JPH09235536A - Resin composition for adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for adhesion capable of directly bonding FRPs mutually without requiring sanding and primer treatment, comprising an epoxy acrylate resin composition prepared by blending a specific epoxy acrylate resin with a polymerizable vinyl monomer. SOLUTION: This resin composition for adhesion comprises an epoxy acrylate resin composition obtained by blending (A) 100 pts.wt. of an epoxy acrylate resin prepared by reacting a bisphenol type epoxy resin with a dimer acid and/or a carboxyl-containing butadiene-based polymer to give a modified epoxy resin and reacting the modified epoxy resin with (meth)acrylic acid with (B) 10-100 pts.wt. of a polymerizable vinyl monomer (e.g. styrene). Preferably 100 pts.wt. of the epoxy acrylate resin is mixed with 5-150 pts.wt. of a filler such as talc, etc., to raise bond strength much higher. Preferably an adhesive is provided with flexibility and bond strength is made much stronger by blending 100 pts.wt. of the epoxy acrylate resin composition with 10-50 pts.wt. of the urethane acrylate resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive resin composition, and more particularly to an adhesive resin composition used for adhesion of FRP.

[0002]

2. Description of the Related Art Epoxy acrylate resin obtained by dissolving a reaction product of an epoxy resin and (meth) acrylic acid in styrene has better workability and curability than epoxy resin alone, and has excellent corrosion resistance and mechanical properties. Because it ’s excellent
Especially FRP tanks and FRPs that require corrosion resistance and corrosion resistance
Widely used as a matrix for pipes and linings.

Epoxy acrylate resin is also used as a primer for adhering metal and FRP because it has excellent adhesiveness to metal. On the other hand, F
The mainstream method for bonding RPs is to bond (laminate) with a co-resin after sanding the bonding surfaces.
It takes manpower and time, but good adhesiveness can be obtained.

[0004]

However, in the sanding step in the conventional method, a large amount of dust is discharged, so that the working environment is very bad. Therefore, in order to prevent the dust, the installation of duct equipment or the operation by a worker is required. You will need to carry a dust mask. Furthermore, unless the FRP itself is cured to a certain extent in the sanding process, there is a problem that the sanding machine will be clogged and the workability will be reduced.

In order to omit the sanding step, there is a method of using a moisture-curable urethane resin for a primer and an adhesive. Urethane-based adhesives have good workability because they do not require surface treatment of FRP and have excellent adhesion to FRP, but they require many steps in manufacturing and work time after primer application is limited. It has been done. Further, in a humid place, the isocyanate group reacts with water at a considerably high rate, so that it has a drawback that it loses its activity as an adhesive.

Therefore, it is an object of the present invention to provide an adhesive resin composition capable of directly adhering FRPs to each other by omitting the steps of sanding and primer application.

[0007]

Means for Solving the Problems As a result of research for solving the above problems, the present inventors have obtained an epoxy acrylate obtained by reacting an epoxy resin having a specific composition with (meth) acrylic acid. Resin is FRP
The inventors have found that the material has excellent adhesive strength without the need for sanding or primer treatment steps, and arrived at the present invention.

That is, the adhesive resin composition of the present invention is a modified epoxy resin (a) obtained by reacting a bisphenol type epoxy resin with a dimer acid and / or a butadiene polymer having a carboxyl group in the molecule. In addition, an epoxy acrylate resin composition obtained by containing 10 to 100 parts by weight of a polymerizable vinyl monomer with respect to 100 parts by weight of an epoxy acrylate resin (b) obtained by reacting (meth) acrylic acid (ha ) Is included.
In the present specification, (meth) acrylic acid means both acrylic acid and methacrylic acid.

As the modified epoxy resin (a) used in the present invention, a bisphenol type epoxy resin and a dimer acid and / or a butadiene polymer having a carboxyl group in the molecule, such as triphenylphosphine and trialkylphosphine, are used. Using a known catalyst, 130 to 20
Epoxy equivalent of 200 to 2 obtained by reacting at a temperature of 0 ° C
000 is suitable. If the epoxy equivalent is less than 200, the adhesiveness will be poor, and if it exceeds 2000, the viscosity will be high and synthesis will be difficult, which is not preferable.

As the bisphenol type epoxy resin, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin can be used. For example, a product manufactured by Nippon Ciba Geigy Co., Ltd. which is synthesized by a reaction of bisphenol A or bisphenol F and epichlorohydrin. Name Araldite GY250, Araldite GY260,
Araldite GY280, Araldite GY6071,
Araldite GY6084, Araldite GY707
2. Yuka Shell Epoxy Co., Ltd. product name Epicoat 8
07, Epicoat 825, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003
Also, trade names of Epiclon 830, Epicron 840, Epicron 850, Epicron 1050 and the like manufactured by Dainippon Ink and Chemicals, Inc. can be used. In the present invention, these epoxy resins can be used alone or in combination of two or more kinds.

The dimer acid is obtained by polymerization of tall oil fatty acid, and has a dibasic acid having 36 carbon atoms as a main component (dimer) and a small amount of monobasic acid having 18 carbon atoms (monomer) and carbon. Number 54 tribasic acid (trimer)
Product name Haridimer 20 manufactured by Harima Kasei Co., Ltd.
0, 250, 300 can be used.

The butadiene-based polymer includes a polybutadiene polymer and a butadiene-acrylonitrile copolymer. The polybutadiene polymer having a carboxyl group in one molecule or the butadiene-acrylonitrile copolymer is Nippon Soda Co., Ltd. Product name NISSO-PB
C-1000, NISSO-PB C-2000, and
Product name Hycar CTBN 130 manufactured by Ube Industries, Ltd.
0X31, Hycar CTBN 1300X8, Hyc
arCTBN 1300X13, HycarCTBN
1300X9 and the like are included, and these can be used alone or in combination of two or more kinds.

The epoxy acrylate resin (b) used in the present invention is a reaction of the modified epoxy resin (a) with (meth) acrylic acid at 90 to 180 ° C. using a known esterification catalyst, polymerization inhibitor and the like. Can be obtained. Its molecular weight is 500 to 5 from the viewpoint of adhesive strength expression.
000 is preferred.

Suitable esterification catalysts are tertiary nitrogen compounds such as triester amine or quaternary salts thereof, substituted imidazoles, and phosphorus compounds such as trialkylphosphine and triphenylphosphine. The addition amount is 0.001 to 10.0 parts by weight based on the epoxy acrylate resin (b). 0.
If it is less than 001 parts by weight, the reaction time becomes long, and if it exceeds 10.0 parts by weight, the adhesive strength of the obtained adhesive is lowered.

Hydroquinone, tertiary butyl catechol, methoquinone and the like are used as a polymerization inhibitor for stably reacting the modified epoxy resin (a) with (meth) acrylic acid. The amount used is 0.00001 to 0.1 part by weight based on the epoxy acrylate resin (b). If it is less than 0.00001 parts by weight, there is no inhibitory effect, and gelation occurs during synthesis, and if it exceeds 0.1 parts by weight, the curing time of the finished resin greatly exceeds an appropriate working time.

At the time of esterification, a polymerizable vinyl monomer can be used as a solvent for the purpose of lowering the viscosity of the reaction system. The epoxy acrylate resin (b) synthesized as described above is dissolved in a polymerizable vinyl monomer and used as an epoxy acrylate resin composition (c).

As the polymerizable vinyl monomer, styrene,
(Meth) acrylic acid esters such as chlorostyrene, divinylbenzene or methyl (meth) acrylate, and polyfunctional (meth) acrylic acid esters such as ethylene glycol di (meth) acrylate are used. these,
They can be used alone or in combination of two or more.

The amount of the polymerizable vinyl monomer compounded is 10 to 1 with respect to 100 parts by weight of the epoxy acrylate resin (b).
It is in the range of 00 parts by weight. If it is less than 10 parts by weight, the working viscosity becomes high, and if it exceeds 100 parts by weight, the adhesive strength is lowered. Practically, it is preferable to use 20 to 100 parts by weight in consideration of working viscosity.

A filler may be added to the epoxy acrylate resin composition (c). As the filler, talc, calcium carbonate, bentonite, etc. are used, and these can be used alone or in combination of two kinds. Use of such a filler is preferable because the adhesive strength becomes higher than when the epoxy acrylate resin composition (c) is adhered alone. The amount of the filler used is in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the epoxy acrylate resin composition (c).

Further, a urethane acrylate resin can be blended in the epoxy acrylate resin composition (c). By blending the urethane acrylate resin, flexibility is imparted to the adhesive and the adhesive strength is further increased.

As the urethane acrylate resin, a known urethane acrylate resin having a molecular weight of 1,000 to 500 is used.
0 can be used. The compounding amount can be 10 to 50 parts by weight of the urethane acrylate resin with respect to 100 parts by weight of the epoxy acrylate resin composition (c). If it is less than 10 parts by weight, it becomes difficult to provide flexibility, and if it exceeds 50 parts by weight, the adhesive strength may be lowered due to defective resin curing.

For the curing of the adhesive resin composition thus obtained, an organic peroxide can be used as a curing catalyst and an organic metal salt can be used as a curing accelerator.
As the organic peroxide, ketone peroxides represented by methyl ethyl ketone peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide can be used. The amount used is in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the epoxy acrylate resin (b). If it is less than 0.5 parts by weight, the curing will be insufficient, and if it exceeds 3.0 parts by weight, the adhesive strength will be reduced.

The organic metal salt used as the curing accelerator includes cobalt salts such as cobalt naphthenate and cobalt octenoate. The amount added is in the range of 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the epoxy acrylate resin (b). If it is less than 0.01 parts by weight, the curing will be insufficient, and if it exceeds 3.0 parts by weight, the adhesive strength will be reduced.

[0024]

EXAMPLES The present invention will be described with reference to the following synthesis examples, examples and comparative examples. Parts and% in Synthesis Examples, Examples and Comparative Examples
Indicates parts by weight and% by weight unless otherwise specified. The molecular weight in each synthesis example was measured under the following conditions. (Measurement of molecular weight) GPC analysis pump 510 column manufactured by Waters Co., Ltd. Ultrastyragel detector manufactured by Waters refractometer solvent tetrahydrofuran column temperature 40 ° C. molecular weight conversion polystyrene

Synthesis Example 1 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 457
g, dimer acid (manufactured by Harima Kasei Co., Ltd., trade name “Haridimer H300”) 500 g, and triphenylphosphine 0.957 g were charged in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser, and generated heat. The reaction was carried out at 160 ° C. for 60 minutes while paying attention to the above to obtain a modified epoxy resin having an acid value of 0. This modified epoxy resin (957 g) was charged with acrylic acid (43 g), hydroquinone (0.1 g) and 2-methylimidazole (2.0 g).
Reaction was carried out at 30 ° C. for 120 minutes to obtain an epoxy acrylate resin having an acid value of 2.5. To this was added 538 g of styrene to obtain a resin part (A) of an adhesive resin composition having a number average molecular weight of 3,400.

Synthesis Example 2 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 700
43 g of dimer acid (manufactured by Harima Kasei Co., Ltd., trade name “Haridimer H300”) and 0.743 g of triphenylphosphine were charged in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser, and generated heat. The reaction was carried out at 160 ° C. for 60 minutes while paying attention to the above to obtain a modified epoxy resin having an acid value of 0. This modified epoxy resin (743 g) was charged with acrylic acid (257 g), hydroquinone (0.1 g), and 2-methylimidazole (2.0 g).
The reaction was carried out at 30 ° C. for 120 minutes to obtain an epoxy acrylate resin having an acid value of 1.5. To this was added 538 g of styrene to obtain a resin part (B) of an adhesive resin composition having a number average molecular weight of 560.

Synthesis Example 3 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 484
g, dimer acid (manufactured by Harima Kasei Co., Ltd., trade name “Haridimer H300”) 449 g, and triphenylphosphine 0.933 g were charged in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser, and generated heat. The reaction was carried out at 160 ° C. for 60 minutes while paying attention to the above to obtain a modified epoxy resin having an acid value of 0. 67 g of acrylic acid, 0.1 g of hydroquinone, and 2.0 g of 2-methylimidazole were added to 933 g of this modified epoxy resin, and 1 while paying attention to heat generation.
The reaction was carried out at 30 ° C. for 120 minutes to obtain an epoxy acrylate resin having an acid value of 2.8. To this was added 538 g of styrene, and the resin part (C) of the adhesive resin composition having a number average molecular weight of 2000
I got

Synthesis Example 4 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 447
g, 518 g of dimer acid (manufactured by Harima Kasei Co., Ltd., trade name “Haridimer H300”), and triphenylphosphine 0.965 g were charged in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser to generate heat. The reaction was carried out at 160 ° C. for 60 minutes while paying attention to the above to obtain a modified epoxy resin having an acid value of 0. To 965 g of this modified epoxy resin, 35 g of acrylic acid, 0.1 g of hydroquinone and 2.0 g of 2-methylimidazole were charged, and 1 while paying attention to heat generation.
The reaction was carried out at 30 ° C. for 120 minutes to obtain an epoxy acrylate resin having an acid value of 2.4. To this was added 538 g of styrene, and the resin part (D) of the resin composition for adhesion having a number average molecular weight of 4,600.
I got

Synthesis Example 5 436 g of bisphenol F type epoxy resin (Dainippon Ink and Chemicals, Inc., trade name "Epiclon 830")
521 g of dimer acid (manufactured by Harima Chemicals Co., Ltd., trade name "Haridimer H300") and 0.957 g of triphenylphosphine were charged in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser, and be careful of heat generation. While reacting at 160 ° C. for 60 minutes, a modified epoxy resin having an acid value of 0 was obtained. This modified epoxy resin (957 g) was charged with acrylic acid (43 g), hydroquinone (0.1 g), and 2-methylimidazole (2.0 g).
The reaction was carried out at 0 ° C for 120 minutes to obtain an epoxy acrylate resin having an acid value of 2.3. To this was added 538 g of styrene to obtain a resin part (E) of an adhesive resin composition having a number average molecular weight of 3,500.

Synthetic Example 6 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 453
g, dimer acid (manufactured by Harima Kasei Co., Ltd., trade name “Haridimer H300”) 496 g, and triphenylphosphine 0.949 g were charged in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser, and generated heat. The reaction was carried out at 160 ° C. for 60 minutes while paying attention to the above to obtain a modified epoxy resin having an acid value of 0. 51 g of methacrylic acid, 0.1 g of hydroquinone and 2.0 g of 2-methylimidazole were charged to 949 g of this modified epoxy resin, and the reaction was carried out at 130 ° C. for 120 minutes while paying attention to heat generation to obtain an epoxy acrylate resin having an acid value of 2.7. . To this was added 538 g of styrene to obtain a resin part (F) of an adhesive resin composition having a number average molecular weight of 3,400.

Synthesis Example 7 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy, trade name "Araldite # 260") 356
g, butadiene acrylonitrile copolymer (manufactured by Ube Industries, Ltd., trade name "Hycar CTBN 1300X3"
1 ”523g, 0.879g triphenylphosphine
Was charged into a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser.
The reaction was carried out at 60 ° C. for 60 minutes to obtain a modified epoxy resin having an acid value of 0. Acrylic acid 121 is added to 879 g of this modified epoxy resin.
g, hydroquinone 0.1 g, and 2-methylimidazole 2.0 g are charged at 130 ° C. for 12 hours while paying attention to heat generation.
Reaction was carried out for 0 minutes to obtain an epoxy acrylate resin having an acid value of 2.1. To this, 538 g of styrene was added and the number average molecular weight was 1
200 resin parts (G) of the resin composition for adhesion were obtained.

Synthesis Example 8 260 g of 2-hydroxyethyl methacrylate was charged into a flask equipped with a stirrer, a gas introduction tube, a thermometer, a condenser and a dropping funnel, and while paying attention to heat generation, the amount of 2,6
-344 g of toluene diisocyanate were added slowly from the dropping funnel. After completion of dropping, the mixture is reacted at room temperature for 3 hours, and then polyethylene glycol 1000 having a molecular weight of 2500
g was charged into the flask, and the temperature in the system was raised to 60 ° C. After reacting for about 3 hours, infrared absorption spectrum shows -NCO
It was confirmed that the absorption at (2260 cm ^-1 ) had disappeared, and the end point was set. This was dissolved in 404 g of styrene to obtain a urethane acrylate resin (H) as an adhesive resin composition having a number average molecular weight of 5000.

Synthesis Example 9 260 g of 2-hydroxyethyl methacrylate was charged into a flask equipped with a stirrer, a gas introduction tube, a thermometer, a condenser and a dropping funnel, and while paying attention to heat generation, the amount of 2,6
-344 g of toluene diisocyanate were added slowly from the dropping funnel. After completion of dropping, the mixture was reacted at room temperature for 3 hours, then 500 g of polyethylene glycol having a molecular weight of 500 was charged into the flask, and the temperature in the system was raised to 60 ° C.
After reacting for about 3 hours, the infrared absorption spectrum shows -NCO (2
It was confirmed that the absorption at 260 cm ^-1 ) had disappeared and the end point was set. This is dissolved in 276 g of styrene to give a number average molecular weight of 1
000 urethane acrylate resin (I) having a resin composition for adhesion was obtained.

Synthesis Example 10 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 682
g, bisphenol A (135 g) and triphenylphosphine (0.817 g) were placed in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser. A modified epoxy resin was obtained. 817 g of this modified epoxy resin, 183 g of methacrylic acid, 0.1 g of hydroquinone, 2-
2.0 g of methylimidazole was charged and reacted for 120 minutes at 130 ° C. while paying attention to heat generation to obtain an epoxy acrylate resin having an acid value of 7.5. To this was added 538 g of styrene to obtain a resin part (J) of an adhesive resin composition having a number average molecular weight of 900.

Synthesis Example 11 Bisphenol A type epoxy resin (manufactured by Nippon Ciba Geigy Ltd., trade name "Araldite # 260") 682
g, bisphenol A (135 g) and triphenylphosphine (0.817 g) were placed in a four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser. A modified epoxy resin was obtained. 817 g of this modified epoxy resin, 183 g of methacrylic acid, 0.1 g of hydroquinone, 2-
2.0 g of methylimidazole was charged and reacted for 120 minutes at 130 ° C. while paying attention to heat generation to obtain an epoxy acrylate resin having an acid value of 7.5. To this was added 538 g of styrene and 23 g of acrylic acid to obtain a resin part (K) of an adhesive resin composition having a number average molecular weight of 900.

For comparison, an ortho unsaturated polyester resin for a septic tank (manufactured by Nippon Yupica Co., Ltd., “Yupika 5144AP”)
T ") was prepared as an adhesive resin composition (L).

To cure the adhesive resin compositions (A) to (K) obtained in Synthesis Examples 1 to 11, the adhesive resin composition 1 is used.
To 00 g, 0.5 g of 6% cobalt naphthenate was used as a curing accelerator, and 2.0 g of tertiary butyl hydroperoxide was used as a curing catalyst. Further, for the curing of the adhesive resin composition (L) prepared for comparison, 100 g of the adhesive resin composition was used with 1.0 g of methyl ethyl ketone hydroperoxide as a curing catalyst.

Examples 1 to 20, Comparative Examples 1 to 9 Resin parts (A to K) of the adhesive resin composition obtained in the above Synthetic Examples 1 to 11 and the adhesive resin composition for comparison (L) Was used to produce an adhesive resin composition. The compounding ratio of each adhesive resin composition is shown in Tables 1-3. Table 1 shows the compounding ratios of the adhesive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3, and Table 2 shows the adhesive resins of Examples 8 to 19 and Comparative Examples 4 to 6 in which a filler was compounded. The composition ratios of the compositions, and Table 3 show Examples 20 to 2 in which a urethane acrylate resin was compounded.
2 shows the compounding ratio of the adhesive resin compositions of Comparative Examples 7 to 9.

Test Example The adhesive strength with FRD was measured by a cross peel test under the following conditions for the adhesive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 9.

[Evaluation Method as Adhesive] (Cross Peel Test) The following FRP plate mold surface having dimensions of 75 × 25 × 3 mm was degreased with acetone. The resin composition was applied to the FRP plate adhesion portion (25 × 25 mm) and sandwiched with clips to prepare a cross peel test piece. After leaving this at room temperature (23 to 25 ° C) for 3 days, the speed is 5 mm /
The cross peel strength was measured in minutes. The results are shown in Tables 1 to 3.
Shown in

(FRP plate production conditions) Resin: Orthophthalic acid type general laminating resin "Yupica 5144APT" manufactured by Nippon Yupica Co., Ltd. Glass: Asahi Fiber Glass Co., Ltd. CM455 3-ply Hardening: Nippon Oil & Fats Co., Ltd. ) Made Permek N 1.0PHR
Room temperature curing

The obtained results are shown in Tables 1 to 3.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

The resin composition for adhesives of the present invention is FRP.
Adhesive force leading to material destruction can be obtained without requiring sanding or primer treatment steps on the material. Furthermore, since the adhesive resin composition of the present invention can omit the conventional FRP surface treatment step, it contributes to the improvement of production efficiency, and since the dust generated by sanding is eliminated, the working environment is significantly improved. To be done.

Claims (4)

[Claims] 1. A modified epoxy resin (a) obtained by reacting a bisphenol type epoxy resin with a dimer acid and / or a butadiene-based polymer having a carboxyl group in the molecule is reacted with (meth) acrylic acid. An epoxy acrylate resin composition (c) obtained by containing 10 to 100 parts by weight of a polymerizable vinyl monomer with respect to 100 parts by weight of the obtained epoxy acrylate resin (b). Resin composition. 2. The adhesive resin composition according to claim 2, further comprising at least one selected from the group consisting of talc, calcium carbonate and bentonite per 100 parts by weight of the epoxy acrylate resin composition (c). An adhesive resin composition containing 5 to 200 parts by weight. 3. The adhesive resin composition according to claim 1, further comprising 10 to 50 parts by weight of a urethane acrylate resin with respect to 100 parts by weight of the epoxy acrylate resin composition (c). An adhesive resin composition comprising: 4. The adhesive resin composition according to any one of claims 1 to 4, wherein the butadiene-based polymer is a polybutadiene polymer or a butadiene-acrylonitonyl copolymer. Stuff.