JPH09125010A - Photosetting type adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosetting type adhesive composition comprising a compound having two or more terminal groups of propenyl ether and a photopolymerization initiator, containing no organic solvent, showing rapid curing rate and low volume shrinkage, further excellent in surface-hardening properties and adhesion. SOLUTION: This composition is prepared by compounding (A) a compound having two or more terminal groups of propenyl ether and (B) a photopolymerization initiator such as triphenylsulfonium phosphate, preferably the amount of component A is 96-98wt.%, while the component B is 2-4wt.%. As a component A, is preferably a urethane oligomer bearing terminal groups of propenyl ether of the formula [m is 0-200; n is 2-200; Q<1> is -OX<2> O-, -N(R<2> )-X<4> -N(R<2> )-(X<2> is a residue of diol such as an alkyldiol, an aryldiol; X<4> is a 2-12C alkylene, an arylene; R<2> is a 2-12C alkyl, an aryl; Q<2> is -OX<2> O-; Z<1> is a residue of a polyvalent isocyanate; Z<2> is a residue of a divalent isocyanate; at least two of R<1> s are propenyl and the rest is H, or an acyl].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable adhesive composition containing a propenyl ether terminal group compound which can be cured by irradiation with light to adhere a coating.

[0002]

2. Description of the Related Art In recent years, adhesives using organic solvents have problems such as toxicity to workers, fire hazard, environmental pollution, drying speed, and waste of solvent. Solvent-free adhesives, which do not contain and utilize curing by irradiation with active energy rays, have been studied.
As solvent-free adhesives, there are radical polymerization type unsaturated polyesters, polyester acrylates, urethane acrylates, silicone acrylates and epoxy acrylates, but radical photopolymerization type curing causes volume shrinkage, adhesion on the adhesive surface, dimensional stability Acrylic resin has a peculiar odor and has a high skin irritation. In addition, since an uncured portion remains in a portion that is not irradiated with ultraviolet rays (UV), that is, a portion having a complicated shape, a portion that does not transmit UV, and a sagging portion, the use place is limited. An epoxy photocationic UV curable resin is a composition that overcomes these problems, but it requires a large amount of UV energy during curing due to its low photoreactivity. Therefore, there are drawbacks that a high UV energy irradiation device is required and that irradiation time is long.
As a method for improving the reactivity of the cationic UV curable resin, a method using an alicyclic epoxy compound as a base resin or a diluent is known (JP-A-5-186755). Gazette). However, this is slower than the reaction rate of the radical UV curable resin, the types of alicyclic epoxies that are industrially available are limited, and it was difficult to obtain a product that satisfies practical performance. .

[0003]

The present invention is directed to an organic solvent,
It is intended to provide a resin composition for an adhesive, which does not contain an irritating monomer or oligomer, is cured at a high speed by irradiating with an active energy ray such as UV, and has excellent adhesiveness and dimensional stability of an adhesive surface. To aim. Therefore, the present invention greatly improves various problems in the prior art, namely, harmfulness to workers, environmental pollution, odor control, curing speed, and physical properties as an adhesive.

[0004]

The present inventor has arrived at the present invention as a result of extensive studies in order to solve the above problems. That is, the present invention is a photocurable adhesive composition comprising a compound (A) having at least two propenyl ether terminal groups and a photopolymerization initiator (B).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) of the present invention includes the following. That is, at least one selected from the group consisting of a (poly) ether oligomer having a propenyl ether end group, a polyester oligomer having a propenyl ether end group, a urethane oligomer having a propenyl ether end group, and a monomer having a propenyl ether end group. And is preferably a urethane oligomer having a propenyl ether end group.

The (poly) ether oligomer having a propenyl ether terminal group in (A) of the present invention is a compound represented by the following general formula (1). ^{X 1 [-O- (AO) m} -R 1] n (1) { wherein, n is an integer of 2 to 200, the n-number of m 0 to
It is an integer of 200 and at least one of m is 1 or more. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene, arylene, aralkylene or cycloalkylene group having 2 to 12 carbon atoms, and when m is 2 or more, A may be the same or different, and the (AO) m portion may be random addition or block addition. good. X ¹ is a polyhydric alcohol residue. ｝

In the general formula (1), A is alkylene,
It is a divalent group selected from the group consisting of arylene, aralkylene and cycloalkylene groups, and examples of alkylene groups that can be used include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene,
Examples include octylene, nonylene, decylene, undecylene and dodecylene. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of alkylene are benzylene, 1
-Phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene and the like. Examples of cycloalkylene groups include:
Examples include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene group and propylene group are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

X ¹ is a polyhydric alcohol residue, and examples of the polyhydric alcohol include the following. For example, glycerin, polyglycerin (glycerin 2-18mer, such as diglycerin, triglycerin, tetraglycerin, etc.), ring-opening polymer of glycidol (polymerization degree of 2 to
5000 compounds), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2-3 trimers, monopentaerythritol, dipentaerythritol, 1,
Examples thereof include 3,5-pentaerythritol, sorbitol, sorbitan sorbitan glycerin condensate, etc. Of these, residues of glycerin and polyglycerin, and residues of trimethylolalkane and dimers and trimers thereof are particularly preferable.

N is usually an integer from 0 to 200 and m
At least one is 1 or more, preferably 1 to 8
0, particularly preferably an integer of 1 to 5. When m exceeds 200, the viscosity is usually high and it becomes difficult to dissolve the initiator.

N is 2 to 200, preferably 3 to 100,
Particularly preferably, it is an integer of 3 to 5. When n exceeds 200, the viscosity is usually high and it becomes difficult to dissolve the initiator. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.

The polyester oligomer having a propenyl ether terminal group in the present invention is represented by the following general formula (2):
Examples thereof include compounds represented by (3) or (4).

[0012] {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by alkylene diol, arylene diol,
It is a residue of any one of polyether diol, polyurethane diol or polycarbonate diol, Y ¹ is a polyvalent carboxylic acid residue, and Y ² is a divalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ² in the general formula (2) is HOX ² OH.
Represented by alkylene diol, arylene diol,
It is the residue of a diol, either a polyether diol, a polyurethane diol or a polycarbonate diol.

Examples of the alkylene diol represented by HOX ² OH include ethylene glycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol and 1,9-nonane diol. , Neopentyl glycol, 1.4-cyclohexanediol and the like. Of these, preferably,
They are ethylene glycol and propylene glycol.

Examples of the arylene diol represented by HOX ² OH include catechol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane and bisphenol A. Of these, bisphenol A is preferred.

Examples of the polyether diol represented by HOX ² OH include poly (oxyethylene) diol,
Examples thereof include poly (oxypropylene) diol, poly (oxytetramethylene) diol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferable.

The degree of polymerization of the above polyether diol is usually 1 to 200, preferably 2 to 100, particularly preferably 3
-20.

Examples of polyurethane diol represented by HOX ² OH include reaction products of the following (i) and (ii). (I) Compound represented by H (OX ⁵ ) m-OH (m is an integer of 0 to 200, X ⁵ is selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms. (Ii) OCN-Z ³ -NCO (in the formula, Z ³ is 2 selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene).
Is the basis of valence)

In the above polyether diol (i), m is usually 0 to 200, preferably 3 to 20.

In the polyether diol (i), X ⁵ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms, and usable alkylene groups. Examples of methylene, ethylene, propylene, butylene,
Pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like.
Examples of alkylene are benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-
Examples thereof include phenyl propylene and 1-phenyl propylene. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene and propylene groups are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

Examples of the diisocyanate of (ii) above include toluene diisocyanate (TDI), p- and m-phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4. -Trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (Desmodur W), 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'- Diphenylmethane diisocyanate,
1,5-tetrahydronaphthalene diisocyanate, naphthalene-1,5′-diisocyanate, bis (2-methyl-3-isocyanatephenyl) methane, 4,4 ′
-Diphenylpropane diisocyanate, tetramethyl xylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI) and the like. Of these, toluene diisocyanate (TD) is preferred.
I), 4,4′-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPD
I), tetramethyl xylene diisocyanate (TMX
DI), 4,4'-dicyclohexylmethane diisocyanate (Desmodur W), 1,6-hexamethylene diisocyanate.

Examples of the polycarbonate diol represented by HOX ² OH include compounds represented by the following general formula. (M is an integer of 1 to 200, X ⁶ has 2 to 12 carbon atoms
Is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups).

In the above general formula, m is usually an integer of 1 to 200, preferably 3 to 20.

In the above polycarbonate diol, X ⁶ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms. Examples of alkylene groups that can be used include , Methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like. Examples of arylene groups are phenylene, naphthylene,
Examples include anthrylene and phenanthrylene. Examples of alkylene are benzylene, 1-phenylene,
2-Phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene and the like can be mentioned. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene and propylene groups are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

[0025] X in the general formula (2) ^3, the same as those shown in the above X ² may be mentioned, X ² and X ³ may be the same or different.

In the general formula (2), Y ¹ is a polyvalent carboxylic acid residue and Y ² is a divalent carboxylic acid residue. Examples of the divalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid. Examples thereof include meritic acid and other polycarboxylic acids. Of these, Y ¹ and Y ² are preferably isophthalic acid, terephthalic acid, and adipic acid.

In the general formula (2), m is usually 1 to 20.
It is an integer of 0, preferably 1-80, particularly preferably 1-20. When m exceeds 200, the viscosity becomes high and it becomes difficult to dissolve the initiator.

In the general formula (2), n is usually 2 to 20.
It is an integer of 0, preferably 3 to 100, particularly preferably 3 to 20. When n is larger than 200, the viscosity becomes high and it becomes difficult to dissolve the initiator. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.

The general formula (3) is {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or arylene group,
X ¹ is a polyhydric alcohol residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. It is represented by｝.

X ¹ in the general formula (3) is represented by the general formula (1)
And the same as those represented by the general formula (2) for X ² , m and n.

The general formula (4) is {In the formula, m is 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are alkylene diols, arylene diols, polyether diols, and polyurethanes represented by HOX ² OH and HOX ³ OH, respectively. X ¹ is a polyhydric alcohol residue, which is the residue of either a diol or a polycarbonate diol. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. }expressed.

X ¹ in the general formula (4) is represented by the general formula (1)
The same ones as those shown in X. ² , X ³ , M
Examples of n and n are the same as those shown in the general formula (2), and X ² and X ³ may be the same or different.

The urethane oligomer having a propenyl ether terminal group in (A) of the present invention is represented by the following general formula (5). {In the formula, m is 0 to 200, n is an integer of 2 to 200, and Q ¹ is -OX ² O- or -N (R ² ) -X ⁴ -N (R
² )-, and Q ² is a group represented by -OX ² O-. X ² is an alkyl diol represented by HOX ² OH, an aryl diol, a polyether diol,
It is the residue of a diol, either a polyester diol or a polycarbonate diol. -N (R ²⁾ -X ⁴
—N (R ² ) — is a diamine residue represented by HN (R ² ) —X ⁴ —N (R ² ) H, and X ⁴ is alkylene, arylene, aralkylene or cycloalkylene having 2 to 12 carbon atoms. And R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms. Z ¹
Is a polyvalent isocyanate residue, and Z ² is a divalent isocyanate residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

In the general formula (5), as the divalent isocyanate for Z ² , the same ones as mentioned in the above formula (ii) can be mentioned. The polyvalent isocyanate in Z ¹ is lysine ester triisocyanate,
Examples include hexamethylene triisocyanate and polyphenyl polyisocyanate.

In the general formula (5), Q ¹ is -OX ² O-.
Or ^{-N (R 2) -X 4 -N} (R 2) - in a group represented, Q ² is a group represented by -OX ² O-. X ² is H
OX ² OH is a diol residue represented by alkylene diol, arylene diol, polyether diol, polyester diol or polycarbonate diol, and X ² is the same as X ² in general (2). can give.

When the HOX ² OH is a polyester diol, the reaction products of the following (iii) and (iv) can be mentioned. (Iii) H (OX ⁷ ) m-OH (m is an integer of 0 to 200, X ⁷ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups having 2 to 12 carbon atoms. in a) (iv) in HOOC-Y ³ -COOH (wherein, Y ³ is 2 selected alkylene, arylene, from the group consisting of groups aralkylene and cycloalkylene
Is the basis of valence)

In the above-mentioned (iii) polyether diol, m is usually 0 to 200, preferably 3 to 20.

In the polyether diol of (iii) above, X ⁷ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups having 2 to 12 carbon atoms. Examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of alkylene are benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene,
2-phenyl propylene, 1-phenyl propylene, etc. are mentioned. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, ethylene group and propylene group are preferable. When the alkylene group becomes long, the solubility of the initiator deteriorates.

Examples of the dicarboxylic acid (iv) include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and polycarboxylic acid. Of these, preferred are isophthalic acid, terephthalic acid, and adipic acid. X ⁴ is the same as X ² in the general formula (2), R ² is the same as that represented by A in the general formula (1), and m and n are the general formulas. The same thing as shown in (2) can be mentioned.

The monomer having a propenyl ether terminal group in (A) of the present invention is represented by the following general formula (6) or general formula (7). ^{X 1 [-O-R 1]} n (6) ( wherein, n is an integer of 2 to 200, X ¹ is a polyhydric alcohol residue .n number of at least two is propenyl group for R ¹ And the rest may be hydrogen atoms, alkyl, acyl or aryl groups.)

In the general formula (6), n is usually 2 to 20.
It is an integer of 0, preferably 2 to 6. When n exceeds 200, the viscosity is high and the handling becomes poor. Examples of X ¹ are the same as those shown in the general formula (1).

[0042] {In the formula, n is 2-200, X ² is a diol residue represented by HOX ² OH, which is any one of alkylene diol, arylene diol, polyether diol, polyurethane diol or polycarbonate diol, and Y
¹ is a polyvalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. } In general formula (7), n is an integer of usually 2 to 200, preferably 2 to 6. When n exceeds 200, the viscosity is high and the handling becomes poor. Examples of Y ¹ and X ² are the same as those given in the general formula (2).

As the photopolymerization initiator (B) used in the present invention, known photocationic polymerization initiators can be used. For example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, P- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, P- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4-diphenyl-sulfonyl) phenyl]
Sulfide-bis-hexafluorophosphate, bis [4-diphenyl-sulfonyl) phenyl] sulfide-bis-hexafluoroantimonate, (2,4
-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate and the like can be mentioned. These are readily available from the market. For example, Asahi Denka Co., Ltd., SP-15
0, SP-170, Ciba-Geigy, IRGACURE 261, Union Carbide, UVR-697
4, UVR-6990 and the like.

In the present invention, a reactive diluent (C) can be used, if necessary, for the purpose of adjusting the viscosity of the resin composition.

Examples of the compound (C) include compounds represented by the following general formula (8). CH ₃ —CH═CH—O—X ² —O—R ³ (8) (In the formula, X ² represents an alkylene diol, arylene diol, polyether diol, polyurethane diol, or polycarbonate diol represented by HOX ² OH. It is a residue of any diol, and R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom. ｝

In the above general formula, X ² is the same as that shown in the general formula (2), and R ³ is an alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom having 2 to 12 carbon atoms. Is.

In the present invention, the proportions of (A) and (B) used are usually 95 to 99.9% by weight of (A), and (B) 0.1.
01 to 5% by weight, preferably (A) 96 to 98% by weight,
(B) It is 2 to 4% by weight.

In the present invention, the content of (C) is usually 5 to 60% by weight, preferably 10 based on the total weight of (A) and (B).
Is about 30% by weight, and when (C) exceeds 60% by weight,
The curing speed is significantly reduced.

In the composition of the present invention, if necessary, a known radical photopolymerizable composition (D) can be used in combination with (A). The content of (D) is usually (A)
0 to 100 parts by weight is used per 100 parts by weight of the component, preferably 10 to 40%.

The resin composition of the present invention may further contain, if necessary, an epoxy resin (eg, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, novolac type epoxy resin, etc.). , Pigments, colorants, inorganic fillers, non-reactive resins, and other various additives can be contained.

The adhesive composition of the present invention described in detail above is
Metals such as iron, copper, aluminum, ferrite, plated steel plate, permalloy; acrylic resin, polyester resin, A
Resins such as BS resin, polyamide resin, polycarbonate resin, vinyl chloride resin; glass, ceramics, etc. can be cured and bonded at high speed, and curing shrinkage at the time of curing and bonding is small, and bonding with excellent dimensional stability is possible. is there.

For adhesion, the composition of the present invention is applied to the adherend in an amount of about 10 to 500 μm, and then the adhesion surface is irradiated with light for curing and adhesion. Examples of usable light include ultraviolet rays emitted from a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp and the like.

[0053]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Examples 1 to 6 and Comparative Examples 1 to 3 Using the formulations prepared according to the formulations shown in Table 1, the photoreactivity (surface curing time, adhesive fixing time) according to the following evaluation methods and evaluation criteria. The adhesive strength and cure shrinkage were evaluated. Table 1 shows the obtained results. Evaluation method of photoreactivity: An adhesive is applied to a slide glass of 76 × 26 mm, and a small glass piece of 7 × 13 mm is attached with an adhesive resin. Then, a predetermined amount of ultraviolet rays was irradiated and the curability was observed. The surface hardening time was defined as the time when the adhesive was rubbed with a cotton swab and the cotton was not adhered. Further, the adhesive fixation time was evaluated as the time until the small glass piece was not collapsed by applying a shearing force of about 3 kgf. Evaluation criteria for photoreactivity: ◎ Adhesive fixing, surface curing (tack free) ○ Adhesive fixing, surface uncured △ Adhesive fixing insufficient, surface uncured × Adhesion unfixed, surface uncured Adhesive strength evaluation method: Laminated adhesive piece Was prepared (adhesive curing conditions were irradiation with a metal halide lamp of about 10 mW / cm 2 for 5 minutes). For the measurement, an adhesive piece was put in a sample holder, and a tensile tester was used to compress the sample with a compression plate at a speed of 5 mm / min, and the shear adhesive strength was measured. [Unit-kgf / cm2] Curing shrinkage evaluation method: The density before and after curing was measured to calculate the curing shrinkage. [Unit:%]

[0055]

[Table 1]

The compounds shown in Table 1 are as follows.
The CH ₃ —CH═CH— group (propenyl group) is Pr.
Abbreviated. Propenyl ether end groups Compound (1): Pr-O- ( CH 2 CH 2 O) 12 -Pr propenyl ether end groups of compound (2): Y: terephthalic acid residue propenyl ether end group compound (3): X: triethylene glycol residue Z: 4,4′-diphenylmethane diisocyanate residue, propenyl ether terminal group compound (4): X: Triethylene glycol residues propenyl ether end groups compound (5): R [O- ( CH 2 CH 2 O) 12 -Pr] 3 R: glycerol residue propenyl ether end groups of compound (6): X ¹ : triethyleneglycerin residue, Y: terephthalic acid residue, X ² : residue of polyurethane diol of the following formula Z: 4,4'-diphenylmethane diisocyanate residue acrylate end group compound (7): Epoxy terminal group compound (8): EP-828 (bisphenol type epoxy resin manufactured by Yuka Shell Co., Ltd. alicyclic epoxy terminal group compound (9): ERL-4221
(UCC made alicyclic epoxy resin) reactive diluent (10): Pr-O- CH 2 CH 2 -OH reactive diluent (11): 2-hydroxyethyl acrylate reactive diluent reactive diluent (12 ): BRL-4206 (alicyclic epoxy resin diluent manufactured by UCC) Photopolymerization catalyst (13): UVR-6974 (P- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, bis [4-diphenyl-sulfonio) phenyl ] 50% diluted product of sulfide-bis-hexafluoroantimonate mixture) Photopolymerization catalyst (14): Irgacure 184 (manufactured by Ciba Geigy)

[0057]

As described above, the photocurable adhesive composition containing the compound having a propenyl ether terminal group has better surface curability and smaller volume shrinkage than the radical polymerization type acrylate resin. The adhesiveness of the adhesive surface is excellent. Further, it is faster curable than an epoxy-based ultraviolet curable resin. From these facts, when the photocurable adhesive composition of the present invention is used, for example, in assembling a small optical component or electronic component, the surface unsuccessful due to oxygen inhibition, which is a drawback of the radical UV curable resin composition, is not observed. It does not cure, it has higher reactivity than the cationic polymerization type epoxy adhesive and can be bonded at high speed, and it can realize an adhesive / adhesive fixed part with good practical performance, and its curing is extremely useful. .

Claims (9)

[Claims] 1. A photocurable adhesive composition comprising a compound (A) having at least two propenyl ether terminal groups and a photopolymerization initiator (B). 2. (A) is selected from the group consisting of (poly) ether oligomers having a propenyl ether end group, polyester oligomers having a propenyl ether end group, urethane oligomers having a propenyl ether end group and monomers having a propenyl ether end group. The composition of claim 1 which is one or more compounds as defined below. 3. The composition according to claim 2, wherein the (poly) ether oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (1). ^{X 1 [-O- (AO) m} -R 1] n (1) { wherein, n is an integer of 2 to 200, the n-number of m 0 to
It is an integer of 200 and at least one of m is 1 or more. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene, arylene, aralkylene or cycloalkylene group having 2 to 12 carbon atoms, and when m is 2 or more, A may be the same or different, and the (AO) m portion may be random addition or block addition. good. X ¹ is a polyhydric alcohol residue. ｝ 4. The composition according to claim 2, wherein the polyester oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (2), general formula (3), or general formula (4). {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by alkylene diol, arylene diol,
It is a residue of any one of polyether diol, polyurethane diol or polycarbonate diol, Y ¹ is a polyvalent carboxylic acid residue, and Y ² is a divalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ {In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or arylene group,
X ¹ is a polyhydric alcohol residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ {In the formula, m is 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are alkylene diols, arylene diols, polyether diols, and polyurethanes represented by HOX ² OH and HOX ³ OH, respectively. X ¹ is a polyhydric alcohol residue, which is the residue of either a diol or a polycarbonate diol. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 5. The composition according to claim 2, wherein the urethane oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (5). {In the formula, m is 0 to 200, n is an integer of 2 to 200, and Q ¹ is -OX ² O- or -N (R ² ) -X ⁴ -N (R
² )-, and Q ² is a group represented by -OX ² O-. X ² is a residue of any one of alkyl diol, aryl diol, polyether diol, polyester diol or polycarbonate diol represented by HOX ² OH. -N (R ²⁾ -X ⁴ -
N (R ²⁾ - is ^{HN (R 2) -X 4 -N} (R 2) a diamine residue represented by H, X ⁴ is alkylene having 2 to 12 carbon atoms, arylene, aralkylene or cycloalkylene group And R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms. Z ¹ is a polyvalent isocyanate residue and Z ² is a divalent isocyanate residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 6. The composition according to claim 2, wherein the monomer having a propenyl ether terminal group is represented by the following general formula (6) or general formula (7). ^{X 1 [-O-R 1]} n (6) ( wherein, n is an integer of 2 to 200, X ¹ is a polyhydric alcohol residue .n number of at least two is propenyl group for R ¹ And the rest may be hydrogen atoms, alkyl, acyl or aryl groups.) {In the formula, n is 2-200, X ² is a diol residue represented by HOX ² OH, which is any one of alkylene diol, arylene diol, polyether diol, polyurethane diol or polycarbonate diol, and Y
¹ is a polyvalent carboxylic acid residue. At least two of n R ¹ 's are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 7. The content of (A) is 95 to 99.9% by weight,
The content of (B) is 0.01 to 5% by weight.
The composition according to any one of 1. 8. A reactive diluent (C) is further added, and the content of (C) is 5 to 60 relative to the weight of the composition.
The composition according to any one of claims 1 to 7, wherein the content of (A) is 50 to 90% by weight, and the content of (B) is 0.01 to 5% by weight. 9. The composition according to claim 8, wherein (C) is a reactive diluent represented by the following general formula (8). CH ₃ —CH═CH—O—X ² —O—R ³ (8) (In the formula, X ² represents an alkylene diol, arylene diol, polyether diol, polyurethane diol, or polycarbonate diol represented by HOX ² OH. It is a residue of any diol, and R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl group or hydrogen atom. ｝