JP3305822B2 - Curable resin composition, adhesive and sealant using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a solventless type used for bonding and sealing various materials such as metal, has a fast curing property, and has good adhesiveness to an oil surface. The present invention also relates to a curable resin composition having excellent heat-resistant adhesive strength and an adhesive and a sealant comprising the curable resin composition.

[0002]

2. Description of the Related Art Conventionally, a welding method is generally used as a method of joining metal materials, and thereafter, various methods such as electrodeposition coating for imparting corrosion resistance and electrostatic coating for improving appearance are used. Painting is being done.

[0003] Since welding is performed at a very high temperature, thermal distortion occurs at a joint or the like, causing stress concentration. Furthermore, welding has problems such as the need for skilled personnel, the need for a large amount of electric power, the difficulty in joining dissimilar metals, and the inability to join with non-metal mixed materials. In addition, in various kinds of coating, the coating film is often heated using an oven for baking and drying, so that a heat history is given to the joint portion and the seal portion.

[0004] On the other hand, the use of an adhesive has advantages such as almost solving the above-mentioned problems of welding depending on how to use it, further increasing the durability by dispersing the stress applied to the joint, and reducing the vibration. The bonding and sealing of various materials with an adhesive has been gradually performed.

For example, epoxy resin adhesives include:
Numerous one-component adhesives using dicyandiamide or the like as a curing agent, two-component adhesives using amine or polyamide as a curing agent, and the like have been proposed. However, with a one-part epoxy adhesive,
A long curing time of about 30 minutes is required even at a temperature of about 150 to 180 ° C., and a two-part epoxy resin adhesive is
In order to prevent poor curing and the like, it is necessary to make the mixing ratio with the curing agent constant and to mix completely uniformly.

The urethane resin-based adhesive includes a moisture-curable one-part urethane resin-based adhesive and a two-part urethane resin-based adhesive containing one liquid containing isocyanates and the other liquid containing a polyol. There are agents. However, the one-part type requires several days to cure, and the two-part type requires quantitative blending and complete uniform mixing, as with the two-part epoxy resin adhesive, and manages humidity to prevent foaming. Each has its own problems, such as the necessity of bonding in a degraded environment. Further, there is a problem that the urethane resin-based adhesive generally has poor adhesion to a metal oil surface.

As the acrylic resin-based adhesive, a two-component adhesive called a so-called SGA has been used for various applications. However, since it contains a large amount of low boiling components, it has a strong odor and a cured product. However, even though it is considered that the heat resistance is not sufficient and rough mixing is sufficient, there is a problem that the two-part type requires careful management.

As the urethane-modified (meth) acrylate-based curable resin composition, a resin composition having good adhesiveness using a urethane-modified (meth) acrylate and an organic peroxide is disclosed in Japanese Patent Application Laid-Open No. 63-165418. , JP-A-63-
165419) has the disadvantage that the adhesive strength is reduced when the joined body is subjected to heat history.
There is also proposed a heat-resistant resin composition (JP-B-55-30527) in which a trivalent or pentavalent organic phosphorus compound is blended with a urethane-modified acrylate resin, but the adhesive strength is insufficient. Not. Therefore, it has good adhesiveness and sufficient adhesiveness to an oil surface, and has a small decrease in adhesiveness even when subjected to a high-temperature (for example, 140 to 200 ° C.) heat history in various kinds of coating and the like. It is desired to develop a sufficiently satisfactory curable resin composition having the following.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art and the like. It is a solventless type, has good adhesiveness to an oil surface, and has a cured product. The present invention provides a curable resin composition which can be used as an adhesive or a sealant having heat resistance to withstand high temperatures, and a laminate and a filler using the curable resin composition.

[0010]

That is, the present invention provides (a)
Urethane-modified (meth) acrylate [I] having at least one or more (meth) acryloyl groups and one or more urethane bonds per molecule and having a polybutylene glycol structure in the molecule, or the urethane-modified (meth)
A total of 40 to 90 parts by weight of the acrylate [I] and the urethane-modified (meth) acrylate [II] other than [I],
(B) 10 to 60 parts by weight of (meth) acrylates other than the urethane-modified (meth) acrylate, and (c) a compound represented by the following general formula (1) based on 100 parts by weight of the total of (a) and (b). 0.1 to 20 parts by weight of a phosphoric acid compound and / or a salt thereof, (d) 10 to 150 parts by weight of an inorganic powder filler having an average particle size of 50 μm or less, and (e) an amount of polymerization effective for curing. It is a curable resin composition containing an initiator.

[0011]

Embedded image [Wherein, R represents CH ₂ ＣＲCR ₁ CO (OR ₂ ) _m] . Here, R ₁ is H or CH ₃ , and R ₂ is —C ₂ H _{4
-, - C 3 H 6 -} , - CH 2 CH (CH 3) -, - C 4
_{H 8 -, - C 6 H} 12 - or _{-C 2 H 4 -O-CO-} C
₅ H ₁₀ - a, m is an integer of from 1 to 10. n is 1 or 2. Further, the present invention is that composed of the curable resin composition
Characteristic adhesives and sealants .

Hereinafter, each component constituting the curable resin composition of the present invention will be described in detail. In the component (a) used in the present invention, "a urethane-modified (meth) having at least one or more (meth) acryloyl groups and one or more urethane bonds per molecule and having a polybutylene glycol structure in the molecule" Acrylate [I]]
Reaction product having two (meth) acryloyl groups per molecule obtained by reacting a (meth) acrylate having a hydroxyl group, a polyisocyanate, and a polyol in which at least one of the polyols used has a polybutylene glycol structure Urethane-modified (meth) acrylate whose main component is a substance.

Specific examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxyethyl (meth) acrylate.
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyhexyl (meth)
Acrylate, hydroxyoctyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate and 2-hydroxy-3-chloropropyl (meth) acrylate.

Examples of the polyisocyanate include an aliphatic polyisocyanate and an aromatic polyisocyanate. Examples of the aliphatic polyisocyanate include hydrogenated diphenylmethane diisocyanate (hydrogenated MDI),
Examples include isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and tetramethyl Xylylene diisocyanate (TMXDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, and the like. Preferred polyisocyanates in the present invention are aliphatic polyisocyanate isophorone diisocyanate (IPDI) and hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), and aromatic polyisocyanate tolylene diisocyanate (TDI).

The urethane-modified (meth) acrylate [I] used in the present invention has a polybutylene glycol structure in the molecule, and this structure has at least one kind of polyol used in the production of the urethane-modified (meth) acrylate. Is a polyol having a polybutylene glycol structure. Urethane-modified (meth) using this polyol having a polybutylene glycol structure
The molecular weight of the acrylate [I] is preferably 1,000 to 40,000 in terms of polystyrene. If the molecular weight is less than 1,000, the cured product becomes too hard and the adhesive strength is reduced. If the molecular weight is more than 40,000, the cured product becomes soft and the heat resistance is reduced. The value of the molecular weight is a weight average molecular weight (Mw) determined by using a GPC system (SC-8010 manufactured by Tosoh Corporation) and creating a calibration curve with commercially available standard polystyrene.

In the present invention, the polyol used for obtaining the above [I] includes polybutylene glycol, a polyol having a polybutylene glycol structure as a part thereof, a polyester polyol comprising polybutylene glycol and a polybasic acid, and polybutylene. Polyester polyols comprising a polyol having a glycol structure as a part thereof and a polybasic acid, polyols having a polybutylene glycol structure as a part thereof, and polyester polyols comprising a polyol not having the structure and a polybasic acid are included. .

Examples of the polyol having a polybutylene glycol structure as a part thereof include polyols having at least one or more kinds of polypropylene glycol structures and / or polyethylene glycol structures in addition to the polybutylene glycol structure.

Examples of polybasic acids which may be used to obtain the above polyester polyols include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, phthalic anhydride, phthalic acid, terephthalic acid , Isophthalic acid, heptic acid, adipic acid, tetrahydroxyphthalic anhydride and the like.

Urethane-modified (meth) acrylate [I]
In the production of the compound (A), a polyol having a polybutylene glycol structure and a polyol not having the structure may be used in combination as a polyol component. Examples of the polyol having no structure include polyalkylene glycol such as polyethylene glycol and polypropylene glycol, polyester polyol, polycaprolactone polyol, polycarbonate diol, bisphenol derivative, and polybutadiene polyol.

The average molecular weight of the polyol used to obtain the urethane-modified (meth) acrylate [I] having a polybutylene glycol structure is from 162 to about 38,000.
0, more preferably 300 to 35,000.

In order to produce the urethane-modified (meth) acrylate [I] from the polyol, polyisocyanate, and (meth) acrylate having a hydroxyl group, these may be reacted by a known method. For example, reacting a polyol with a (meth) acrylate having a hydroxyl group after reacting a polyisocyanate with a polyol, reacting a polyol after reacting a polyisocyanate with a (meth) acrylate having a hydroxyl group, or reacting a polyol with a polyisocyanate and a hydroxyl group And a (meth) acrylate having the same. At this time, usually a catalyst such as dibutyltin dilaurate is used, and the reaction temperature is about 50 to 100 ° C.

The amount of the component (a) in the composition of the present invention is 40 to 90 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). When the amount is less than 40 parts by weight, it is difficult to obtain heat resistance, and when the amount is more than 90 parts by weight, the viscosity becomes high, so that there is a problem in workability.

A urethane-modified (meth) acrylate [I] other than the urethane-modified (meth) acrylate [I]
I] is a urethane-modified (meth) acrylate having no polybutylene glycol structure, and may be used as long as the object of the present invention is not impaired. Examples of such urethane-modified (meth) acrylates include those produced using polyols such as polyalkylene glycols such as polyethylene glycol and polypropylene glycol, various polyester polyols, polycaprolactone polyols, polycarbonate polyols, bisphenol derivatives, and polybutadiene diols. No.

The above [I] and [II] can be used alone or in combination of two or more.

Urethane-modified (meth) acrylate [I
The compounding amount of I] is 50 parts by weight or less, more preferably 40 parts by weight or less based on 100 parts by weight of the total of the urethane-modified (meth) acrylates [I] and [II]. If the amount exceeds 50 parts by weight, heat resistance and adhesiveness may be reduced.

Examples of the (meth) acrylate other than the urethane-modified (meth) acrylate as the component (b) used in the present invention include various monofunctional monomers and polyfunctional monomers. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate,
Phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, alkyloxy (poly) ethylene glycol mono (meth) acrylate, alkyloxy (poly) propylene glycol mono ( (T) acrylate, phenoxy (poly) ethylene glycol mono (meth) acrylate, phenoxy (poly) propylene glycol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, di Cyclopentenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 3-
Chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, morpholine (meth) acrylate, Ethoxycarbonylmethyl (meth) acrylate, ethylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth)
Acrylates, monofunctional (meth) acrylates such as 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride, and polyethylene glycol di (meth) acrylate, polyglycerol di (meth) acrylate, and polypropylene glycol di (meth) acrylate , Polybutylene glycol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) There are polyfunctional (meth) acrylates such as acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate and various epoxy (meth) acrylates, and these are one kind or two or more kinds. They can be used together. Among these, from the viewpoint of odor and foam prevention during curing,
The (meth) acrylate preferably has a boiling point of 100 ° C or higher, and particularly preferably 150 ° C or higher.

The amount of the (meth) acrylate other than the urethane-modified (meth) acrylate of the component (b) may be determined in consideration of the heat resistance and workability of the cured product of the composition. With respect to a total of 100 parts by weight of the modified (meth) acrylate and the (meth) acrylate other than the urethane-modified (meth) acrylate of the component (b), 1
0 to 60 parts by weight, preferably 20 to 50 parts by weight.

The composition of the present invention comprises, as other components,
Radical polymerizable diallyl maleate, diallyl phthalate, triallyl isocyanurate, compounds having an allyl group such as allyl glycidyl ether, maleic acid, maleic anhydride, unsaturated acids such as itaconic acid, styrene,
Divinylbenzene, α-methylstyrene, vinylpyrrolidone, vinylcaprolactam, alkyl vinyl ether and the like may be used as long as the object of the present invention is not impaired.

The phosphoric acid compound represented by the general formula (1) as the component (c) used in the present invention includes, for example, (meth) acryloyloxyethyl acid phosphate,
(Meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxyisopropyl acid phosphate, (meth) acryloyloxy polyoxyethylene glycol acid phosphate, (meth)
Acryloyloxy polyoxypropylene glycol acid phosphate, caprolactone-modified (meth) acryloyloxyethyl acid phosphate, di (meth) acryloyloxyethyl acid phosphate,
Di (meth) acryloyloxypropyl acid phosphate, di [caprolactone-modified (meth) acryloyloxyethyl] acid phosphate and the like can be mentioned.

The salt of the phosphoric acid compound represented by the general formula (1) as the component (c) used in the present invention has a hydroxyl group bonded to a phosphorus atom, which is not in the form of a salt in the formula. Are preferred. The substance which forms a salt with the phosphoric acid compound is an organic compound having an amino group, for example, an alkanolamine, in consideration of the solubility of the salt in other components in the composition, and the like. Compounds having both acryloyl groups are preferred. Specific examples of the salt include, for example, acryloyloxyethyl acid phosphate-monoethanolamine half salt, (meth) acryloyloxyethyl acid phosphate-dimethylaminoethyl (meth) acrylate half salt, (meth) acryloyloxyethyl acid phosphate- And diethylaminoethyl (meth) acrylate half salt.

The phosphoric acid compound and the salt thereof of the component (c) are 1
They can be used alone or in combination of two or more. (C)
The component is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total of the urethane-modified (meth) acrylate of the component (a) and the (meth) acrylate of the component (b). 15 parts by weight is desirable. If the amount is less than 0.1 part by weight, the effect of improving the adhesiveness of the composition is small, and if it exceeds 20 parts by weight, the adhesiveness of the composition is not improved,
Rather, they tend to decrease, and the storage stability of the composition deteriorates.

As the polymerization initiator of the component (e) used in the present invention, a thermal polymerization initiator, a photopolymerization initiator and a combination thereof are preferred. Specific examples of the thermal polymerization initiator and the photopolymerization initiator used as the polymerization initiator are shown below.

Examples of the thermal polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-trimethylcyclohexane peroxide, methylcyclohexane peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. Are peroxyketals 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane,
1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy)
Octane, normal butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (tert-butylperoxy) butane and the like are hydroperoxides such as tertiary butyl hydroperoxide and cumene hydro. Peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,
5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like are dialkyl peroxides such as ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, α, α'-bis (tert-butylperoxy-meta-isopropyl) benzene,
2,5-dimethyl-2,5-di (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-
Di (tert-butyl peroxide) hexyne-3
Etc. of diacyl peroxides, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, laurinoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, succinic acid peroxide, Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, and the like are peroxydicarbonates such as diisopropylperoxydicarbonate, di-2-ethylkihexylperoxydicarbonate, and di-n-propylpropylperoxide. Oxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, dimethoxyisopropyl peroxy Dicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate and the like, of peroxyesters, tertiary butyl peroxy acetate,
Tertiary butyl peroxyisobutyrate, tertiary butyl peroxypivalate, tertiary butyl peroxydecanate, cumyl peroxy neodecaneate, tertiary butyl peroxy-2-ethylhexanate, tertiary butyl peroxy −3,3,3
5-trimethylhexanate, tertiary butyl peroxy laurate, tertiary butyl peroxybenzoate, ditertiary butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary butyl Peroxy maleic acid, tertiary butyl peroxy isopropyl carbonate, cumyl peroxy octate, tertiary hexyl peroxy neodecaneate, tertiary hexyl peroxy pivalate, tertiary butyl peroxy neo hexanate, tertiary hexyl Peroxyneohexanate, cumylperoxyneohexanate, etc., and other peroxides include acetylcyclohexylsulfonyl peroxide, tertiary butyl Organic peroxides such as oxy-allyl carbonate.

In the present invention, in consideration of the stability and curing time of the composition, the thermal polymerization initiator is preferably an organic peroxide having a decomposition temperature of 80 ° C. to 160 ° C. for obtaining a half-life of 10 hours. Among these, peroxyketals, peroxyesters and hydroperoxides are preferable, and in particular, peroxyketals such as 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, Tertiary butyl peroxybenzoates of peroxyesters and cumene hydroperoxide of hydroperoxides are preferred.

Examples of the thermal polymerization initiator other than the organic peroxide include azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), azonitrile compounds. 1 'azopis (cyclohexane-1-carbonitrile), 2-phenylazo-4
-Methoxy-2,4-dimethylvaleronitrile and the like,
Azoamidine compounds such as 2,2'-azobis (2-methylpropionamidine) dihydrochloride are used as cyclic azoamidine compounds such as 2,2'-azobis [2- (2-imidazolin-2-yl) propane]. Are the azoamide compounds of 2,2'-azobis {2-methyl-normal- [1,1-bis (hydroxymethyl)-
2-hydroxyethyl] propionamide {, 2,2 '
-Azobis {2-methyl-normal- [1,1-bis (hydroxymethyl) ethyl] propionamide} and 1-[(1-cyano-1-methylethyl) azo] formamide are the same as alkylazo compounds, 2'-azobis (2,4,4-trimethylpentane) and the like.

The curing temperature of the curable resin composition using the above-mentioned thermal polymerization initiator is usually in the range of 100 ° C. to 250 ° C., and more preferably 110 ° C. to 220 ° C. 100
When the curing is performed at a temperature lower than 0 ° C., the curing time becomes longer, and a problem such as insufficient curing of the resin composition may occur. The strength of the resin composition tends to decrease.

Examples of the photopolymerization initiator include benzophenyl and its derivatives, benzyl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin derivatives such as benzyl dimethyl ketal, and diethoxy. Examples include acetophenone and other acetophenone derivatives, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and its derivatives, camphorquinone, and the like.

These polymerization initiators may be used alone or in combination of two or more. Of course, a thermal polymerization initiator and a photopolymerization initiator can be used in combination. The amount of the polymerization initiator used is a total of 10 (a) component, (b) component, (c) component and optionally other radical polymerizable components.
0.1 to 10 parts by weight is preferably based on 0 parts by weight. 0.
If the amount is less than 1 part by weight, the curing becomes slow, and if it exceeds 10 parts by weight, the curing speed does not improve, but rather the heat resistance may decrease.

The curable composition of the present invention can be made into a room-temperature curable resin composition by using a redox curing system. In that case, an organic peroxide and a curing accelerator are used. As the organic peroxide, those described above can be used. Examples of the curing accelerator include thiourea derivatives, amines, condensation products of aldehydes and amines, organic acid salts, and organic chelate compounds. Examples of the thiourea derivatives include diethyl thiourea, dibutyl thiourea, ethylene thiourea, and tetramethyl thiourea. And thioamide compounds such as urea and mercaptobenzimidazole. As amines, N, N-dimethyl-p-toluidine, N, N-
Dimethylaniline, ethylenediamine, triethanolamine and the like can be mentioned. Examples of the condensation reaction product of an aldehyde and an amine include a condensation reaction product of butyraldehyde and aniline. As organic acid salts, cobalt naphthenate,
Examples thereof include copper naphthenate and zinc naphthenate. Examples of the organic chelate compound include copper acetylacetonate, iron acetylacetonate, vanadium acetylacetonate, and cobalt acetylacetonate. These curing accelerators may be used alone or in combination of two or more. In addition, by dividing the composition containing neither the organic peroxide nor the curing accelerator into two, adding the organic peroxide to one and the curing accelerator to the other,
It is also possible to use a two-part curable resin composition.

The inorganic powder filler of the component (d) used in the present invention includes crystalline silica powder, fused silica powder, spherical silica powder, silica powder such as fumed silica, alumina powder including spherical powder, and silicon carbide. Powder, silicon nitride powder, boron nitride powder, talc powder, calcium carbonate powder, glass beads, shirasu balloon, titanium oxide powder and the like are exemplified. The inorganic powder filler used is preferably silica or alumina, and when used in combination with another inorganic powder filler, it is preferred that 50% by weight or more of the filler is silica or alumina.

In the present invention, the inorganic powder filler having an average particle diameter of 50 μm or less is used, and the average particle diameter is preferably 30 μm or less in consideration of the adhesiveness and heat resistance. If the average particle size exceeds 50 μm, the adhesiveness and heat resistance decrease. The average particle size is represented by a value measured by a powder particle size analyzer (Granulometer 751 manufactured by New Metals End Chemicals Corporation).

The use of several kinds of these inorganic powder fillers can be used without any problem. The amount of the inorganic powder filler used is 10 to 150 parts by weight, preferably 20 to 12 parts by weight, based on 100 parts by weight of the components (a) and (b) in total.
It is about 5 parts by weight. When the amount is less than 10 parts by weight, it is difficult to obtain heat resistance, and when the amount is more than 150 parts by weight, the viscosity of the composition is too high, so that workability is deteriorated and a cured product becomes brittle.

An organic filler may be used in combination with the inorganic powder filler within a range that does not impair the object of the present invention. Examples thereof include urethane resin powder, (meth) acrylic resin powder, silicone resin powder, fluororesin powder, and phenol. Resin powder, recycled rubber powder and the like can be mentioned. Further, in order to improve the strength and heat resistance of the cured product, various types of glass fibers, various types of aramid fibers, and fibrous materials such as nylon fibers may be used in combination.

The curable resin composition of the present invention may contain a small amount of a polymerization inhibitor for improving the storage stability. As polymerization inhibitors, methylhydroquinone,
Hydroquinone, catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone,
2,5-di-tert-butylhydroquinone, P-benzoquinone, 2,5-diphenyl-P-benzoquinone,
2,5-di-tert-butyl-P-benzoquinone, picric acid, phenothiazine, tert-butyl catechol, 2-butyl-4-hydroxyanisole, 2,6
It is possible to use commonly used polymerization inhibitors such as -ditert-butyl-P-cresol.

The amount of the polymerization inhibitor to be used is 0.001 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the components (a) and (b) in total. is there. When the amount is less than 0.001 part by weight, the storage stability of the composition is not improved, and when the amount is more than 3 parts by weight, the adhesion tends to decrease and the curing time is prolonged.

The curable resin composition of the present invention contains various commonly used elastomers, antioxidants, ultraviolet absorbers, plasticizers, thickeners, and thixotropic agents within a range not to impair the object of the present invention. Further, additives such as a silane coupling agent, a titanate coupling agent, a chelating agent, a dye, a pigment, a flame retardant, and a surfactant may be used.

To cure the curable resin composition of the present invention, heating, light irradiation, or a combination thereof is preferable depending on the polymerization initiator contained therein. Further, the redox curable composition using an organic peroxide and a curing accelerator together can not only cure at room temperature but also accelerate the curing by heating. The composition of the present invention can be cured by irradiation with active energy rays, in which case the composition does not necessarily need to contain a polymerization initiator.

As a method of heating and curing the composition, for example, a method using hot air such as an oven or a dryer, a method using infrared rays including near-infrared rays and far-infrared rays such as lamps and heaters, and a direct heater etc. A method of heating and the like can be used, and as a method of photo-curing, for example, there is a method of using visible light and ultraviolet light, and a method of using active energy rays such as an electron beam.

The curable resin composition of the present invention can be used to form a laminated body or a filling which is bonded or sealed. Preferred materials used to obtain a laminate or a filling using the curable resin composition of the present invention include, for example, various metal materials including plated ones, various plastic materials, various ceramic materials, and the like. However, among the above, the above metal materials are preferable.

The curable resin composition of the present invention has excellent oil surface adhesiveness and a high curing speed, and the cured product exhibits excellent adhesive strength, heat resistance, flexibility and toughness. In particular, the specific inorganic powder filler greatly contributes to the improvement of the adhesiveness, the curing shrinkage is reduced, and the strength of the cured product is improved.Thus, the curable resin composition of the present invention is combined with the above-mentioned various properties. Demonstrate unprecedented overall excellent characteristics.

[0051]

EXAMPLES The present invention will be specifically described below with reference to examples.

Reference Example 1 [Synthesis example of urethane-modified (meth) acrylate] Isophorone diisocyanate as polyisocyanate
1 part by weight and 0.005 part by weight of dibutyltin dilaurate as a catalyst are placed in a reaction vessel, and the reaction temperature is 50 ° C.
Then, 60.3 parts by weight of polybutylene glycol having an average molecular weight of 1,000 was gradually added as a polyol to cause a reaction. Further, the reaction solution is heated and maintained at 70 ° C., and has a hydroxyl group-containing (meth)
The reaction was carried out by gradually adding 13.6 parts by weight of 2-hydroxyethyl methacrylate as an acrylate. The isocyanate group in this reaction solution was analyzed using an infrared absorption spectrum, and the reaction was continued until the absorption of the isocyanate group disappeared.

Using the urethane-modified (meth) acrylate obtained by the above method, the compositions of Examples and Comparative Examples were blended to obtain compositions. The laminate using the obtained composition was evaluated for adhesive strength and heat resistance by the following methods (a), (b) and (c).

(A) Tensile shear bond strength test (Example 1)
To 24, 27, 28 and Comparative Examples 1 to 14) A commercially available 1.6 t (mm) cold-rolled (SPCC) oil-side steel plate was cut into 25 × 100 (mm) to obtain a test piece. After wiping the surface with a rag, the curable resin composition was applied to the surface, and two test pieces were stuck together. This was left to cure for 15 minutes in a 150 ° C. oven (PH-200, manufactured by Tabai Espec) to obtain a laminate. After the laminate is returned to room temperature, a tensile shear tester (RTM-
Using 1T, UTM-5T, manufactured by Orientec Co., Ltd.), the tensile shear strength (JISK-6850) was measured. The formulations are shown in Tables 1 to 8 and 14, and the measurement results are shown in Tables 9-1.
3 and 15.

(B) Tensile adhesive strength test (Examples 25 to 25)
26) Commercially available white plate glass of 3.0 t (mm) was 12.7 × 1
After being cut to 2.7 (mm) to obtain a test piece, the surface of the test piece was wiped with a dry rag, and then the surface (12.7 × 1
(2.7 mm), the curable resin composition was applied, and two test pieces were stuck together. 4,000 (mJ / cm ² )
(UV irradiation furnace, F450-20, manufactured by Somar Co.) to cure the composition to obtain a laminate. An iron jig for a tensile bond strength test was bonded to each of two surfaces of 12.7 × 12.7 mm of the laminate, and a tensile shear tester (RTM-1T, UTM-5T, manufactured by Orientec Co., Ltd.) ) Using a tensile adhesive strength (JIS K-68).
49) was measured. Table 14 shows the composition and Table 15 shows the measurement results.
Shown in

(C) Heat resistance The laminate obtained by the above methods (a) and (b) is
After the heat treatment under the conditions described in (1) and (2), the adhesive strength was measured by the methods (A) and (B) above. The results are shown in Tables 9 to 13 and Table 15 together with the broken state. 60 minutes in a 180 ° C. oven 60 minutes in a 200 ° C. oven 60 minutes in a 220 ° C. oven

Examples 1 to 4 70 parts by weight of a urethane-modified (meth) acrylate having a polybutylene glycol structure in the molecule shown in Table 1 having an isocyanate component of IPDI and different average molecular weights, and methoxydiethylene glycol 30 parts by weight of methacrylate, 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane based on 100 parts by weight of these 2 parts by weight and spherical silica powder 50 having an average particle size of 10 μm
Parts by weight were added and blended.

Comparative Example 1 A urethane-modified acrylate having a polyester polyol (EG adipate) structure of ethylene glycol and adipic acid in the molecule shown in Table 6 and containing 70 parts by weight of an isocyanate component of IPDI, and methoxydiethylene glycol methacrylate 30 Parts by weight, these 100
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butyl-peroxy) -3,3,5-trimethylcyclohexane, and an average particle diameter of 10 μm with respect to parts by weight. Was added and blended.

Comparative Example 2 A urethane-modified acrylate having a bisphenol A-modified ethylene oxide structure in the molecule shown in Table 6 in which the isocyanate component is TDI 70 parts by weight, methoxydiethylene glycol methacrylate 30 parts by weight, and 100 parts by weight thereof With respect to 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate,
1-bis (tert-butylperoxy) -3,3
2 parts by weight of 5-trimethylcyclohexane and an average particle size of 1
50 parts by weight of 0 μm spherical silica powder was added and blended.

Comparative Example 3 As shown in Table 6, 70 parts by weight of a urethane-modified acrylate having a polycarbonate diol structure in the molecule and having an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate and 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane with respect to 0 parts by weight, and an average particle diameter of 10 μm. Was added and blended.

Example 5 The isocyanate component of a urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 1 in which the isocyanate component is TDI, 70 parts by weight, methoxydiethylene glycol methacrylate 30 parts by weight, and 100 parts by weight thereof 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 50 parts by weight of spherical silica powder having an average particle size of 10 μm Parts were added and blended.

Example 6 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 2 and containing 70 parts by weight of an isocyanate component of IPDI, 30 parts by weight of phenoxyethyl methacrylate, and 100 parts by weight of these 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle diameter of 10 μm Parts were added and blended.

Example 7 30 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 2 having an isocyanate component of IPDI, 70 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 50 parts by weight of silica powder was added and blended.

Example 8 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 2 having an isocyanate component of IPDI (50 parts by weight), methoxydiethylene glycol methacrylate (50 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 50 parts by weight of silica powder was added and blended.

Example 9 As shown in Table 2, 90 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule and having an isocyanate component of IPDI, 10 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 50 parts by weight of silica powder was added and blended.

Comparative Example 4 30 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 6 having an isocyanate component of IPDI, 70 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 50 parts by weight of silica powder was added and blended.

Example 10 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 2 having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 4 parts by weight of tertiary butyl peroxybenzoate, and 50 parts by weight of silica powder having an average particle diameter of 10 μm were added to the parts by weight.

Example 11 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 3 and having an isocyanate component of TDI was 70 parts by weight, methoxydiethylene glycol methacrylate was 30 parts by weight, and 100 parts by weight thereof. Then, 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 4 parts by weight of tertiary butyl peroxybenzoate and 50 parts by weight of silica powder having an average particle diameter of 10 μm were added and blended.

Example 12 70 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 3 having an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of cumene hydroperoxide, and 50 parts by weight of silica powder having an average particle size of 10 μm based on parts by weight.
Parts by weight were added and blended.

Example 13 70 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule and having an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
1 part by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 2 parts by weight of 10 parts by weight 50 parts by weight of silica powder was added and blended.

Example 14 70 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 3 having an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
10 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and an average particle diameter of 10 μm. 50 parts by weight of silica powder was added and blended.

Example 15 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 3 having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
20 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of an average particle diameter of 10 parts by weight. 50 parts by weight of silica powder was added and blended.

Example 16 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 4 and containing 70 parts by weight of an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
1 part by weight of methacryloyloxyethyl acid phosphate monoethanolamine half salt, 1,1-bis (tert-butylperoxy)-
2 parts by weight of 3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Example 17 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 4 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of methacryloyloxyethyl acid phosphate monoethanolamine half salt, 1,1-bis (tert-butylperoxy)-
2 parts by weight of 3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Comparative Example 5 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 6 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of tri-n-butyl phosphite and 1,1-bis (tert-butylperoxy)-
2 parts by weight of 3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Comparative Example 6 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 7 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of tri-n-butylphosphine, 1,1-bis (tert-butylperoxy)-
2 parts by weight of 3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Comparative Example 7 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 7 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of tri-n-butyl phosphate and 1,1-bis (tert-butylperoxy)-
2 parts by weight of 3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Comparative Example 8 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 7 having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (mono / di) ethyl phosphate and 1,1-bis (tert-butylperoxy) based on parts by weight
2 parts by weight of -3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle diameter of 10 μm were added and blended.

Comparative Example 9 As shown in Table 7, a urethane-modified acrylate having a polybutylene glycol structure in the molecule and having an isocyanate component of IPDI was 70 parts by weight, methoxydiethylene glycol methacrylate was 30 parts by weight,
5 parts by weight of triethyl phosphate with respect to parts by weight,
1,1-bis (tert-butylperoxy) -3,
2 parts by weight of 3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle diameter of 10 μm were added and blended.

Comparative Example 10 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 7 and containing 70 parts by weight of an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of diethyl phosphite, 1 part by weight
1-bis (tert-butylperoxy) -3,3
2 parts by weight of 5-trimethylcyclohexane and an average particle size of 1
50 parts by weight of 0 μm silica powder was added and blended.

Comparative Example 11 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 8 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
25 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and silica having an average particle diameter of 10 μm with respect to parts by weight. Powder 5
0 parts by weight were added and blended.

Example 18 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 4 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 10 parts by weight of silica powder was added and blended.

Example 19 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 4 having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 100 parts by weight of silica powder was added and blended.

Example 20 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 4 and having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 125 parts by weight of silica powder was added and blended.

Example 21 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 5 having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 150 parts by weight of silica powder was added and blended.

Comparative Example 12 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 8 and containing 70 parts by weight of an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 5 parts by weight of silica powder was added and blended.

Example 22 70 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 5 having an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 2 parts by weight of an average particle diameter of 30 μm. 50 parts by weight of silica powder was added and blended.

Example 23 As shown in Table 5, 70 parts by weight of a urethane-modified acrylate having a polybutylene glycol structure in the molecule and having an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 2 parts by weight of an average particle diameter of 1 μm. Silica powder 5
0 parts by weight were added and blended.

Comparative Example 13 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 8 and containing 70 parts by weight of an isocyanate component of IPDI, 30 parts by weight of methoxydiethylene glycol methacrylate,
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and an average particle diameter of 60 μm. 50 parts by weight of silica powder was added and blended.

Example 24 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 5 having an isocyanate component of IPDI (70 parts by weight), methoxydiethylene glycol methacrylate (30 parts by weight),
5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 10 parts by weight of 10 parts by weight. 50 parts by weight of alumina powder was added and blended.

Example 25 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 14 and having an isocyanate component of IPDI and an average molecular weight of 3,500 was used.
Parts by weight, 30 parts by weight of methoxydiethylene glycol methacrylate, 100 parts by weight thereof, 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 0.5 parts by weight of benzyldimethyl ketal, and silica powder 50 having an average particle diameter of 10 μm. Parts by weight were added and blended.

Example 26 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 14 and having an isocyanate component of IPDI and an average molecular weight of 3,500
Parts by weight, 30 parts by weight of 2-hydroxyethyl methacrylate, 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate, 0.5 part by weight of benzyldimethyl ketal, and an average particle diameter of 10
50 parts by weight of μm silica powder was added and blended.

Example 27 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 14 having an isocyanate component of IPDI and an average molecular weight of 3,500 35
Parts by weight and a urethane-modified (meth) polyol having a polyester structure of ethylene glycol and adipic acid
35 parts by weight of an acrylate having an isocyanate component of IPDI and an average molecular weight of 3,000, 30 parts by weight of methoxydiethylene glycol methacrylate, and 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate based on 100 parts by weight of 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Example 28 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 14 having an isocyanate component of IPDI and an average molecular weight of 3,500 was used.
Parts by weight and a urethane-modified (meth) polyol having a polyester structure of ethylene glycol and adipic acid
21 parts by weight of an acrylate having an isocyanate component of IPDI and having an average molecular weight of 3,000, 30 parts by weight of methoxydiethylene glycol methacrylate, and 100 parts by weight, 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate; 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

Comparative Example 14 A urethane-modified acrylate having a polybutylene glycol structure in the molecule shown in Table 14 and having an isocyanate component of IPDI and an average molecular weight of 3,500 was obtained.
Parts by weight and a urethane-modified (meth) polyol having a polyester structure of ethylene glycol and adipic acid
42 parts by weight of an acrylate having an isocyanate component of IPDI and an average molecular weight of 3,000, 30 parts by weight of methoxydiethylene glycol methacrylate, and 100 parts by weight thereof, 5 parts by weight of (2-hydroxyethyl) methacrylic acid phosphate; 2 parts by weight of 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and 50 parts by weight of silica powder having an average particle size of 10 μm were added and blended.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

[0104]

[Table 9]

[0105]

[Table 10]

[0106]

[Table 11]

[0107]

[Table 12]

[0108]

[Table 13]

[0109]

[Table 14]

[0110]

[Table 15]

Example 29 and Comparative Example 15 In Example 29, the composition obtained in Example 1 was used, and in Comparative Example 15, the composition obtained in Comparative Example 2 was used. 1
Inch iron pipe (outside diameter about 34mm, inside diameter about 28mm)
Was cut on a glass plate such that the space became an upright cylindrical shape, and then the cylindrical space was filled with the above composition, and then placed in a 150 ° C. oven. For 15 minutes to cure the composition and obtain a fill. Then, in order to examine the heat resistance of the filler, the filler was heat-treated in an oven at 220 ° C. for 60 minutes, taken out, allowed to cool at room temperature, and then observed in the filler where the composition was cured. In Comparative Example 15, the cured product was separated from the inner wall surface of the pipe, and many cracks were generated in the cured product.
In No. 9, peeling and cracking were not observed, and the appearance was good.

[0112]

As described above, the curable resin composition of the present invention is a solvent-free type composition having good adhesiveness to oil surface materials and excellent heat resistance of the cured product. Things. Further, the laminate and the filling using the curable resin composition of the present invention are also excellent in heat resistance.

Continuation of the front page (56) References JP-A-4-74735 (JP, A) JP-A-2-135211 (JP, A) JP-A-3-250014 (JP, A) JP-A-63-235317 (JP) JP-A-58-174475 (JP, A) JP-A-56-99210 (JP, A) JP-A-62-143909 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08F 290/00-290/14 C08F 299/00-299/08 C08G 18/67 C09J 4/00-4/06 C09J 175/14-175/16 C09K 3/10

Claims (4)

(57) [Claims] (A) a urethane-modified (meth) acrylate having at least one (meth) acryloyl group and at least one urethane bond per molecule and having a polybutylene glycol structure in the molecule [I] Or the sum of the urethane-modified (meth) acrylate [I] and the urethane-modified (meth) acrylate [II] other than [I] is 40
To 90 parts by weight, (b) 10 to 60 parts by weight of (meth) acrylates other than the urethane-modified (meth) acrylate, and 100 parts by weight of the total of (a) and (b),
(C) 0.1 to 20 parts by weight of a phosphoric acid compound represented by the following general formula (1) and / or a salt thereof, (d) 10 to 150 parts by weight of an inorganic powder filler having an average particle diameter of 50 μm or less, and ( e) A curable resin composition containing an effective amount of a polymerization initiator for curing. Embedded image [Wherein, R represents CH ₂ ＣＲCR ₁ CO (OR ₂ ) _m] . Here, R ₁ is H or CH ₃ , and R ₂ is —C ₂ H _{4
-, - C 3 H 6 -} , - CH 2 CH (CH 3) -, - C 4
_{H 8 -, - C 6 H} 12 - or _{-C 2 H 4 -O-CO-} C
₅ H ₁₀ - a, m is an integer of from 1 to 10. n is 1 or 2. ] 2. The curable resin composition according to claim 1, wherein the polymerization initiator is a thermal polymerization initiator and / or a photopolymerization initiator. 3. The curable resin composition according to claim 1,
An adhesive characterized in that: 4. The curable resin composition according to claim 1,
A sealant, characterized in that: