KR20140017509A - Anaerobically curable composition - Google Patents

Abstract

The present invention relates to an anaerobic curable composition containing the following components (a) to (e): (a) a compound having at least one radical polymerizable functional group in a molecule; (b) an organic peroxide; (c) o-benzoic sulfide; (d) an epoxy resin that is solid at room temperature having glycidyl functional groups in the side chain of the molecular skeleton; And (e) curing agents for epoxy resins.

Description

Anaerobic Curable Composition {ANAEROBICALLY CURABLE COMPOSITION}

TECHNICAL FIELD This invention relates to the anaerobic curable composition which mainly produces outgas less than the conventional thing in the anaerobic curable composition used mainly as an adhesive agent of an electronic component.

The anaerobic curable composition is composed of a (meth) acryloyl group-containing compound as a main component, and is stable during contact with air or oxygen, and remains in a liquid state for a long time without gelation, and rapidly cures when air or oxygen is blocked or excluded. It is to have the property. By using such a property, the anaerobic curable composition is used for bonding, fixing of screws, bolts and the like, fixing of fitting parts, bonding between flange faces, sealing, filling of casting holes occurring in cast parts, and the like.

Moreover, in the electric field, especially in the motor field, the anaerobic curable composition is used for the fitting adhesion of a bearing part from the productivity.

In recent years, electronic devices such as a hard disk drive device, which is an external storage device, require more precision, and there is a concern that the gas generated from the member may adversely affect the component parts of the electronic device. For example, in a hard disk device, the space in which the hard disk is accommodated is kept clean. Even a small amount of fine particles, when mixed between the disc and the magnetic head, may cause a crash and a defective read / write. In particular, since the gas generated from the adhesive is more likely to be generated than other members, the reduction thereof is required (Patent Documents 1 and 2). However, in the present situation, the anaerobic curable composition cannot satisfy the requirements when used in an electronic device.

In order to reduce the outgas of an ultraviolet curable composition and an anaerobic curable composition, the unreacted acryl component is mix | blended with the prescription which reduces the addition amount of a volatile monomer, and the polyfunctional (meth) acryloyl-group containing compound, and mix | blending a peroxide with rapid thermal decomposition. (Mainly, monofunctional (meth) acryloyl group-containing compound) is designed to be as small as possible. Therefore, especially the use of the monofunctional (meth) acryloyl group containing compound is restrict | limited, and the viscosity, fluidity, and adhesive force of the target adhesive agent may not be obtained.

In order to exhibit the characteristics of fluidity | liquidity, initial stage curability, adhesive force, etc., when the monofunctional (meth) acryloyl-group containing compound was added, there existed a fault that the outgas increased. Moreover, since the bifunctional or more (meth) acryloyl-group containing compound cannot refine | purify normally, acrylic acid etc. which are unreacted materials remain | survive, and this may be the cause of outgas.

Moreover, it is known that outgas is reduced by mix | blending an epoxy resin with anaerobic curable resin (patent document 3). However, when the ratio of the anaerobic curable composition increases, the outgas increases, and when the ratio of the epoxy resin increases, the outgas decreases, but there is a problem that the initial curing property is slowed.

Japanese Patent Laid-Open No. 2004-015955 Japanese Patent Laid-Open No. 11-41845 Japanese Patent Laid-Open No. 2004-331879

This invention is made | formed in view of the said situation, and an object of this invention is to provide the anaerobic curable composition which suppresses the outgas generated from an anaerobic curable composition, and is excellent in initial stage sclerosis | hardenability, and excellent in adhesive force. Moreover, an object of this invention is to provide the electrical and electronic component with little outgas generation using such an anaerobic curable composition.

The gist of the present invention will be described next. Embodiment of this invention overcomes the above-mentioned conventional problem. That is, the present invention has the following points.

[1] an anaerobic curable composition containing the following components (a) to (e):

(a) a compound having at least one radically polymerizable functional group in a molecule;

(b) an organic peroxide;

(c) o-benzoic sulfide;

(d) an epoxy resin that is solid at room temperature having glycidyl functional groups in the side chain of the molecular skeleton; And

(e) Curing agent for epoxy resins.

[2] The anaerobic curable composition according to [1], wherein the epoxy equivalent of the component (d) is 190 to 900.

[3] The anaerobic curable composition according to [1] or [2], wherein the component (e) is 3 to 60 parts by weight based on 100 parts by weight of the component (a).

[4] The anaerobic curable composition according to any one of [1] to [3], wherein the component (d) is a glycidyl group-containing vinyl polymer.

[5] The anaerobic curable composition according to any one of [1] to [4], wherein the component (d) is a copolymer of a monomer having an ethylenically unsaturated group and a glycidyl group and a monomer containing an ethylenically unsaturated group.

[6] The anaerobic curable composition according to any one of [1] to [5], wherein the component (e) is an imidazole compound.

[7] The anaerobic curable composition according to any one of [1] to [6], which is an adhesive for an electronic component for bonding the electronic component.

[8] The anaerobic curable composition according to any one of [1] to [6], which is an adhesive for a hard disk.

As described above, the anaerobic curable composition of the present invention suppresses the outgas generated from the anaerobic curable composition, and is excellent in initial curability and adhesive strength, and therefore, such as electronic components such as hard disk drive devices and optical parts such as optical lenses. It is very effective as an adhesive and a sealing agent in the place where outgas generate | occur | produces and becomes a problem.

The details of the invention are described below.

<Component (a): Compound Having Radical Polymerizable Functional Group>

As a compound which has a radically polymerizable functional group of (a) component used for this invention, the compound which has an ethylenically unsaturated group normally used for an adhesive agent, coating material, etc. can be used. As (a) component, it is a (meth) acryloyl-group containing compound, for example, A monofunctional, bifunctional, trifunctional, polyfunctional monomer, oligomer, etc. can be used. These can be used alone or as a mixture of two or more kinds.

As the monofunctional monomer, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acryl Rate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxy tetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxy tetraethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (Meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, 2-ethylhexyl polyethylene glycol (meth ) Acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, modified butyl (meth) acrylate, epichlorohydrin modified phenoxy (meth) acrylate Ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, etc. are mentioned. Among them, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxy from the viewpoint of initial curing properties Propyl (meth) acrylate is preferred.

As a bifunctional monomer, 1, 3- butylene glycol di (meth) acrylate, 1, 4- butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6, for example Hexane glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene oxide Modified neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, hydroxy pivalic acid ester neopentyl glycol diacrylate, caprolactone modified hydroxy pivalic acid ester neopentyl glycol diacryl Neopentylglycol-modified trimethylolpropanedi (meth) acrylate, stearic acid-modified pentaerythritoldi (meth) acrylate, dicyclopentenyl diacrylate Bit, the work as an ethylene oxide modified dicyclopentenyldialcohol (meth) acrylate, di (meth) acrylate and the like isocyanurate.

As the trifunctional monomer, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, and propylene oxide modified trimethylolpropane Tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, etc. Can be.

As the polyfunctional monomer, for example, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl modified dipentaerythritol penta Acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

These polymerizable monomers can be used individually or as a mixture of 2 or more types.

In addition, the said polymerizable monomer can contain a polymeric oligomer for the purpose of adjusting the viscosity of an anaerobic curable composition, or adjusting the characteristic of the hardened | cured material. As this polymerizable oligomer, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, etc. are mentioned, for example. As (a) component, urethane (meth) acrylate and epoxy (meth) acrylate are preferable, More preferably, it is epoxy (meth) acrylate. These polymerizable oligomers can be used individually or as a mixture of 2 or more types.

As a specific example of an epoxy (meth) acrylate, the reactant of epoxy resins, such as a bisphenol-type epoxy resin, a phenol novolak-type epoxy resin, the terminal glycidyl ether of the alkylene oxide adduct of bisphenol A or bisphenol F, and (meth) acrylic acid The compound etc. which are obtained by etc. are mentioned.

Among these, Preferably, it is a compound obtained by the reaction materials of epoxy resins, such as terminal glycidyl ether of bisphenol-type epoxy resin, bisphenol A, or the alkylene oxide adduct of bisphenol F, and (meth) acrylic acid, etc., More preferably, It is a compound obtained by the reaction material of bisphenol-type epoxy resin and (meth) acrylic acid, etc.

As a commercial item of the compound obtained by the reaction material of a bisphenol-type epoxy resin and (meth) acrylic acid, etc., EH1010 (epoxy di (meth) acrylate, the product made by Shin-Nakamura Chemical Industries, Ltd.), biscot # 540 (product made by Osaka Chemical Industries, Ltd.), Epoxy ester 3000M, Epoxy ester 3000A (made by Kyoeisha), etc. are mentioned. As a commercial item of the compound obtained by epoxy resins, such as terminal glycidyl ether of the alkylene oxide adduct of bisphenol A or bisphenol F, and the reaction product of (meth) acrylic acid, etc., BPE-100 (made by Shin-Nakamura Kagaku Kogyo Co., Ltd.), biscoat # 700 (Osaka Yuki Kagaku Kogyo Co., Ltd.) etc. are mentioned.

<(b) Component: Organic Peroxide>

The organic peroxide of (b) component used for this invention is a radical initiator conventionally used in the anaerobic curable composition, It does not specifically limit, For example, cumene hydroperoxide, t-butyl hydroperoxide, p-methane Hydroperoxides such as hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, other ketone peroxides, diallyl peroxides, and peroxyesters Organic peroxides, such as these, etc. are mentioned. These organic peroxides can be used alone or as a mixture of two or more thereof. Of these, hydroperoxides are preferably used from the viewpoint of reactivity.

As for the compounding quantity of this (b) component, 0.1-5 weight part is preferable with respect to 100 weight part of total weight of the polymerizable monomer, oligomer, and polymer of (a) component. In this case, when less than 0.1 weight part, it is inadequate to generate a polymerization reaction, and when more than 5 weight part, the storage stability of an anaerobic curable composition falls.

<(c) component: o-benzoic sulfimide>

(C) component used in this invention is o-benzoic sulfimide, and is used for an anaerobic curable composition normally with (b) component. By mix | blending said (c) component, favorable anaerobic sclerosis | hardenability can be achieved. It is preferable that 0.1-5 weight part of addition amounts of (c) component are mix | blended with respect to 100 weight part of (a) component. When less than 0.1 weight part, there exists a possibility that initial stage sclerosis | hardenability may fall, and when it exceeds 5 weight part, the effect of suppressing generation | occurrence | production of outgas of hardened | cured material may become inadequate.

<(d) component: The epoxy resin which is solid at normal temperature which has glycidyl functional group in the side chain of a molecular skeleton>

The epoxy resin which is solid at normal temperature which has glycidyl group in the side chain of the molecular skeleton which is (d) component used for this invention is a compound which has at least 1 glycidyl group in the side chain of a molecular skeleton at least, and is effective in suppressing outgas. It is a component having. For example, a phenol novolak-type epoxy resin, an ortho cresol novolak-type epoxy resin, a dicyclopentadiene type epoxy resin, a glycidyl group containing vinyl type polymer, etc. are mentioned, The compound which is a solid at normal temperature (25 degreeC) is mentioned. Used. Moreover, these can also be used individually or in mixture of 2 or more types. Of these, glycidyl group-containing vinyl polymers, phenol novolak-based epoxy resins, and orthocresol novolak-type epoxy resins are preferred from the effect of suppressing outgas, and more preferably glycidyl group-containing vinyl resins. It is a type | system | group polymer and an ortho cresol novolak-type epoxy resin, Especially preferably, it is a glycidyl group containing vinyl type polymer.

The epoxy equivalent of (d) component becomes like this. Preferably it is 190-900, More preferably, it is 200-650, Especially preferably, it is 210-400. If it is outside the range of 190-900, there exists a possibility that the effect of suppressing generation | occurrence | production of outgas may become inadequate. In addition, epoxy equivalent is measured by the method of JISK-7236 (2001).

As for the weight average molecular weight of (d) component, 500-40,000 are preferable in polystyrene conversion, More preferably, it is 1,000-20,000. The weight average molecular weight is measured by gel permeation chromatography (GPC). When the weight average molecular weight is less than 500, since the toughness of the cured product is impaired, a decrease in adhesion occurs. When the weight average molecular weight exceeds 40,000, the effect of suppressing the generation of outgas becomes insufficient, and the composition becomes remarkably high viscosity, so workability is lowered.

(d) It is preferable to add 1-200 weight part with respect to 100 weight part of total amounts of the polymerizable monomer, oligomer, and polymer of (a) component, More preferably, it is 5-100 weight part, Especially preferably, 10 to 70 parts by weight. In this case, when less than 1 weight part, since the outgas of hardened | cured material will increase, there exists a possibility that the objective of this invention may not be achieved. When more than 200 weight part, the anaerobic curability of the composition of this invention falls, and there exists a possibility that the initial stage sclerosis | hardenability of hardened | cured material may fall.

As the glycidyl group-containing vinyl polymer corresponding to the component (d), a copolymer of a monomer having an ethylenically unsaturated group and a glycidyl group and a monomer containing an ethylenically unsaturated group is preferable in terms of excellent outgas suppression effect of the cured product. Do.

As a monomer which has an ethylenically unsaturated group and glycidyl group, it is (meth) acrylic-acid glycidyl, (alpha)-ethyl acrylate glycidyl, (alpha)-n-propyl acrylate glycidyl, and (alpha)-n-butyl acrylate glycidyl, for example. Acrylic esters having a glycidyl group in ester moieties such as (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, allyl glycidyl ether, and glycidyl p-vinylbenzoate And glycidyl diene carboxylates such as methyl glycidyl itaconate, ethyl glycidyl maleate, vinyl glycidyl sulfonate, glycidyl-β-vinyl acrylate and glycidyl sorbate. have. Among these, it is preferable to use glycidyl (meth) acrylate.

As a monomer copolymerizable with the monomer which has the ethylenically unsaturated group and glycidyl group which are the structural components of the glycidyl-group containing vinyl type polymer corresponding to (d) component, the monomer which has an ethylenically unsaturated group is mentioned, for example. Specifically, (meth) acrylic-acid alkylester, (meth) acrylic-acid dicyclopentanyl, fumaric acid alkylester, styrene, (alpha)-alkylstyrene, acrylonitrile, isobutylene, butadiene, isoprene, vinyl acetate, divinyl, for example Butyral etc. are mentioned. Among these, (meth) acrylic-acid alkylester is used suitably from the point of compatibility with (a) component.

Among the glycidyl group-containing vinyl polymers corresponding to component (d), those having particularly excellent outgas resistance and adhesive strength, which are required properties of the present application, are particularly preferred compounds such as glycidyl (meth) acrylate and alkyl (meth) acrylate. Of copolymers. As an example of this compound, muffle loop G-0150M, G-2050M, G-017581 (made by Nippon Yushi), etc. are mentioned.

Moreover, by using together the (d) component and the epoxy resin which is not contained in (d) component, it is used preferably at the point which can control outgas suppression, viscosity adjustment, and initial stage curability.

The epoxy resin which is not contained in (d) component is bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, dimeric glycidyl ester type epoxy resin, polyalkylene ether type epoxy resin, for example. , A biphenyl type epoxy resin, a naphthalene type epoxy resin, an alicyclic epoxy resin, a heterocyclic containing epoxy resin, a glycidyl amine type epoxy resin, etc. are mentioned, These can also be used individually or in mixture of 2 or more types. Of these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferably used from the viewpoints of workability and initial curing properties.

<(e) component: Hardening agent for epoxy resins>

(E) component used for this invention is a hardening | curing agent for epoxy resins. The component (e) acts as a curing agent for the component (d). As (e) component, a heterocyclic secondary amine, a heterocyclic tertiary amine, an aromatic tertiary amine, an azole compound, an imidazole compound, etc. are mentioned, for example.

Examples of the heterocyclic secondary amines include 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroquinaldine and the like. As heterocyclic tertiary amine, quinoline, methylquinoline, quinaldine, quinoxalinephenazine, etc. are mentioned. Examples of the aromatic tertiary amines include N, N-dimethyl-anisidine, N, N-dimethylaniline, and the like. Examples of the azole compound include 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, 3 Mercaptobenzotriazole etc. are mentioned. As an imidazole compound etc., 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, etc. are mentioned. Among these, an imidazole compound is used preferably from a viewpoint of adhesive strength.

The component (e) is preferably added in an amount of 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, particularly preferably based on 100 parts by weight of the total weight of the polymerizable monomer, oligomer and polymer of the component (a). Is 10 to 40 parts by weight. If less than 3 parts by weight, outgas is generated from the cured product, and thus the object of the present invention cannot be achieved. When more than 60 weight part, since the amount of hardening | curing agent components is excessive and unreacted (e) component remains after hardening, there exists a possibility that adhesive strength may fall.

The anaerobic curable composition of this invention can add the component which accelerate | stimulates superposition | polymerization other than the said component. As these components, an amine compound, a mercaptan compound, a hydrazine compound, etc. are mentioned besides o-benzoic sulfimide.

Amine compounds are heterocyclic secondary amines such as 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroquinaldine, quinoline, methylquinoline, quinaldine, quinoxalinephenazine and the like. Aromatic tertiary amines such as heterocyclic tertiary amines, N, N-dimethyl-anisidine, N, N-dimethylaniline, 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, Azole compounds such as benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, 3-mercaptobenzotriazole, and the like, and the like, but are not limited thereto.

Examples of the mercaptan compound include linear mercaptans such as n-dodecyl mercaptan, ethyl mercaptan, and butyl mercaptan, but are not limited thereto.

Examples of the hydrazine compound include 1-acetyl-2-phenylhydrazine, 1-acetyl-2- (p-tolyl) hydrazine, 1-benzoyl-2-phenylhydrazine, 1- (1 ', 1', 1'-trifluoro Rho) acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2- (p-bromophenyl) hydrazine, 1-acetyl-2- (p-nitrophenyl) hydrazine, 1-acetyl-2- (2'-phenylethylhydrazine), ethylcarbazate, p-nitrophenylhydrazine, p-trisulfonylhydrazide, and the like, but are limited thereto. It doesn't work.

With respect to the present invention, various elastomers, fillers, storage stabilizers, antioxidants, light stabilizers, adhesion aids, photoinitiators, plasticizers, dyes, such as acrylic rubbers, urethane rubbers, styrene copolymers, etc., without impairing the object of the present invention. Additives such as pigments, flame retardants and surfactants.

With respect to the present invention, for the purpose of improving the elastic modulus, flowability, and the like of the cured product, a filler having a degree of not impairing storage stability may be added. Specifically, organic powder, inorganic powder, metallic powder, etc. are mentioned.

As a filler of inorganic powder, glass, fumed silica, alumina, mica, ceramics, silicon rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dry clay mineral, dry diatomaceous earth, etc. are mentioned. As for the compounding quantity of an inorganic powder, about 0.1-100 weight part is preferable with respect to 100 weight part of (A) component. When less than 0.1 weight part, an effect is small, and when larger than 100 weight part, fluidity | liquidity of a composition runs short and workability | operativity falls.

The fumed silica filler is blended for the purpose of adjusting the viscosity of the anaerobic curable composition or improving the mechanical strength of the cured product. Preferably, those hydrophobized with organochlorosilanes, polyorganosiloxanes, hexamethyldisilazane and the like are used. As a specific example of fumed silica, commercial items, such as the brand name Aerosil R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, R202 by Nippon Aerosil, are mentioned, for example.

As a filler of organic powder, polyethylene, polypropylene, nylon, crosslinked acrylic, crosslinked polystyrene, polyester, Teflon (trademark), polyvinyl alcohol, polyvinyl butyral, polycarbonate is mentioned, for example. As for the compounding quantity of organic powder, about 0.1-100 weight part is preferable with respect to 100 weight part of (a) component. When less than 0.1 weight part, an effect is small, and when larger than 100 weight part, fluidity | liquidity of a composition runs short and workability | operativity falls.

You may add a storage stabilizer with respect to this invention. As a storage stabilizer, radical absorbing agents, such as benzoquinone, hydroquinone, and hydroquinone monomethyl ether, metal chelating agents, such as ethylenediamine tetraacetic acid or its 2-sodium salt, oxalic acid, acetylacetone, o-aminophenol, etc. can also be added.

Antioxidant can also be added with respect to this invention. As antioxidant, For example, (beta) -naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert- butyl hydroquinone, 2,5-di-tert Quinone compounds such as -butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone and 2,5-di-tert-butyl-p-benzoquinone; Phenothiazine, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di- tert-butyl-p-cresol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] , Zenpropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 branched alkyl ester, 2,4-dimethyl-6- (1-methylpentadedecyl) phenol, diethyl [ [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a , a ', a "-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propio Nate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy- 2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, of N-phenylbenzeneamine and 2,4,6-trimethylpentene Reaction product, 2,6-di-tert-butyl-4- (4,6-bis (octylti) ) -1,3,5-triazin-2-ylamino) phenol-based compounds such as phenol, picric acid, citric acid; Tris (2,4-di-tert-butylphenyl) phosphite, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] di Oxaphosphine-6-yl] oxy] ethyl] amine, bis (2,4-di-tert-butylphenyl) pentaerythritoldiphosphite, bis [2,4-bis (1,1-dimethylethyl) -6 -Methylphenyl] ethyl ester phosphoric acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-bisphenyl] -4,4'-diylbisphosphonite, 6- [3- (3-tert Phosphorus such as -butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine compound; Dilauryl 3,3'- thiodipropionate, dimyristyl 3,3'- thiodipropionate, distearyl 3,3'- thiodipropionate, pentaerythryl tetrakis (3- Sulfur compounds such as laurylthiopropionate) and 2-mercaptobenzimidazole; Amine-based compounds such as phenothiazine; Lactone-based compounds; Vitamin E-based compounds, and the like. Among them, phenol compounds are suitable.

Light stabilizers may also be added for the present invention. As the light stabilizer, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] Ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2 , 6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1 -Dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, decandiodioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1 Reaction product of dimethylethylhydroperoxide with octane, N, N ', N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6- Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine.1,3,5-triazineN, N'-bis (2,2,6,6-tetra Polycondensate of methyl-4-piperidyl-1,6-hexamethylenediamine with N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol Polymerized product of 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3,20-diazaspiro [5 · 1 · 11 · 2] henicoic acid -21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecylester / tetradecylester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5,1,11,2] henicoic acid-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazacyclo- [5,1,11,2]- Henicoic acid -20-propane acid dodecyl ester / tetrade Silester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6 Higher fatty acid esters of tetramethyl-4-piperidinol, 1,3-benzenedicarboxyamide, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) Dudamine type compound; Benzophenone compounds such as octabenzone; 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [ 2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl ) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl3- (3- (2H-benzotriazol-2-yl)- Reaction products of 5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, benzotriazole type, such as 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol compound; Benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; Triazine compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol; and the like. Especially preferably, it is a hindered amine compound.

An adhesion imparting agent can also be added with respect to this invention. Examples of the adhesion agent include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, and γ-methacryloxypropyl Trimethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Oxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ- C5, such as urea propyl triethoxysilane, hydroxyethyl methacrylate phosphate ester, methacryloxy oxyethyl acid phosphate, methacryloxy oxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl methacrylate phosphate, etc. Additives synthesized from oils (Nipbon "Queentone" (dicyclopentadiene resin) made from Xeon Corporation, "alcon" made by Arakawa Chemical Industries, "neo polymer" made by Nippon Seki Co., Ltd.), etc. are mentioned. Among these, hydroxyethyl methacrylate phosphate ester, methacryloxyoxyethyl acid phosphate, methacryloxyoxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl methacrylate phosphate, etc. are preferable. As for content of an adhesive imparting agent, 0.05-30 mass parts is preferable with respect to 100 mass parts of (a) component, More preferably, it is 0.2-10 mass parts.

Drying oil can also be added with respect to this invention in order to improve the sclerosis | hardenability of the place which contacts air. As dry oil, what is called glycerin ester of unsaturated fatty acids, such as linseed oil and voile oil, etc. are mentioned, for example.

The anaerobic curable composition of this invention can be manufactured by a conventionally well-known method. For example, a predetermined amount of (a) component, (b) component, (c) component and (d) component, and other components arbitrarily are mix | blended, and mixing means, such as a mixer, Preferably it is 10-10. It can manufacture by mixing at the temperature of 70 degreeC preferably 0.1 to 5 hours. Although the anaerobic curable composition of this invention can be used as a one-component composition in this way, Preferably it is used as a two-component composition. At this time, it is preferable that one liquid contains the epoxy resin which has glycidyl functional group in the side chain of the molecular skeleton which is (d) component, and the other liquid contains the epoxy resin hardening | curing agent which is (e) component. In this way, by dividing the component (d) and the component (e) into separate liquids, unnecessary reactions can be suppressed during storage, thereby improving storage stability. Also in such a two-part composition, each liquid can be manufactured by mixing by the said method. In addition, two liquids are mixed and used at the time of use.

Since the anaerobic curable composition of this invention suppresses generation | occurrence | production of the outgas of hardened | cured material, and is excellent in initial stage hardenability and excellent in adhesive force, outgassing, such as electronic components, such as a hard disk drive device, and optical components, such as an optical lens, is generated. It is very effective as an adhesive agent and a sealing agent of the location which become a problem. In particular, it is suitably used for electronic devices, such as a hard disk drive apparatus, for which the adhesive agent of low outgas is required.

<Examples>

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited to these Examples.

The test method used in the Example and the comparative example is as follows.

<Production of Resin Composition>

Each component was extract | collected by the mass part shown to Tables 1-6, 30 minutes was mixed with the planetary mixer at normal temperature, the resin composition was adjusted, and it measured as follows about various physical properties. In addition, the detailed adjustment amount is according to Tables 1-6, and all numerical values are represented by a mass part.

<a component>

a1: EH1010 (epoxydi (meth) acrylate, the product made by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

a2: BPE-100 (ethoxylated bisphenol A di (meth) acrylate, the product made by Shin-Nakamura Chemical Industries, Ltd.)

a3: Light ester HO (2-hydroxyethyl (meth) acrylate, the Kyoesha Chemical company make)

a4: Light ester IBX (isobornyl acrylate, Kyoesha Chemical Co., Ltd. make)

a5: 3G (triethylene glycol di (meth) acrylate, the product made by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

<b component>

b1: cumene hydroperoxide (1 hour half life temperature 188.2 degreeC, the Nippon Yushi Corporation make)

<c component>

c1: o-benzoic sulfidem

<d component>

d1: Murup G0150M (solid at room temperature, weight average molecular weight 10,000, epoxy equivalent 370, copolymer of glycidyl methacrylate and methyl methacrylate, manufactured by Nippon Yushi Corp.)

d2: N-695 (solid at room temperature, epoxy equivalent 214, softening point 90 to 100 ° C, cresol novolac epoxy resin, manufactured by DIC Corporation)

<comparative component of the d component>

d3: Murup G01100 (solid at room temperature, weight average molecular weight 12,000, epoxy equivalent 170, homopolymer of glycidyl methacrylate, manufactured by Nippon Yushi)

d4: Muff loop G0115S (solid at room temperature, weight average molecular weight 11,000, epoxy equivalent 1000, copolymer of glycidyl methacrylate and styrene, manufactured by Nippon Yushi)

d5: Epicoat 154 (solid at room temperature, epoxy equivalent 176 to 180, phenol novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

<Comparative Component to Component d>

d1 ': EXA-835LV (liquid at room temperature, epoxy equivalent 160 to 170, bisphenol F type epoxy resin, manufactured by DIC Corporation)

d2 ': YP-70 (solid at room temperature, the weight average molecular weight 50,000-70,000, epoxy equivalent 11,000-17,000, the copolymerization phenoxy resin of bisphenol A and bisphenol F, the Shin-Il Chem Chemical Co., Ltd.)

<e component>

e1: acidamide A-100 (modified imidazole, Sanwa Chemical Co., Ltd. make)

e2: 1B2MZ (1benzoyl-2-methylimidazole, the product made by Shikoku Kasei Kogyo Co., Ltd.)

The test piece used for the set time test and the adhesive strength test was obtained by dissolving 0.5 parts of copper 2-ethylhexanoate in 100 parts of acetone as a primer using material SPCC-SD, 100 mm × 25 mm (JIS G 3141: 2009). What was previously apply | coated to the test piece and dried was used.

<Set time test>

About 0.06 g of each composition obtained above was dripped at the said test piece, and the time which does not move by hand by overlapping the same test piece was made into set time.

Shear Adhesion Test

Similarly, after baking 1 hour at 90 degreeC making the end of 1 cm of test pieces overlap, tensile strength was measured at normal temperature.

<Outgas test>

20 mg of each resin composition is weighed, measured by SEIKO Instruments Corporation heat loss measuring apparatus TG / DTA220 at 90 ° C. for 3 hours continuously, the first 1 hour is the baking time, and the weight loss of 2 hours after the end of baking is measured. did.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various corrections and changes can be added without deviating from the range and mind of this invention.

This application is based on the JP Patent application 2010-288276 of an application on December 24, 2010, The content is taken in here as a reference.

Since the anaerobic curable composition of this invention suppresses generation | occurrence | production of the outgas of hardened | cured material, is excellent in initial stage sclerosis | hardenability, and is excellent in adhesive force, it is an adhesive agent and sealing agent of the location which generate | occur | produces outgas, such as HDD and an optical component, and becomes a problem. It is very effective and industrially useful in that it can be applied to a wide range of fields.

Claims (8)

Anaerobic curable composition containing the following (a)-(e) component:
(a) a compound having at least one radically polymerizable functional group in a molecule;
(b) organic peroxides;
(c) o-benzoic sulfide;
(d) an epoxy resin that is solid at room temperature having glycidyl functional groups in the side chain of the molecular skeleton; And
(e) Curing agent for epoxy resins. The anaerobic curable composition of Claim 1 whose epoxy equivalent of the said (d) component is 190-900. The anaerobic curable composition according to claim 1 or 2, wherein the component (e) is 3 to 60 parts by weight based on 100 parts by weight of the component (a). The anaerobic curable composition according to any one of claims 1 to 3, wherein the component (d) is a glycidyl group-containing vinyl polymer. The anaerobic curable composition according to any one of claims 1 to 4, wherein the component (d) is a copolymer of a monomer having an ethylenically unsaturated group and a glycidyl group, and a monomer containing an ethylenically unsaturated group. The anaerobic curable composition according to any one of claims 1 to 5, wherein the component (e) is an imidazole compound. The anaerobic curable composition according to any one of claims 1 to 6, which is an adhesive for an electronic component for joining the electronic component.  The anaerobic curable composition according to any one of claims 1 to 6, which is an adhesive for a hard disk.