaluated. The evaluation results are shown in Table 6. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 12]
Resin composition l was produced in the same manner as in [Example 12], except that the heat treatment was not performed according to the formulation shown in Table 3 below. The evaluation results are shown in Table 4.
From these, it was judged that the resin composition l was poor in storage stability with respect to the resin composition L of [Example 12].
Furthermore, according to the composition of Table 5, a curable resin composition l was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 6.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 12], and tackiness was evaluated. The evaluation results are shown in Table 6 below. It was found that the obtained cured product had no tackiness and was cured normally.

Example 13
According to the composition in Table 3, a resin composition M was produced in the same manner as in [Example 13]. The evaluation results are shown in Table 4.
It turned out that the resin composition M is excellent in storage stability with respect to the resin composition m of [Comparative Example 13] described later.
Furthermore, according to the composition of Table 5, a curable resin composition M was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 6. The curability of the curable resin composition M was within an acceptable range.
A cured product was produced in the same manner as in [Example 1] except that the curing condition was changed to 150 ° C. for 4 hours, and tackiness was evaluated. The evaluation results are shown in Table 6. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 13]
Resin composition m was produced in the same manner as in [Example 13] except that the heat treatment was not performed in accordance with the formulation shown in Table 3 below. The evaluation results are shown in Table 4.
From these, it was judged that the resin composition m had poor storage stability with respect to the resin composition M of [Example 13].
Furthermore, according to the composition of Table 5, a curable resin composition m was produced by the same method as in [Example 1]. The evaluation results are shown in Table 6.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 13], and tackiness was evaluated. The evaluation results are shown in Table 6. It was found that the obtained cured product had no tackiness and was cured normally.

Example 14
A curable resin composition C ′ was prepared in the same manner as in [Example 1] using the resin composition C in [Example 3] according to the formulation in Table 5. Table 6 shows the evaluation results. The curability of the curable resin composition C ′ was practically acceptable.

[Comparative Example 14]
Resin composition n was produced in the same manner as in [Comparative Example 1] except that boric acid ester was not blended according to the blending in Table 3 below. The evaluation results are shown in Table 4.
After storage at 25 ° C. for 30 days, the resin composition n was clouded and the storage viscosity could not be measured.
From these, it was judged that the resin composition n had poor storage stability with respect to the resin compositions A to H of [Examples 1 to 7].
Furthermore, according to the composition of Table 5, a curable resin composition n was produced in the same manner as in [Example 1]. Evaluation results are shown in Table 6.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6. It was found that the obtained cured product had no tackiness and was cured normally.
Moreover, Tg of hardened | cured material was 133 degreeC and hardness (Shore D) was 88. According to the bending test, the maximum stress was 126 MPa, and the elastic modulus was 3200 MPa, which had sufficient hardness.
No abnormalities such as bubbles were observed in the cross section of the cured product.

[Comparative Example 15]
Resin composition o was produced in the same manner as in Example 1 except that the heat treatment was performed at 40 ° C. for 1 hour in accordance with the formulation shown in Table 3 below. The evaluation results are shown in Table 4.
After storage at 25 ° C. for 30 days, the resin composition o was cloudy.
Moreover, although it tried to measure storage viscosity, the viscosity continued to rise during the measurement, and it did not stop and measurement was not possible. When the measurement cell was opened after 5 minutes, the viscosity increased inside, and the rotor did not rotate normally.
From these, it was judged that the resin composition o had poor storage stability with respect to the resin compositions A to H of [Examples 1 to 7].
Further, according to the formulation shown in Table 5, a curable resin composition was produced in the same manner as in [Example 1]. The evaluation results are shown in Table 6.
Moreover, the hardened | cured material was manufactured by the method similar to the said [Example 1], and tackiness was evaluated. The evaluation results are shown in Table 6. It was found that the obtained cured product had no tackiness and was cured normally.

[Comparative Example 16]
In the same manner as in [Example 1] except that bisphenol F type epoxy was blended instead of compound V having at least one thiirane ring in [Production Example 1], Composition p was produced. The evaluation results are shown in Table 4.
From these, it was found that the resin composition p was excellent in storage stability.
Furthermore, according to the composition of Table 5, a curable resin composition p was produced in the same manner as in Example 1.
The evaluation results are shown in Table 6. Although the gel time at 100 ° C. and 150 ° C. was measured, it did not gel even after 30 minutes, and the curability was poor.

Example 15
Using the curable resin composition D of [Example 4], fiber reinforced plastic (CFRP) was produced by the following procedures (1) to (6).
(1) A PET film was laid on a hot plate and heated to 40 ° C.
(2) A 10 cm square carbon fiber woven fabric (manufactured by Toray Industries, Inc.) was laid on the hot plate, and the curable resin composition was placed thereon and smoothed using a metal screw roller.
(3) Further, the curable resin composition was placed, the CF woven fabric was shifted 90 °, placed thereon, the fiber-reinforced resin was placed, and smoothed using a metal screw roller.
(4) The above operations (2) to (3) were repeated, and a prepreg containing 10 CF fabrics was produced by the hand lay-up method.
(5) The upper and lower sides of the prepreg were sandwiched between PET films coated with a release agent, and further sandwiched between SUS plates, and the shape was adjusted with a press.
(6) The prepreg was heated at 150 ° C. for 10 minutes with a vacuum hot press while being sandwiched between SUS plates. Further, it was heated in an oven at 150 ° C. for 1 hour to obtain CFRP.
When the obtained CFRP was visually confirmed, it was confirmed that it was cured normally and had no tackiness.

Example 16
A glass fiber fabric (manufactured by Nittobo Co., Ltd.) was used instead of the carbon fiber fabric (manufactured by Toray Industries, Inc.) used in [Example 15].
The fiber reinforced plastic (GFRP) was manufactured in the same manner as in [Example 15] except for the other conditions.
When the obtained GFRP was visually confirmed, it was confirmed that the GFRP was cured normally and had no tackiness.

Example 17
Instead of the curable resin composition D of [Example 15], the curable resin composition K of [Example 11] was used, and a fiber reinforced plastic ( CFRP) was produced.
When the obtained CFRP was visually confirmed, it was confirmed that it was cured normally and had no tackiness.

[Comparative Example 17]
In place of the curable resin composition D of [Example 15], the curable resin composition k of [Comparative Example 11] was used, and a fiber reinforced plastic ( CFRP) was produced.
Although an attempt was made to evaluate, the curable resin composition k partially solidified during the operation of (Example 15) (4), and CFRP could not be molded normally.

Table 3 shows the composition of the resin composition.
Table 4 shows the evaluation of the resin composition.
Table 5 shows the composition of the curable resin composition.
Table 6 shows the evaluation of the curable resin composition and the cured product.

  The resin composition obtained by the method for producing a resin composition of the present invention is used for industrial use as a prepreg, fiber reinforced plastic, parts such as automobiles, airplanes, windmills, display materials, and structural materials using the same. Have potential.

Claims (23)

(Step 1): (A) a step of blending (B) an ester compound with a compound having at least one thiirane ring;
(Step 2): After the (Step 1), a step of performing heat treatment at 50 ° C. or higher,
Having
A method for producing a resin composition. In the compound (A) having at least one thiirane ring,
The method for producing a resin composition according to claim 1, wherein a compound having at least one oxirane ring is contained. (A) the compound having at least one thiirane ring,
The manufacturing method of the resin composition of Claim 1 or 2 which has a polyphenol skeleton.   The method for producing a resin composition according to any one of claims 1 to 3, wherein the compound (A) having at least one thiirane ring has a S conversion of 5% or more.   The manufacturing method of the resin composition as described in any one of Claims 1 thru | or 4 whose said (B) ester compound is an inorganic acid ester compound.   The resin composition according to any one of claims 1 to 5, wherein the ester compound (B) is at least one compound selected from the group consisting of a phosphite ester or a borate ester. Method.   The method for producing a resin composition according to claim 6, wherein the (B) ester compound has an aromatic ring.   The method for producing a resin composition according to claim 6 or 7, wherein the (B) ester compound has an alkyl group having 4 or more carbon atoms. With respect to 100 parts by mass of the compound (A) having at least one thiirane ring,
The blending amount of the (B) ester compound is 0.1 to 5 parts by mass.
The manufacturing method of the resin composition as described in any one of Claims 1 thru | or 8.   The manufacturing method of the resin composition as described in any one of Claims 1 thru | or 9 whose temperature of the heat processing of the said (process 2) is 80-120 degreeC. A resin composition obtained by the method for producing a resin composition according to any one of claims 1 to 10,
A resin composition having a viscosity at 25 ° C. of 50 Pa · s or less.   The resin composition according to claim 11, wherein the storage stability index β is 5 or less.   The resin composition according to claim 11 or 12, wherein the haze after storage at 25 ° C for 30 days is 50% or less.   The resin composition according to any one of claims 11 to 13, wherein the haze after storage at 60 ° C for 7 days is 50% or less. The resin composition according to any one of claims 11 to 14,
(C) a curing agent;
A curable resin composition.   The curable resin composition according to claim 15, wherein the (C) curing agent is a latent curing agent.   The curable resin composition according to claim 15 or 16, wherein the (C) curing agent is a microcapsule-type latent curing agent.   The curable resin composition according to any one of claims 15 to 17, wherein the (C) curing agent is an imidazole compound-containing microcapsule type latent curing agent having a core and a shell.   The curable resin composition according to any one of claims 15 to 18, wherein a gel time at 150 ° C is 60 seconds or less.   Hardened | cured material obtained by thermosetting the curable resin composition as described in any one of Claims 15 thru | or 19. A curable resin composition according to any one of claims 15 to 19,
Reinforcing fibers,
Comprising a prepreg. A curable resin composition according to any one of claims 15 to 19,
Reinforcing fibers,
Comprising
A prepreg having a multi-layer structure. A curable resin composition according to any one of claims 15 to 19,
Reinforcing fibers,
Comprising
A fiber-reinforced plastic that has been cured.