JPS6155554B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a radically curable adhesive composition with excellent adhesive properties. An object of the present invention is to provide a composition that has excellent adhesion to metals and the like. As is well known, various resins are known as radical curable resins, such as unsaturated polyester resins, urethane-modified acrylate resins, epoxy acrylate resins, and ester acrylate resins.
It is widely used in applications such as laminates, linings, and paints because it has the advantage of being easy to adjust pot life and curing time and to be easy to handle. However, it has not always been possible to obtain satisfactory adhesion to metals, etc., and as a result, adhesives are only used in extremely limited applications, and improvements in adhesion are limited to the applications of these resins. It was strongly requested to expand the field. Some of the present inventors have already proposed that a resin composed of a urethane-modified acrylate containing 11 or more propylene oxide units in the molecular chain and a polymerizable monomer has excellent adhesive properties (Unexamined Japanese Patent Publication No. Showa 52-
No. 155694). However, although this resin has excellent adhesive properties, it was found that, for example, the adhesive strength between metals or between metal and cloth was not sufficient, and that improvements were needed. did. The present inventors proposed the above (Japanese Unexamined Patent Publication No. 51-155694
As a result of our intensive research in order to further improve the adhesive strength of the above resin, we discovered that if epoxy acrylate or epoxy acrylate resin is blended with the urethane-modified acrylate resin, the adhesive strength can be greatly improved. reached. Additionally, surprisingly, when epoxy acrylate or epoxy acrylate resin is blended with the urethane-modified acrylate resin of the present invention, the adhesive strength is superior to that when each is used alone. I found it. That is, the present invention is based on the following general formula () (In the formula, R ₁ is a divalent organic residue, R ₂ is an organic diisocyanate residue, R ₃ is a polyhydric alcohol residue, R ₄ is hydrogen or a methyl group, m is a number from 0 to 5, and n is 1 ~
Shows the number 3. However, R ₁ and/or R ₃
11 or more propylene oxide units

Contains [expression]. ) urethane-modified acrylate (A), epoxy acrylate (B), and a copolymerizable monomer (C) that can be polymerized with (A) or (B), where (A):(B) is the weight Ratio: 30:70~90:
10 is a radical curable adhesive composition. The urethane-modified acrylate in the present invention is a propylene oxide unit having 11 or more divalent organic residues (R ₁ ) or polyhydric alcohol residues (R ₃ ) in the above general formula ().

contains [formula] or propylene oxide units in both residues R ₁ and R ₃

A compound containing [Formula] whose total number is 11 or more. Examples of the divalent organic residue (R ₁ ) containing a propylene oxide unit include those derived from the following compounds having two alcoholic hydroxyl groups. For example, propylene glycol, dipropylene glycol, polypropylene glycol higher than tripropylene glycol, aliphatic dihydric alcohols such as polyethylene oxide/propylene oxide block copolymer, the following general formula () (In the formula, A is a divalent phenol residue or an alicyclic group 2
dihydric alcohols, or dihydric carboxylic acids, such as aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, adipic acid, sebacic acid, and azelain. A terminal hydroxyl group-containing bisester obtained from an aliphatic dicarboxylic acid such as an acid, dodecane dicarboxylic acid, etc., and a dihydric alcohol mainly consisting of a dihydric alcohol having a propylene oxide unit, such as bis(2-hydroxypropyl) terephthalate, Bis(2-hydroxypropyl)isophthalate, bis(2-
hydroxypropyl)orthophthalate, bis(2-hydroxypropyl)adipate, bis(2-hydroxypropyl)sebacate, bis(2-hydroxypropyl)azelaate, bis(2-hydroxypropyl)dodecanedicarboxylate, bis[2-( 2-hydroxypropoxy)propyl]terephthalate, bis[2-(2
-hydroxypropoxy)propyl]isophthalate, bis[2-(2-hydroxypropoxy)
[propyl] orthophthalate, or terephthalic acid oligoester containing a terminal hydroxyl group containing a propylene oxide unit as a glycol component, isophthalic acid oligoester, orthophthalic acid oligoester, adipic acid oligoester, sebacic acid oligoester, azelaic acid oligoester,
Examples include dodecanedicarboxylic acid oligoester. Examples of the dihydric alcohol represented by the general formula () include propylene oxide and 2.2-
Bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(2,6-dibromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)
Compounds obtained by reacting dihydric phenols such as ether, bis(4-hydroxyphenyl)sulfone, pyrocatechol, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, or these aromatic hydrogenated dihydric alcohols,
For example, 2,2-bis[4-(2-hydroxypropoxy)cyclohexyl]propane, 2,2-bis[4-(2-hydroxypropoxy)cyclohexyl]propane,
-Bis[4-(2-hydroxypropoxy)phenyl]propane, bis[4-(2-hydroxypropoxy)phenyl]methane, 2,2-bis[2,6-dibromo-4-(2-hydroxypropoxy)phenyl] ] propane, etc., and adducts with a large number of moles of propylene oxide added.
Specifically, the dihydric alcohol containing 11 or more propylene oxide units is an adduct of bisphenol A with 11 moles of propylene oxide (average molecular weight
866), propylene oxide of bisphenol A 15
These include a molar adduct (average molecular weight 1098) and an 11 molar propylene oxide adduct of hydrogenated bisphenol A (average molecular weight 876). The polyhydric alcohol residue (R ₈ ) containing a propylene oxide unit is selected from compounds having two alcoholic hydroxyl groups similar to the divalent organic residue (R ₁ ) containing a propylene oxide unit in the above general formula (). In addition to the derived groups, propylene oxide adducts such as trimethylolethane, trimethylolpropane, pentaerythritol, and glycerin are also included. Other divalent organic residues (R ₁ ) in the general formula () include the following groups derived from compounds having two alcoholic hydroxyl groups. For example, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,6
-hexanediol, 2,2,4-trimethyl-
1,3-pentanediol, dibromoneopentyl glycol, dichloroneopentyl glycol, 1,4-cyclohexanedimethanol, 1.
4-cyclohexanediol, bis(2-hydroxyethyl) terephthalate, bis(2-hydroxyethyl)isophthalate, bis(2-hydroxyethyl)orthophthalate, bis(2,2-
Dimethyl-3-hydroxypropyl) terephthalate, bis(2,2-dimethyl-3-hydroxypropyl)isophthalate, bis(2,2-dimethyl-3-hydroxypropyl)orthophthalate, bis[2-(2-hydroxyethoxy) ) ethyl] terephthalate, bis[2-(2-hydroxyethoxy)ethyl]isophthalate, bis[2
-(2-hydroxyethoxy)ethyl]orthophthalate, terephthalic acid oligoester containing a terminal hydroxyl group, isophthalic acid oligoester, orthophthalic acid oligoester, adipic acid oligoester, sebacic acid oligoester, azelaic acid oligoester, dodecanedicarboxylic acid Oligoesters such as oligoesters, fumaric acid oligoesters, and maleic acid oligoesters (however, these oligoesters do not contain propylene oxide units as glycol components), 2.
2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]methane, 2,2-bis(4-
hydroxycyclohexyl)propane, 2,2-
Examples include bis[4-(2-hydroxyethoxy)cyclohexyl]propane. The other polyhydric alcohol residue (R ₃ ) in the general formula () is derived from a compound having two alcoholic hydroxyl groups similar to the divalent organic residue (R ₁ ) in the general formula (). In addition to groups derived from compounds having three or more alcoholic hydroxyl groups, such as trimethylolethane, trimethylolpropane, pentaerythritol, and glycerin, it also includes groups derived from compounds having three or more alcoholic hydroxyl groups. The organic diisocyanate residue (R ₂ ) in the general formula () includes divalent groups derived from the following organic diisocyanates. for example,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane
Examples include 4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, and 1,3-bis(isocyanatemethyl)cyclohexane. As a method for obtaining the urethane-modified acrylate resin of the present invention, for example, alcoholic hydroxyl groups can be
The urethane prepolymer containing terminal isocyanate groups is reacted with an organic diisocyanate compound at -OH group/-NCO group < 1 (molar ratio) in a medium inert to isocyanate groups. There is a method in which a urethane-modified acrylate obtained by reacting with a contained acrylate or methacrylate is dissolved in a polymerizable monomer. Examples of compounds having two or more alcoholic hydroxyl groups capable of reacting with isocyanates include dihydric alcohols containing 11 or more propylene oxide units, such as polypropylene glycol (containing 11 or more propylene oxide units), and p in the general formula () above. An aromatic dihydric alcohol in which the sum of and q is 11 or more, preferably 11 to 17, such as a propylene oxide adduct of bisphenol A (containing 11 or more propylene oxide units), is preferred. These propylene oxide units
A dihydric alcohol containing 11 or more alcoholic hydroxyl groups may be used together with other compounds having two alcoholic hydroxyl groups. In particular, it is desirable to use it together with a hydroxyl group-containing terephthalic acid oligoester. A hydroxyl group-containing terephthalic acid oligoester is a bisester or oligoester with a molecular weight of 200 to 2000 and an acid value of 20 or less, consisting of a dicarboxylic acid component of which 50 mol% or more is terephthalic acid and a dihydric alcohol. It is ester. Divalent carboxylic acid components other than terephthalic acid in this oligoester include isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, succinic acid,
Adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, halogenated phthalic acid, 3,6-
Saturated dicarboxylic acids and phthalic acids such as endomethylene-1,2,3,6-tetrahydrophthalic acid,
These include unsaturated dicarboxylic acids such as maleic acid, citraconic acid, and itaconic acid. The dihydric alcohol components of this oligoester include ethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, 1,6-hexanediol, and diethylene glycol. , dipropylene glycol,
Polyethylene glycol, polypropylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanediol, dimethylolcyclohexane,
Examples include glycols such as hydrogenated bisphenols, alkylene oxide adducts of hydrogenated bisphenols, alkylene oxide adducts of bisphenols, and alkylene oxide adducts of halogenated bisphenols. Specifically, the oligoesters include bis(hydroxyethyl) terephthalate, bis(2
- Refers to oligoesters containing a terminal hydroxyl group, ranging from those with a small molecular weight such as bisesters of terephthalic acid such as -hydroxypropyl) terephthalate and bis(4-hydroxybutyl) terephthalate, to oligoesters with a molecular weight of up to 2,000 consisting of terephthalic acid and the above-mentioned dihydric alcohols. do. The reaction ratio of the compound having two alcoholic hydroxyl groups and the organic diisocyanate is such that the molar ratio of the hydroxyl groups to the isocyanate groups is less than 1 [-OH
group/-NCO group<1 (molar ratio)], preferably 0.4 to
It is 0.8. Examples of media inert to the isocyanate groups used in the above reaction include polymerizable monomers such as styrene, vinyltoluene, methyl acrylate, methyl methacrylate, diallyl phthalate, and non-polymerizable monomers such as benzene, toluene, and methylene chloride. Examples include compounds. Examples of the catalysts used include triethylenediamine, triethylamine, dibutyltin dilaurylate, and dimethyloctyltin. This reaction is preferably carried out at a reaction temperature of 20 to 80°C, particularly 50 to 80°C. The alcoholic hydroxyl group-containing acrylate or methacrylate that can react with the terminal isocyanate group-containing urethane prepolymer obtained by this reaction is one obtained by reacting acrylic acid or methacrylic acid or a functional derivative thereof with a polyhydric alcohol, or There are those obtained by reacting an acid or methacrylic acid with a compound having an epoxy group. Examples of such compounds include ethylene glycol monoacrylate, ethylene glycol monomethacrylate, propylene glycol monoacrylate,
Propylene glycol monomethacrylate, 1.
3-propanediol monoacrylate, 1.3
-Propanediol monomethacrylate, 1.3
-Butanediol monoacrylate, 1,3-butanediol monomethacrylate, 1,4-butanediol monoacrylate, 1,4-butanediol monomethacrylate, 1,6-hexanediol monoacrylate, 1,6-hexanediol monomethacrylate , diethylene glycol monoacrylate, diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, polyethylene glycol monoacrylate or monomethacrylate, polypropylene glycol monoacrylate or monomethacrylate, monoacrylates and monomethacrylates of dihydric alcohols, Methylolethane monoacrylate, trimethylolethane monomethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, glycerin monoacrylate Acrylates, monoacrylates and diacrylates, monomethacrylates and dimethacrylates of trihydric alcohols such as glycerin monomethacrylate, glycerin diacrylate, glycerin dimethacrylate, or pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol Examples include diacrylates and triacrylates of polyhydric alcohols having a valence of 4 or more, such as trimethacrylate, or dimethacrylates and trimethacrylates. Especially ethylene glycol monoacrylate, ethylene glycol monomethacrylate, molecular weight approx.
1500 polypropylene glycol monoacrylates and methacrylates are preferred. The reaction ratio of the urethane prepolymer containing terminal isocyanate groups and the alcoholic hydroxyl group-containing acrylate or methacrylate is such that the hydroxyl groups are equal moles or more to the isocyanate groups [-OH groups/-NCO
group≧1 (molar ratio)], preferably 1.05 to 1.8. This reaction is carried out in the medium used in the first stage reaction, in another medium, or in the absence of a medium. The reaction temperature is preferably 80°C or lower. The epoxy acrylate (B) in the present invention is
For example, these are compounds produced by the following two typical methods. That is, in the presence of a catalyst, α and β
- A method of reacting an unsaturated acid with an epoxy compound (Japanese Patent Publication No. 45-15988, U.S. Patent No. 3,373,211) and a method of reacting a compound containing a polymerizable double bond and an epoxy group in the molecule with a polyhydric phenol ( etc. Publication No. 47-43536, JP-A-51-80394). Examples of α/β-unsaturated acids used in the former method include acrylic acid, methacrylic acid, and crotonic acid, and examples of epoxy compounds include the following general formulas (), (), and (). (In the formula, n is 0 to 4, R is a hydrogen atom, a lower alkyl group, or a halogen atom) (In the formula, n is 1 to 5, R is a hydrogen atom or a lower alkyl group) (In the formula, n is 1 to 20, R is a hydrogen atom or a lower alkyl group) In addition to the compounds represented by the following, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, dipentene oxide,
3', 4'-epoxy-6'-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-
Examples include 3,4-epoxycyclohexane. Compounds containing a polymerizable double bond and an epoxy group used in the latter method include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, allyl-2,3-epoxybutyl ether, allyl-2,3-epoxy- There are 2-methylpropyl ether, diglycidyl maleate, etc., and polyhydric phenols include 2,2-bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl).
Propane, 2,2-bis(3,5-dichloro-4
-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)
Propane, 2,2-bis(2-methyl-4-hydroxyphenyl)propane, 2,2-bis(2-
Hydroxy-4-tert-butylphenyl)propane, 2,2-bis(2-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3,5-dibromo-
4-hydroxyphenyl)butane, 2,2-bis(2-chloro-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone,
Bis(4-hydroxyphenyl)ether, 4.
4'-dihydroxydiphenyl, 3,3',5,5'-
Tetrachloro-4,4'-dihydroxydiphenyl, 3,3',5,5'-tetrabromo-4,4'-dihydroxydiphenyl, 3-hydroxyphenyl salicylate, hydroquinone, catechol,
2,6-tert-butylhydroquinone, mono-
tert-butylhydroquinone, p-tert-butylcatechol, pyrogallol, resorcinol, tannic acid, 1,5-dihydroxynaphthalene,
Examples include 1,4-dihydroxynaphthalene. The above reaction involves styrene, vinyltoluene,
It can also be carried out in a medium of polymerizable monomers such as methyl acrylate, methyl methacrylate and diallyl phthalate, or non-polymerizable compounds such as benzene, toluene and methylene chloride. Further, this reaction is preferably carried out in the presence of a known catalyst such as a quaternary ammonium salt. In the present invention, the copolymerizable monomer (C) that can be polymerized with (A) or (B) includes styrene-related monomers such as styrene, vinyltoluene, chlorostyrene, tert-butylstyrene, divinylbenzene, and α-methylstyrene. Monomer, methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, ethylene glycol methacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, trimethylolpropane trimethacrylate, Acrylic acid ester monomers such as trimethylolpropane triacrylate, diallyl phthalate,
Allyl monomers such as triallyl cyanurate,
Representative examples include vinyl acetate and dibutyl fumarate. In the present invention, urethane-modified acrylate (A)
The mixing ratio of epoxy acrylate (B) is (A):(B) = 30:70 to 90:10 by weight, preferably
The time is 40:60 to 90:10. Further, the proportion of the polymerizable monomer (C) in the composition is 5 to 60% by weight, preferably 10 to 40%. In the present invention, the blending ratio of urethane-modified acrylate (A) and epoxy acrylate (B) and the blending ratio of copolymerizable monomer (C) are extremely important requirements for adhesive properties. In other words, the blending ratio of urethane-modified acrylate (A) and epoxy acrylate (B) is
When the ratio is outside the range of 30:70 to 95:5, the adhesion strength not only does not improve as compared to when each component is used alone, but also significantly decreases in some cases. Urethane modified acrylate
It is extremely characteristic and the key point of the present invention that only when the blending ratio of (A) and epoxy acrylate (B) is within the above range, the adhesive strength is improved compared to when each is used alone. On the other hand, when the blending ratio of the copolymerizable monomer (C) exceeds 60%, the adhesive strength decreases and the curability also deteriorates. Further, if the blending ratio is less than 5%, the viscosity is too high and practical workability cannot be obtained. The radical curable adhesive composition of the present invention can be cured in the same manner as general radical curable resins. Curing methods using polymerization initiators include benzoyl peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, etc. A known organic peroxide is used, and if necessary, an accelerator such as dimethylaniline or cobalt naphthenate is used in combination. Other curing methods include curing by irradiation with electron beams, radiation, ultraviolet rays, etc. In this case, a sensitizer may be added if necessary. In addition to the above organic peroxide, accelerator or sensitizer, the radical curable adhesive composition of the present invention includes:
Polymerization inhibitors, fillers, reinforcing materials, colorants, pigments, and the like can be appropriately selected and blended. The radically curable adhesive composition of the present invention has excellent adhesive strength and can be used in various applications as an adhesive for metals, plastics, cloth, paper, wood, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples, but of course the present invention is not limited to these Examples. Adhesive strength was evaluated by measuring tensile shear adhesive strength according to JISK6850-1972 and peel strength according to JISK6301-1971. In the examples, parts simply mean parts by weight,
% means weight %. The viscosity was measured at 25°C using a B-type rotational viscometer. Curing of the adhesive composition was performed using methyl ethyl ketone peroxide (55%, dimethyl phthalate solution)
1.0% by weight and cobalt naphthenate (Co content 6
%, mineral spirit solution) was added and allowed to harden at room temperature. Note that the steel plates and aluminum plates used in the examples were sandblasted. Synthesis Example 1 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 375 parts of styrene and 11 moles of propylene oxide adduct of bisphenol A (average molecular weight 866) were added.
Prepared with 866 parts and 0.08 parts of hydroquinone,
348 parts of 2,4-tolylene diisocyanate was added and the mixture was reacted for 2 hours at a reaction temperature of 80°C to obtain a urethane prepolymer containing terminal isocyanate groups. Then ethylene glycol monomethacrylate 286
of the mixture was added, and the mixture was reacted at a reaction temperature of 80° C. for 3 hours to obtain a urethane-modified acrylate resin (2). Viscosity is 37
It was poise. Synthesis Example 2 In the same reaction vessel as Synthesis Example 1, 288 parts of styrene,
518 parts of a propylene oxide 5 mole adduct of bisphenol A (average molecular weight 518) and 0.08 parts of hydroquinone were charged, 348 parts of 2,4-tolylene diisocyanate was added, and the mixture was reacted at a reaction temperature of 80°C for 2 hours to form terminal isocyanate groups. A containing urethane prepolymer was obtained. Next, 286 parts of ethylene glycol monomethacrylate was added, and the reaction temperature was 80°C.
A urethane-modified acrylate resin () was obtained by time reaction. The viscosity was 46 poise. Synthesis Example 3 Epikote 834 (average molecular weight 470, Siel Chemical Co., Ltd.) was added to a reaction vessel equipped with a thermometer, stirrer, and reflux condenser.
Co., Ltd.), 181 parts of methacrylic acid, and 0.06 parts of hydroquinone, 1.19 parts of trimethylbenzylammonium chloride was added as a catalyst, and esterification was carried out at 120°C, and the reaction rate was 95% as determined by acid value measurement. The reaction was allowed to proceed until the reaction reached the above level. The obtained epoxy acrylate was dissolved in styrene and 35
% styrene-containing epoxy acrylate resin ()
And so. The viscosity was 11 poise. Synthesis Example 4 In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 146 parts of adipic acid, 1420 parts of Epicoat 828 [average molecular weight 355, manufactured by Ciel Chemical Co., Ltd.], 361 parts of methacrylic acid, and 0.2 parts of hydroquinone were added. prepare the parts,
8 parts of benzyldimethylamine was added as a catalyst, esterification was carried out at 120°C, and the reaction was allowed to proceed until the reaction rate reached 95% or more as determined by acid value measurement. 1038 parts of styrene and 0.1 part of hydroquinone at the end of the reaction
After stirring for 30 minutes, an epoxy acrylate resin containing 35% styrene was obtained. Viscosity is 13
It was poise. Synthesis Example 5 In a reaction vessel equipped with a thermometer, a stirrer, and a reflux type condenser, add Epikote 834 [average molecular weight 470, Ciel Chemical Co., Ltd.]
Co., Ltd.], 151 parts of acrylic acid, and 0.06 parts of hydroquinone, and added 1.19 parts of trimethylbenzylammonium chloride as a catalyst.
Esterification is carried out at ℃ and the reaction rate is determined by acid value measurement.
React until the concentration is 95% or more, and at the end of the reaction, add 95 parts of ethylene glycol methacrylate and styrene.
239 parts were added and dissolved to obtain an epoxy acrylate resin (2). The viscosity was 9.8 poise. Example 1 The urethane-modified acrylate resin () and the epoxy acrylate resin () obtained in Synthesis Example 1 and Synthesis Example 3 were blended in various proportions, and the adhesive strength between steel plates was measured. The results are shown in Table 1.

[Table] Example 2 As in Example 1, urethane-modified acrylate resin () and epoxy acrylate resin () were blended in various proportions, and the adhesive strength between aluminum plates was measured. The results are shown in Table 2.

[Table] *) The aluminum plate was cut.
Example 3 Urethane-modified acrylate resin () and epoxy acrylate resin () were blended in various proportions, and the adhesive strength between a polyester canvas having a basis weight of 540 g/m ² and a steel plate was measured. The results are shown in Table 3.

[Table] Comparative Example 1 The urethane-modified acrylate resin () obtained in Synthesis Example 2 and the epoxy acrylate resin () obtained in Synthesis Example 3 were blended in various proportions, and in the same manner as in Example 1, steel sheets were bonded. Adhesive strength was measured. The results are shown in Table 4.

[Table] Example 4 The urethane-modified acrylate resin () and the epoxy acrylate resin () obtained in Synthesis Example 1 and Synthesis Example 4 were blended in various proportions, and the adhesive strength between steel plates was measured. The results are shown in Table 5.

[Table] Example 5 The urethane-modified acrylate resin () and epoxy acrylate resin () obtained in Synthesis Example 1 and Synthesis Example 5 were blended in various proportions to obtain a fabric weight of 540g/
The adhesive strength between a polyester canvas of m ² and a steel plate was measured. The results are shown in Table 6.

【table】

Claims (1)

[Claims] First-order general formula () (In the formula, R ₁ is a divalent organic residue, R ₂ is an organic diisocyanate residue, R ₃ is a polyhydric alcohol residue, R ₄ is hydrogen or a methyl group, m is a number from 0 to 5, and n is 1 ~
Shows the number 3. However, R ₁ and/or R ₃
11 or more propylene oxide units:
Contains [expression]. ) Urethane-modified acrylate (A), epoxy acrylate
(B), and (A) or a copolymerizable monomer (C) that can be polymerized with (B), with a weight ratio of (A):(B) of 30:70 to 90:10.
A radically curable adhesive composition.