JPS637206B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel modified epoxy curable compositions. Conventionally known epoxy resins generally have sufficient shear strength for practical use when used to bond metals such as iron, aluminum, nickel, stainless steel, etc., but their strength in the "peeling" direction is poor and poses a practical problem. It was hot. Further, ordinary epoxy resins have poor adhesion to soft vinyl chloride, rubber sheets, etc., and molded products of polystyrene, polyacrylate, etc. However, in order to improve these essential drawbacks of epoxy resins, various modifications have been made, such as urethane-modified epoxy, rubber-modified epoxy, acrylonitrile/styrene-modified epoxy, and nylon epoxy, but none of them are sufficient. do not have. Among these, in the case of urethane-modified epoxy and rubber-modified epoxy, the peeling strength against metal after heat curing is certainly improved, but the peeling strength after room temperature curing is insufficient, and they also contain polymers such as acrylonitrile and styrene. Although the modified epoxy improves the peel strength after curing at room temperature and the adhesion to soft PVC as the acrylonitrile content increases, it also has the drawback of poor water resistance.
Similarly, nylon epoxy also tends to have poor water resistance. However, as a result of intensive studies by the present inventors in order to improve these drawbacks, we have developed a composition in which a polymer is dispersed in a compound containing more than one 1,2-epoxy group per molecule on average. (However, the epoxy equivalent of the compound containing the 1,2-epoxy group is 150~
800, and the polymer contains, as monomer units, units derived from isocyanate prepolymer adducts of hydroxyacrylates and units derived from other ethylenically unsaturated monomers, and the polymer has Monomer 1,2-
(obtained by polymerization in a compound containing an epoxy group, and present in a proportion of 10 to 100% by weight based on the compound containing a 1,2-epoxy group) as a resin component. It has been found that a curable composition free from such drawbacks can be obtained. That is, the present invention provides (a) an isocyanate prepolymer adduct of hydroxyacrylates in a compound containing more than one 1,2-epoxy group per molecule on average and having an epoxy equivalent of 150 to 800; (b ) A modified curable composition comprising a curing agent for epoxy compounds. The compound containing a 1,2-epoxy group used in the present invention has the formula (Here Z is hydrogen atom, methyl group, ethyl group)
An epoxy resin having an average of more than one substituted or unsubstituted glycidyl ether group in the molecule, represented by the formula (Here, Z is a hydrogen atom, methyl group, or ethyl group)
An epoxy resin having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule, represented by the formula (Here, Z is a hydrogen atom, methyl group, or ethyl group)
It includes epoxy resins having more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule on average. Particularly preferred epoxy compounds are epoxy resins having an epoxy equivalent of 150 to 800. The above-mentioned epoxy resins having more than one substituted or unsubstituted glycidyl ether group in the molecule include epoxy resins obtained by glycidyl etherification of phenolic hydroxyl groups and epoxy resins obtained by glycidyl etherification of alcoholic hydroxyl groups. Preferred examples of such epoxy resins include polyglycidyl ethers of polyhydric phenols having one or more aromatic nuclei, and polyhydric phenols having one or more aromatic nuclei. Examples include polyglycidyl ethers of alcoholic polyhydroxyl compounds derived by addition reaction with alkylene oxides having 2 to 4 carbon atoms. Phenol-based polyglycidyl ether is produced by, for example, reacting a polyhydric phenol having at least one aromatic nucleus with epihalohydrin in a conventional manner in the presence of a basic catalyst such as sodium hydroxide or a reactive amount of a basic compound. An epoxy resin containing a polyglycidyl ether as a main reaction product, a polyhydric phenol having at least one aromatic nucleus, and an epihalohydrin are reacted by a conventional method in the presence of an acidic catalyst such as boron trifluoride. An epoxy resin such as that obtained by reacting the polyhalohydrin ether obtained at least with a basic compound such as sodium hydroxide, or at least one
A polyhalohydrin ether obtained by reacting a polyhydric phenol having aromatic nuclei with epihalohydrin in the presence of a catalytic amount of a basic catalyst such as triethylamine in a conventional manner and a basic compound such as sodium hydroxide. It is an epoxy resin obtained by reaction. Similarly, alcohol-based polyglycidyl ether is a combination of a polyhydroxyl compound derived by an addition reaction between a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms, and epihalohydrin. The main reaction product is a polyglycidyl ether such as that obtained by reacting a polyhalohydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide in the presence of an amount of an acidic catalyst such as boron fluoride. It is an epoxy resin containing as. Here, the polyvalent phenols having at least one aromatic nucleus include mononuclear polyvalent phenols having one aromatic nucleus and polynuclear polyvalent phenols having two or more aromatic nuclei. Examples of such mononuclear polyhydric phenols include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Also, as an example of polynuclear polyhydric phenol, the general formula [In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group or a phenylene group, and a phenylene group is preferred for the purpose of the present invention. Y′ and Y ₁ may be the same or different, and include a methyl group, n-propyl group,
alkyl groups, preferably with up to 4 carbon atoms, such as n-butyl, n-hexyl, n-octyl, or halogen atoms, such as chlorine, bromine, iodine or fluorine, or methoxy groups, Alkoxy groups such as methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy are preferably alkoxy groups having up to 4 carbon atoms. When a substituent other than a hydroxyl group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and z are integers having a value ranging from 0 (zero) to a maximum value corresponding to the number of hydrogen atoms in the aromatic ring Ar that can be substituted with a substituent, and can be the same or different values. R ₁ is for example

[Formula] -O-, -S-, -SO-, -SO ₂ -, or alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethylhexamethylene group group, octamethylene group, nonamethylene group, decamethylene group or alkylidene group, such as ethylidene group, propylidene group, isopropylidene group, isobutylidene group, amylidene group, isoamylidene group, 1-phenylethylidene group or cycloaliphatic group such as 1,4 -Cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group, or alkoxy- and aryloxy-substituted alkylidene group or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene, 3-ethoxy Pentamethylene group, 1,4-(2-methoxycyclohexane) group, phenoxyethylene group, 2-
phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7-phenylpentamethylene group, 2
-Phenyldecamethylene group or aromatic group such as phenylene group, naphthylene group or halogenated aromatic group such as 1,4-(2-chlorophenylene) group, 1,4-(2-fluorophenylene) group
or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-(2-methoxyphenylene) group, 1,4-(2-ethoxyphenylene) group
group, 1,4-(2-n-propoxyphenylene)
groups, 1,4-(2-phenoxyphenylene) groups or alkyl-substituted aromatic groups such as 1,4-
(2-methylphenylene) group, 1,4-(2-ethylphenylene) group, 1,4-(2-n-propylphenylene) group, 1,4-(2-n-butylphenylene) group, 1,4- (2-n-dodecylphenylene) group, or R 1 is a divalent group such as a divalent hydrocarbon group such as a (2-n-dodecylphenylene) group, or R ₁ is, for example, It can also be a ring fused to one of the Ar groups, as in the case of the compound represented by R ₁
can also be a polyalkoxy group, such as a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polyphenylethoxy group, or R ₁ can be, for example, a polydimethylsiloxy group,
It can be a group containing a silicon atom such as a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R ₁ is an aromatic ring, a tertiary-amino group,
There are polynuclear dihydric phenols which can be two or more alkylene or alkylidene groups separated by an ether bond, a carbonyl group or a sulfur or sulfur-containing bond such as a sulfoxide. Particularly preferred among such polynuclear divalent phenols is the general formula (In the formula, Y′ and Y ₁ have the same meanings as above, m
and z are values of 0 to 4, and R ₁ is preferably 1 to 4.
alkylene or alkylidene group or formula with 3 carbon atoms

【formula】

[Formula] or

It is a polynuclear divalent phenol represented by the following formula. Examples of such dihydric phenols include 2,2-bis-(p-
hydroxyphenyl)-propane, 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)-methane, bis-(4-hydroxyphenyl-methane, bis-(4-hydroxy-
2,6-dimethyl-3-methoxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 1,2-bis-(4-hydroxyphenyl)-ethane, 1,1 -bis-(4-hydroxy-2-chlorophenyl)-ethane, 1,1
-bis-(3,5-dimethyl-4-hydroxyphenyl)-ethane, 1,3-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,
2'-bis(3,5-dichloro-4-hydroxyphenylpropane, 2,2-bis(3-phenyl-
4-hydroxyphenyl)-propane, 2,2-
Bis-(3-isopropyl-4-hydroxyphenyl)-propane, 2,2-bis-(2-isopropyl-4-hydroxyphenyl)-propane,
2,2-bis-(4-hydroxynaphthyl)-propane, 2,2-bis-(4-hydroxyphenyl)-pentane, 3,3-bis-(4-hydroxyphenyl)-pentane, 2,2 -Bis- (4-
hydroxy-phenyl)-heptane, bis-(4
-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)-cyclohexylmethane,
1,2-bis(4-hydroxyphenyl)-1,
bis-(hydroxyphenyl) alkanes such as 2-bis-(phenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-1-phenylpropane or 4,4'-dihydroxybiphenyl,
2,2'-dihydroxybiphenyl, dihydroxybiphenyl such as 2,4'-dihydroxyphenyl or bis-(4-hydroxyphenyl)-sulfone, 2,4'-dihydroxydiphenylsulfone, chloro-2, Di-(hydroxyphenyl)-sulfone or bis- such as 4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-4,4'-dihydroxydiphenylsulfone (4-hydroxyphenyl)-ether, 4,3'-(or 4,
2'-or 2,2'-dihydroxy-diphenyl) ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis-(4-hydroxy-3-isobutylphenyl)-ether, bis-
(4-hydroxy-3-isopropylphenyl)
-ether, bis-(4-hydroxy-3-chlorophenyl)-ether, bis-(4-hydroxy-3-fluorophenyl)-ether, bis(4-hydroxy-3-bromphenyl)-ether, bis-(4 -hydroxynaphthyl)-ether, bis-(4-hydroxy-3-chlornaphthyl)-ether, bis-(2-hydroxybiphenyl)-ether, 4,4'-dihydroxy-
2,6-dimethoxy-diphenyl ether, 4,
Di-(hydroxyphenyl)- such as 4'-dihydroxy-2,5-diethoxydiphenyl ether
Contains ethers, including 1,1-bis-(4-hydroxyphenyl)-2-phenyl)-2-phenylethane, 1,3,3-trimethyl-1-(4
-Hydroxyphenyl)-6-hydroxyindan, 2,4-bis-(p-hydroxyphenyl)
-4-Methylpentane is also suitable. Furthermore, another preferred group of such polynuclear divalent phenols has the general formula (wherein R ₃ is a methyl or ethyl group, R ₂ is an alkylidene group having 1 to 9 carbon atoms or other alkylene group, and p is 0 to 4), for example, 1,4-bis-( 4-
hydroxybenzyl)-benzene, 1,4-bis-(4-hydroxybenzyl)-tetramethylbenzene, 1,4-bis-(4-hydroxybenzyl)tetraethylbenzene, 1,4-bis-(p
-hydroxycumyl)-benzene, 1,3-bis(p-hydroxycumyl)-benzene, and the like. Other polynuclear polyhydric phenols include, for example, initial condensates of phenols and carbonyl compounds (e.g., initial condensates of phenolic resins, condensation reaction products of phenol and acrolein, condensation reaction of phenols and glyoxal). products, condensation reaction products of phenol and pentanediallyl, condensation reaction products of resorcinol and acetone, xylene-phenol-formalin initial condensate), condensation products of phenols and polychloromethylated aromatic compounds (e.g. phenol and bischloromethylxylene). Therefore, a polyhydroxyl compound is a compound obtained by reacting the above-mentioned polyhydric phenol having at least one aromatic nucleus with an alkylene oxide in the presence of a catalyst that promotes the reaction between an OH group and an epoxy group. --ROH (herein R is an alkylene group derived from alkylene oxide) or (and) --(RO) _o H (herein R is an alkylene group derived from alkylene oxide, one polyoxyalkylene chain may contain different alkylene groups, and n is an integer of 2 or 2 or more indicating the number of polymerized oxyalkylene groups). be. In this case, the ratio of the polyhydric phenol and alkylene oxide is 1:1 (mol:mol)
Preferably, the ratio of alkylene oxide to OH groups of the polyhydric phenol A is 1:1-10, preferably 1:1-3 (equivalent: equivalent). Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, etc., but those that generate side chains when reacting with the polyhydric phenol to form an ether bond are particularly preferred, and such alkylene oxides include Among these, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide are preferred, with propylene oxide being particularly preferred. A particularly preferred group of such polyhydroxyl compounds has the general formula (In the formula, Y′, Y ₁ , m, z and R ₁ are the same as those in the above formula, R is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ have values of 1 to 3.) ) is a polyhydroxyl compound represented by Yet another preferred group of such polyhydroxyl compounds has the general formula (In the formula, R ₁ , R ₂ , R ₃ are the same as those in the above formula, R is an alkylene group having 2 to 4 carbon atoms, n ₁ and
n ₂ is a value of 1 to 3). Also, epihalohydrin has the general formula (Here, Z is a hydrogen atom, a methyl group, an ethyl group,
Examples of such epihalohydrins include epichlorohydrin, epibromohydrin, 1,2-epoxy-2-methyl-3-chloropropane, and 1,2-epoxy-2-methyl-3-chloropropane. Epoxy-2-
Examples include ethyl-3-chloropropane. As the acidic catalyst that promotes the reaction between the epihalohydrin and the polyhydric phenol or polyhydroxyl compound, Lewis acids such as boron trifluoride, stannic chloride, zinc chloride, and ferric chloride, and derivatives exhibiting these activities ( For example, boron trifluoride-ether complex compound) or a mixture thereof can be used. Similarly, basic catalysts that promote the reaction between epihalohydrin and polyhydric phenol include alkali metal hydroxides (e.g., sodium hydroxide), alkali metal alcoholates (e.g., sodium ethylate),
Tertiary amine compounds (e.g. triethylamine, triethanolamine), quaternary ammonium compounds (e.g. tetramethylammonium bromide),
Alternatively, a mixture of these can be used, and either the glycidyl ether is produced simultaneously with such a reaction, or the halohydrin ether produced as a result of the reaction is ring-closed by a dehydrohalogenation reaction to form the glycidyl ether. The basic compounds that generate
(sodium hydroxide), alkali metal aluminates (eg, sodium aluminate), etc. are conveniently used. Of course, these catalysts and basic compounds can be used as they are or as solutions in appropriate inorganic and/or organic solvents. Epoxy resins having more than one substituted or unsubstituted glycidyl ester group in the molecule include polyglycidyl esters of aliphatic polycarboxylic acids or aromatic polycarboxylic acids, for example, Also included are epoxy resins obtained by polymerizing glycidyl methacrylate synthesized from the epihalohydrin shown and methacrylic acid. Examples of epoxy resins having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule include aromatic amines (e.g., aniline or aniline having an alkyl substituent in the nucleus); An epoxy resin obtained from an epihalohydrin represented by the above general formula, an epoxy resin obtained from an initial condensate of an aromatic amine and an aldehyde (for example, an aniline-formaldehyde initial condensate, an aniline-phenol formaldehyde initial condensate) and an epihalohydrin, etc. can be mentioned. In addition, conventionally known epoxy resins such as the various epoxy resins described in "Manufacture and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi) may be used. One of the essential monomer units of the polymer of the present invention
The isocyanate prepolymer adduct units of hydroxyacrylates can be obtained by reacting hydroxyacrylates with isocyanate prepolymers in advance and then polymerizing them, or by reacting them with isocyanate prepolymers after polymerization. Here, hydroxyacrylates are esters of polyhydroxy compounds and so-called acrylic acids such as acrylic acid and methacrylic acid, specifically 2-hydroxyethyl acrylate, 2-
Examples include, but are not limited to, hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and methacrylates instead of these acrylates. On the other hand, isocyanate prepolymers are obtained by reacting polyether polyols, polyester polyols, or other polyols with polyisocyanates at a ratio of excess isocyanate groups, so the reaction itself is not a well-known method for producing ordinary polyurethane prepolymers. be. Preferred examples of the above polyether polyols include those having the general formula R[(OR ₁ ) _o OH] _p (where R is a polyhydric alcohol residue; (OR ₁ ) _o is an alkylene group having 2 to 4 carbon atoms. A polyoxyalkylene chain consisting of an oxyalkylene group having; n
is a number indicating the degree of polymerization of the oxyalkylene group and is a number corresponding to a molecular weight of 500 to 4,000, preferably 700 to 3,000; p is 2 to 8, preferably 2 to 4). Preferred examples of the polyhydric alcohol corresponding to R in the above general formula include aliphatic dihydric alcohols (e.g. ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentyl glycol), trihydric alcohols (e.g. glycerin,
Trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-
Methyl-1,2,3-propanetriol, 2-
Methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,
4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-
pentanetriol, pentamethylglycerin,
pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolpropane, etc.), tetrahydric alcohol (e.g. erythritol, pentaerythritol, 1,2,3,4)
-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3,4,5-hexanetetrol, etc.),
Pentahydric alcohols (e.g. adonite, arabite,
(ex. Also, preferred as the above polyhydric alcohol are 2-
It is a tetrahydric alcohol, and propylene glycol, glycerin, etc. are particularly preferred. Further, the polyether polyol represented by the above general formula can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to such a polyhydric alcohol by a conventional method so as to have a desired molecular weight. I can do it. Further, examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide, but it is particularly preferable to use propylene oxide. Examples of the polyester polyol used to obtain the urethane prepolymer include conventionally known polyesters produced from polycaribonic acid and polyhydric alcohols, and polyesters obtained from lactams. Examples of such polycarboxylic acids include benzenetricarboxylic acid, adipic acid, succinic acid, superric acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid,
Any suitable carboxylic acid such as terephthalic acid, isophthalic acid, thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or the like can be used. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-butanediol.
pentanediol, 1,6-hexanediol,
Bis-(hydroxymethylchlorohexane), diethylene glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, glycerin or any suitable polyhydric alcohol similar thereto. It can be used. The NCO group-containing urethane prepolymer used in the present invention is made of, for example, the above-mentioned polyether polyols, polyester polyols, or mixtures thereof, or mixtures of these and OH-containing glycerides such as castor oil, and polyisocyanate. It can be obtained by reacting. In addition, the polyisocyanate has the general formula (Here, ゜ is a benzene ring or naphthalene ring, -
NCO is a nuclear-substituted isocyanate group, Z is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, and n is 0, 1 or 2). 2,6-toluylene diisocyanate, 1,4-naphthylene diisocyanate,
1,5-naphthylene diisocyanate, 1,3-
Phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzole-2,4-diisocyanate): General formula (Here, ゜ is a benzene ring or naphthalene ring, -
(CH ₂ ) _n NCO is a nuclear-substituted alkylene isocyanate group, Z is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, m is 1 or 2, and n is a diisocyanate represented by 1 or 2) (Example: ω,ω′-diisocyanate-1,2-dimethylbenzole, ω,ω′-diisocyanate-
1,3-dimethylbenzole): General formula (Here A is -CH ₂ -,

[Formula] An alkylene group having 3 or less carbon atoms, 〇 is a benzene ring or a naphthalene ring, Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, n
is 0,1 or 2) (e.g. 4,4'-diphenylmethane diisocyanate, 2,2'-dimethyldiphenylmethane-4,
4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate), general formula (where Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, m is 0 or 1, and n is 0, 1 or 2) (e.g. biphenyl-2,4' -Diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-
Diisocyanate (e.g. dicyclohexane-4,
4′-diisocyanate, ω,ω′-diisocyanate-1,2-dimethylbenzene, ω,ω′-diisocyanate-1,3-dimethylbenzene), 2
Diisocyanates containing substituted urea groups obtained by the reaction of 1 mol of diisocyanate and 1 mol of water (e.g. urea diisocyanate obtained by the reaction of 1 mol of water and 2 mol of 2,4-toluylene diisocyanate) , uretdione diisocyanate obtained by bimolecular polymerization of aromatic diisocyanate by a known method; propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-
Diisocyanate, 2-methylpentane-2,4
-Diisocyanate, octane-3,6-diisocyanate, 3,3-dinitropentane-1,5
-diisocyanate, octane-1,6-diisocyanate, hexamethylene diisocyanate, etc. As a method for producing an isocyanate prepolymer adduct of hydroxyacrylates, for example, the above-mentioned hydroxyacrylates and NCO group-containing urethane prepolymers may be mixed in the same manner as in the production of ordinary NCO group-containing urethane prepolymers, without a catalyst or using known metal-based, , a method of reacting in the presence of an amine catalyst in _N2 gas at a temperature of 70 to 100°C for 2 to 5 hours, or a method of reacting hydroxyacrylates with the above polyether polyols, polyester polyols, and mixtures thereof with isocyanate. There are two methods: a method in which hydroxyacrylates are simultaneously charged and reacted using a method for producing a normal urethane prepolymer, and a method in which hydroxyacrylates are polymerized and then reacted with an NCO group prepolymer etc. in the same manner as above. Other ethylenically unsaturated monomers that are a component of the polymer of the present invention include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, styrene, α-methylstyrene, methylstyrene, ethylstyrene, Chlorstyrene, iodostyrene, bromostyrene, fluorostyrene,
Cyanostyrene, nitrostyrene, acrylic acid,
Methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, methyl methacrylate, methacrylic anhydride, acrylic anhydride, acrylonitrile, methacrylonitrile,
N,N-dimethylacrylamide, vinyl acetate, vinyl formate, vinyl acrylate,
Vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl iodide, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl-2
- Ethylhexyl ether, vinyl methyl ketone, vinyl ethyl ketone, N-vinylpyrrolidone, divinyl sulfide, dimethyl fumarate, dimethyl maleate, crotonic acid, itaconic acid, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, Acrylic alcohol and other similar compounds are included. Free radical generating catalysts suitable for the polymerization reaction of ethylenically unsaturated monomers include well-known free radicals.
Radical type catalysts for vinyl polymerization reactions, such as hydrogen peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-
Peroxides such as t-butyl peroxide, lauroyl peroxide, butyryl peroxide and the like, or azo compounds such as azo-bis-isobutyronitrile and others, or persulfates, perborons, etc. and peroxide compounds such as acid salts, persuccinic acid, di-isopropyl-peroxy-dicarbonate and the like. The novel modified epoxy compound of the present invention is usually produced by adding an isocyanate prepolymer adduct of hydroxyacrylates and other ethylenically unsaturated monomers to an epoxy resin, and thoroughly stirring the mixture under pressure in an autoclave whose interior is purged with nitrogen. The reaction is carried out at a reaction temperature of 100 to 130°C for 2 to 5 hours, and after the reaction is completed, unreacted substances are distilled off under reduced pressure.
Alternatively, hydroxyacrylates and other ethylenically unsaturated monomers are first polymerized in an epoxy resin by the above reaction method, and the hydroxyl group-containing product is then treated with the urethane polymer containing terminal isocyanate groups. It is also possible to react the polymers in known manner. The modified epoxy resin obtained by the present invention is cured with a commonly used curing agent for epoxy resins. Examples of the curing agent used in the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
Aliphatic amines such as pentaethylenehexamine;
Polyamides obtained by reacting the above aliphatic amines with fatty acids and polymerized fatty acids; cycloaliphatic amines such as metaxylylene diamine, isophorone diamine, and methylenebiscyclohexylamine;
Other modified aliphatic amines; aromatic amines and modified aromatic amines such as metaphenylene diamine, diaminodiphenylmethane, diaminodiphenyl sulfone; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnazic anhydride Acid anhydrides such as acids; imidazole,
_BF3・Monoethylamine, dicyandiamide,
Examples include ionic polymerization type catalysts such as 2,4,6-tris(dimethylaminomethyl)phenol and benzyldimethylamine. Generally, aliphatic amines, cyclic amines, polyamides, modified aliphatic amines, and modified aromatic amines are used alone or in combination with tertiary amines, phenols, etc. as accelerators for room temperature curing. used. Further, aromatic amines and acid anhydrides are used after being heated and cured depending on the characteristics of the curing agent. The curable composition can also contain various other components depending on the desired properties and use. For example, inorganic fillers such as talc, mica, silica, titanium dioxide, carbon black, calcium carbonate, clay, glass fiber, DBP,
Plasticizers such as DOP, castor oil, polyvinyl chloride,
Organic fillers, pigments, etc. may also be included. The present invention will be further explained in detail by showing production examples and examples below. Note that parts in the examples are based on weight. Production example 1 Adekal resin EP-4100 (epoxy equivalent: 190, viscosity (25℃) 100PS) 400 parts, benzoyl peroxide 3
A portion of the mixture was placed in an autoclave and the temperature of the mixture was heated to 80°C in a stream of nitrogen gas. Next, P-2000 (manufactured by Asahi Denka Kogyo Co., Ltd., bifunctional polyether, hydroxyl value 58 (mgKOH/g), viscosity (25℃)
330 cps), 1000 parts of 2-hydroxyethyl methacrylate, 130 parts of 2-hydroxyethyl methacrylate, and 250 parts of methylene bis(4-phenyl isocyanate) are reacted in _N2 gas at 85°C for 3 hours to obtain an isocyanate preform of 2-hydroxyethyl methacrylate. polymer adducts
A mixture of 30 parts of styrene and 40 parts of acrylonitrile was added dropwise to this, and the temperature was then raised to 100°C.
and react for 3 hours. Remove unreacted monomers, undecomposed catalyst, and catalyst residue by 100%
It was distilled off under reduced pressure of 10 mmHg at ℃ to obtain a new modified epoxy resin (A) (epoxy equivalent: 265). Production Example 2 400 parts of epoxy resin (bisphenol A type, epoxy equivalent: 190) and 4 parts of azobisisobutyronitrile are placed in a 4-necked flask, and the mixture is heated to 90°C while blowing nitrogen gas. A mixture of 20 parts of styrene, 20 parts of acrylonitrile and 20 parts of 2-hydroxyethyl acrylate is then added dropwise over a period of 2 hours. Then stir at 100°C for 2 hours. After removing unreacted monomers, undecomposed catalyst, and catalyst residue at 100°C under a reduced pressure of 10 mmHg of mercury for 1 hour, P-1000 (manufactured by Asahi Denka Kogyo Co., Ltd., bifunctional polyether, hydroxyl value 100-200) (mgKOH/g), viscosity (25°C): 140 cps) and 348 parts of toluene diisocyanate by a known reaction.
20 parts of NCO group-containing urethane prepolymer was further added and the reaction was carried out at 100°C for 3 hours to obtain a new modified epoxy resin (B). The obtained epoxy resin had an epoxy equivalent weight of 250. Production example 3 Adekaljin EP-4000 (epoxy equivalent 320,
400 parts of viscosity (25°C) 30 poise) and 4 parts of azobisisobutyronitrile were placed in an autoclave and the mixture was heated to 80°C while blowing nitrogen gas. Next, 1000 parts of P-1000 (bifunctional polyether manufactured by Asahi Denka Kogyo Co., Ltd., hydroxyl value: 100-120 (mgKOH/g), viscosity (25°C) 140 cps) and 348 parts of toluene diisocyanate were added in a known manner. The NCO group-containing urethane prepolymer obtained by the reaction is further
2- obtained by reacting at 90℃ for 3 hours in _N2 gas
Add 40 parts of isocyanate prepolymer adduct of hydroxyethyl acrylate and add styrene to this.
A mixture of 30 parts of acrylonitrile, 20 parts of acrylonitrile, and 30 parts of butadiene was added dropwise, and then the temperature was raised to 100°C and reacted under pressure for 3 hours. Remove unreacted monomers, undecomposed catalyst, and catalyst residue by 100%
It was removed under reduced pressure of 10 mmHg at ℃ to obtain a new modified epoxy resin (C) (epoxy equivalent: 396). Examples 1 to 3, Comparative Examples 1 to 3 A curing agent was added to the modified epoxy resin obtained in Production Examples 1 to 3, and the resin was cured, and its physical properties were measured. Table 1 shows the results.
~3. For comparison, an example using a commercially available epoxy resin is also shown. Physical properties were measured by the following method. Γ Tensile shear strength (Fe/Fe) ASTM-D-
According to 1002. Γ T type peeling strength (Fe/Fe) 25mm x 200mm x 0.6mm test piece with adhesive area of 25mm
x150mm and peel off at 90° to the adhesive surface.

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Claims (1)

[Scope of Claims] 1 (a) In a compound containing more than one 1,2-epoxy group per molecule on average and having an epoxy equivalent weight of 150 to 800, an isocyanate prepolymer adduct of hydroxyacrylates and , and other ethylenically unsaturated monomers as structural units, a modified epoxy resin composition is polymerized and dispersed in the above compound at a ratio of 10 to 100% by weight based on the above compound; (b) A modified curable composition containing a curing agent for epoxy compounds.