JP2000313869A - Curable resin composition for adhesion and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition for adhesive which has an excellent productivity, workability and heat stability and exerts a good adhesion property which leads to the breakage of FRP materials, even under an elevated temperature atmosphere, and to provide a its preparation process. SOLUTION: A curable resin composition for adhesion is prepared by adding an isocyanate compound (D), a hardener (E) and an accelerator (F) to a resin composition (C) comprising a radically polymeriable composition (A) containing a (meth)acryloyl group and a butadiene/acrylonitrile copolymer in a molecule and a radically polymerizable unsaturated monomer (B). In a preparation process of a curable resin composition for adhesion, this component (A) and component (B) are mixed to obtain the resin composition (C), which is subsequently added with components (D), (E) and (F).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition for bonding, and more particularly to a curable resin composition for bonding suitably used for bonding between FRP molded articles.

[0002]

2. Description of the Related Art FRP molded using an unsaturated polyester resin or an epoxy (meth) acrylate resin and a reinforcing material such as glass fiber is used for various tanks, pipes, and body protective lining materials such as metal and concrete. Widely used as.

[0003] In some cases, these FRPs require an operation of bonding FRP members such as partition plates and pipes after molding. Generally, such bonding between FRPs is performed by using an adhesive mainly composed of the same resin as the FRP member after sanding is performed as a pretreatment of the bonding surface.

[0004]

However, the conventional bonding operation involving a sanding operation has a large burden on countermeasures against a large amount of dust generated by sanding. As a countermeasure against dust, it is necessary to install a dust collection duct and wear a dust mask from the viewpoint of worker health. Further, there is a problem that the work labor and the time required for the work lower the productivity.

In recent years, moisture-curable urethane-based resins and urethane methacrylate-based resins which do not require the above sanding work have been used as primers and adhesives. However, the working time of these adhesives after the application of the primer is limited, or in a humid place, it reacts with moisture to cause a decrease in adhesiveness. A problem such as a decrease occurs, and a problem that stability of adhesiveness is lacking is pointed out.

Accordingly, it is an object of the present invention to provide an adhesive curable resin composition which enables direct bonding between FRPs without the need for a sanding operation or a primer step, and which is excellent in productivity, workability, thermal stability and adhesiveness. An object of the present invention is to provide a product and a method of manufacturing the same.

[0007]

That is, the present invention provides a radical polymerizable composition (A) containing a (meth) acryloyl group and a butadiene-acrylonitrile copolymer in the molecule.
And a radical polymerizable unsaturated monomer (B), and an isocyanate compound (D), a curing agent (E), and a curing accelerator (F). The present invention provides a resin composition. The present invention also provides
When the resin composition (C) is a radical polymerizable composition (A) 10
Radical polymerizable unsaturated monomer (B) 4
An object of the present invention is to provide the curable resin composition for adhesion prepared by mixing 0 to 180 parts by weight. The present invention also provides
1 to 50 parts by weight of the isocyanate compound (D) and 0.1 to 50 parts by weight of the curing agent (E) are added to 100 parts by weight of the resin composition (C).
An object of the present invention is to provide the above-mentioned curable resin composition for adhesion, in which about 20 parts by weight and 0.1 to 10 parts by weight of a curing accelerator (F) are blended. The present invention also provides the above curable resin composition for adhesion, further comprising a thixotropic agent. The present invention also provides a resin composition comprising a radical polymerizable composition (A) containing a (meth) acryloyl group and a butadiene-acrylonitrile copolymer in a molecule, and a radical polymerizable unsaturated monomer (B). (C), and subsequently, an isocyanate compound (D), a curing agent (E) and a curing accelerator (F) are blended with the resin composition (C). Is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The radical polymerizable composition (A) containing a (meth) acryloyl group and a butadiene-acrylonitrile copolymer in the molecule is firstly a carboxyl group-terminated butadiene-acrylonitrile copolymer and an intramolecular And a vinyl polymerizable monomer having a glycidyl group in the presence of a reaction catalyst, a polymerization inhibitor and, if necessary, a radical polymerizable unsaturated monomer.

Second, an epoxy group-terminated butadiene-acrylonitrile copolymer is reacted with an unsaturated monobasic acid in the presence of a reaction catalyst, a polymerization inhibitor and, if necessary, a radical polymerizable unsaturated monomer. Can be manufactured.

Third, a vinyl group-terminated butadiene-acrylonitrile copolymer can be used by dissolving it in a radical polymerizable unsaturated monomer.

The carboxyl group-terminated butadiene-acrylonitrile copolymer used in the production of the radical polymerizable composition (A) includes, for example, Hiker CT polymers such as Hiker CTBN manufactured by BF Goodrich, USA. Can also be used.

The epoxy group-terminated butadiene-acrylonitrile copolymer used in the production of the radically polymerizable composition (A) includes, for example, Hiker ET polymers such as Hiker ETBN manufactured by BF Goodrich, USA. Any of them can be used.

The vinyl-terminated butadiene-acrylonitrile copolymer used for the production of the radically polymerizable composition (A) includes, for example, Hiker VT polymers such as Hiker VTBN manufactured by BF Goodrich, USA. Any of them can be used.

Examples of the vinyl polymerizable monomer having a glycidyl group in the molecule used for producing the radical polymerizable composition (A) include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether and the like.

The unsaturated monobasic acid used for producing the radically polymerizable composition (A) includes acrylic acid, methacrylic acid and the like, and these may be used in combination.

The radical polymerizable unsaturated monomer used in the production of the radical polymerizable composition (A) may be the same as the radical polymerizable unsaturated monomer (B) in the present invention. it can. The radical polymerizable unsaturated monomer (B) will be described below.

The reaction catalyst used for producing the radically polymerizable composition (A) includes triethylamine,
Compounds containing a tertiary nitrogen such as pyridine derivatives, imidazole derivatives and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine;
Or phosphorus compounds such as trimethylphosphine and triphenylphosphine. The amount of reaction catalyst used is
0.1 parts by weight based on 100 parts by weight of the radical polymerizable composition (A).
It is selected from the range of 001 to 2 parts by weight.

The polymerization inhibitor used in producing the radically polymerizable composition (A) includes hydroquinone,
Known polymerization inhibitors such as methylhydroquinone and phenothiazine are used, and the amount thereof is selected from the range of 0.001 to 2 parts by weight based on 100 parts by weight of the radically polymerizable composition (A).

The reaction temperature is usually preferably from 100 to 150 ° C. The reaction time is not particularly limited, but is generally preferably about 2 to 8 hours.

In the present invention, the radically polymerizable composition (A) generally comprises a radically polymerizable unsaturated monomer (B)
And used as the resin composition (C). Examples of the radical polymerizable unsaturated monomer (B) include (meth) acrylic esters such as styrene, chlorostyrene, divinylbenzene and methyl (meth) acrylate, and polyfunctional such as ethylene glycol di (meth) acrylate. (Meth) acrylic esters and the like.

The amount of the radical polymerizable unsaturated monomer (B) to be used is usually in the range of 40 to 180 parts by weight, preferably 60 to 120 parts by weight, per 100 parts by weight of the radical polymerizable composition (A). It is in the range of parts by weight. The radically polymerizable unsaturated monomer used in the production of the radically polymerizable composition (A) is included in the radically polymerizable unsaturated monomer (B). That is, when a radically polymerizable unsaturated monomer is used during the production of the radically polymerizable composition (A), the amount of the radically polymerizable unsaturated monomer (B) relative to the radically polymerizable composition (A) is reduced. The radically polymerizable unsaturated monomer (B) is preferably added later so as to fall within the above range.

The resin composition (C) thus obtained
Is mixed with an isocyanate compound (D), a curing agent (E) and a curing accelerator (F) to obtain a curable resin composition for bonding.

The isocyanate compound is usually used for the reaction at the stage of synthesizing the resin composition, but when used at the time of synthesis, the molecular weight increases and liquefaction becomes difficult. This tendency is particularly remarkable in the case of polyisocyanate.

According to the present invention, there is one feature that the isocyanate compound (D) is compounded simultaneously with the curing agent (E) and the curing accelerator (F), thereby providing excellent adhesiveness. can do. For example, JP-A-9-2
Japanese Patent No. 35536 discloses an adhesive resin composition in which a polymerizable vinyl monomer and a urethane acrylate resin are blended with an epoxy acrylate resin, but this technique uses urethane acrylate instead of an isocyanate compound alone. Therefore, there is room for improvement in the adhesiveness.

Examples of the isocyanate compound include diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; Polyisocyanates such as name duranate 24A-100, TPA-100, THA-100 can be used. The use of polyisocyanate is preferred from the viewpoint of safety and adhesiveness.

The amount of the isocyanate compound (D) to be used is not particularly limited, but is preferably 100%.
A suitable range is 1 to 50 parts by weight with respect to parts by weight.

If the amount of the isocyanate compound (D) is less than 1 part by weight per 100 parts by weight of the resin composition (C), the molecular weight of the resin composition does not increase and the strength does not increase. It is difficult to exhibit the improvement in adhesiveness due to the addition. If the amount is more than 50 parts by weight, it reacts with moisture in the air to cause a foaming phenomenon, which may lower the adhesiveness.

Examples of the curing agent (E) include ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide, hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide, and tertiary butyl peroxide. Peroxyesters such as octoate, dialkyl peroxides such as dicumyl peroxide, diacyl peroxides such as lauryl peroxide and benzoyl peroxide can be used, but diacyl peroxides such as benzoyl peroxide are preferred. It is.

The amount of the curing agent (E) used depends on the amount of the resin composition (C)
Usually about 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight.

Examples of the curing accelerator (F) include organic metal salts such as cobalt naphthenate and cobalt octylate; quaternary ammonium salts such as dimethylbenzylamine; β-diketones such as acetylacetone; dimethylaniline;
N, N-dimethyl-p-toluidine, N, N-bis (2
Although amines such as -hydroxypropyl) -p-toluidine can be used, preferred are amines such as N, N-bis (2-hydroxypropyl) -p-toluidine.

The amount of the curing accelerator (F) to be used is usually about 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the resin composition (C).

As the thixotropic agent (thixotropic agent) which can be incorporated in the curable resin composition for adhesion of the present invention, inorganic hydrophilic silica powder, hydrophobic silica powder, and organic amides can be used. May be used in combination. As the inorganic type, for example, Aerosil # 200 of Nippon Aerosil Co., Ltd.
And Cabotir TS-720 of Cabot Corporation, and Kaleisha's Taren 7200-20 and Kusumoto Kasei's Dispalon 6900-10S of organic type.

The amount of the thixotropic agent used is 100 parts of the resin composition (C).
Usually about 0.1 to 30 parts by weight with respect to parts by weight,
Preferably it is 1 to 15 parts by weight.

Further, the curable resin composition for adhesion of the present invention may contain a filler such as silica, talc, bentonite or calcium carbonate as an inorganic filler or a tin catalyst as a reaction catalyst of an isocyanate compound. Can be.

[0035]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples,% and parts mean weight% and parts by weight, respectively.

Synthesis Example 1 In a vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, 142 g of glycidyl methacrylate, a carboxyl-terminated butadiene-acrylonitrile copolymer (B.
Hiker CTBN1300X manufactured by F Goodrich
13) 1790 g, triethylamine 5.8 g, hydroquinone 0.6 g, and styrene 644 g were charged and reacted at 120 ° C. for 3.5 hours while flowing air. When the acid value was 3, 1288 g of styrene was further added, and the viscosity was 4.1 p.
Thus, a resin composition (C) having an s / 25 ° C. was obtained. Further, as a thixotropic agent, Cavosil TS-100 was added to 100 parts of the resin composition (C).
720 parts were blended to obtain a resin composition (Ca) having a viscosity of 300 ps / 25 ° C.

Synthesis Example 2 An epoxy-terminated butadiene-acrylonitrile copolymer (manufactured by BF Goodrich, Hiker-ETB) was placed in a vessel equipped with a stirrer, thermometer, reflux condenser, and gas inlet tube.
N1300X40) 2300 g, methacrylic acid 86 g,
7 g of triethylamine, 0.7 g of hydroquinone and 1193 g of styrene were charged and reacted at 120 ° C. for 3 hours while flowing air.
3 g was added to obtain a resin composition (C) having a viscosity of 5.0 ps / 25 ° C. Further, 5 parts of Cavosil TS-720 as a thixotropic agent and 10 parts of silica as a filler were mixed with 100 parts of the resin composition (C) to obtain a resin composition (Cb) having a viscosity of 240 ps / 25 ° C. .

Synthesis Example 3 A vinyl-terminated butadiene-acrylonitrile copolymer (manufactured by BF Goodrich, Hiker VTBN) was placed in a vessel equipped with a stirrer, thermometer, reflux condenser, and gas inlet tube.
1300X13) 500 g, hydroquinone 0.1 g,
500 g of styrene was measured and heated to 100 ° C. Immediately after the hydroquinone and Hiker VTBN1300X13 were dissolved in styrene, the mixture was cooled to obtain a resin composition (C) having a viscosity of 5.8 ps / 25 ° C. Further, the resin composition (C) 100
And 10 parts of Cavosil TS-720 as a thixotropic agent were blended with the resin composition having a viscosity of 350 ps / 25 ° C.
c) was obtained.

For comparison, one equivalent of a bisphenol-based epoxy resin having an epoxy equivalent of 900 was reacted with one equivalent of methacrylic acid and dissolved in styrene (40%) to prepare an epoxy methacrylate resin as a resin composition (Cd). .

Further, in place of the isocyanate compound (D) to be added to the resin composition (C), 4 equivalents of tolylene diisocyanate were added to Uniol D-1 manufactured by NOF Corporation.
No. 00, 2 equivalents of hydroxyethyl methacrylate and 35% of styrene.
100 urethane methacrylate resins were prepared for comparison.

Examples 1-4 Based on 100 parts of the resin composition of Synthesis Examples 1-3, 3 parts of 50% benzoyl peroxide as a curing agent and N, N-bis (2-hydroxypropyl)-as a curing accelerator were used. p-
Toluidine was added in an amount of 0.5 part, and an isocyanate compound was further added at the ratio (part) shown in Table 1 to obtain a curable resin composition for bonding.

COMPARATIVE EXAMPLE 1 To 100 parts of the resin composition (Cd), 1.5 parts of methyl ethyl ketone peroxide as a curing agent and 0.5 parts of 6% cobalt naphthenate as a curing accelerator were added. A curable resin composition was obtained.

Comparative Example 2 To 100 parts of the resin composition (Cd), 1.5 parts of methyl ethyl ketone peroxide as a curing agent and 0.5 parts of 6% cobalt naphthenate as a curing accelerator were added. The compounds were added at the ratios (parts) shown in Table 1 to obtain a curable resin composition for bonding.

Comparative Example 3 To 100 parts of the resin composition (Cb) produced in Synthesis Example 2, 1.5 parts of methyl ethyl ketone peroxide was used as a curing agent, and 0.5% of 6% cobalt naphthenate was used as a curing accelerator. To obtain a curable resin composition for adhesion.

Comparative Example 4 To 100 parts of the resin composition (Ca) prepared in Synthesis Example 1, 1.5 parts of methyl ethyl ketone peroxide was used as a curing agent, and 0.5% of 6% cobalt naphthenate was used as a curing accelerator. And the above urethane methacrylate resin was added at the ratio (part) shown in Table 1 to obtain a curable resin composition for bonding.

The curable resin compositions for adhesion of the respective examples and comparative examples produced as described above were subjected to the following adhesion test.

(Preparation of Adhesive FRP Plate) Resin: Showa Polymer Co., Ltd., unsaturated polyester resin "Rigolac KN-5370BQT" Glass fiber: Nitto Defense Co., Ltd., MC-450 6 ply (sheet) Curing Conditions: Nippon Yushi Co., Ltd., Permec N 1.2% Production method: A mold release agent was applied to the mold surface in a 20 ° C. atmosphere, and laminated using resin and glass fiber. FRP board thickness is 5mm
And The glass content was 36%. Curing: Used for adhesion test after leaving at 20 ° C. for 2 weeks.

(Evaluation Test Method as Adhesive) Bending Peeling Test Method A laminated FRP plate was measured for a test piece (75 mm × 25 mm).
Then, a smooth surface laminated in contact with the mold surface is used as an adhesion surface, and a portion of the adhesion area (25 mm × 25 mm) from the end of the test piece is degreased with acetone. The curable resin composition for adhesion was applied to the adhesion portion of the two test pieces, and fixed with an overlapping clip. The thickness of the curable resin composition for adhesion was adjusted to 0.5 mm by spraying glass beads on the adhesion surface. After 1 day, the bonded test piece was moved at a speed of 3 mm in an atmosphere of 20 ° C. and 40 ° C.
/ Min. In addition, the energy from loading to breaking was also measured.

Tables 1 and 2 show the results of evaluation tests of the curable resin composition for adhesion as an adhesive.

[0050]

[Table 1]

[0051]

[Table 2]

Polyisocyanate: Coronate 2096 manufactured by Nippon Polyurethane Co., Ltd.
(Trimer of 1,6-hexanediol diisocyanate): Duranate TPA-100 (1,1) manufactured by Asahi Kasei Corporation
6-Hexanediol diisocyanate trimer) Destruction state I: Interfacial peeling of adhesive surface II: Cohesive failure of adhesive III: FRP material fracture

As is clear from Table 1, Examples 1 to 4 showed the results of FRP material destruction or adhesive cohesion destruction in 20 ° C. and 40 ° C. atmospheres, and showed good adhesiveness.

On the other hand, as apparent from Table 2, Comparative Example 1
In Nos. 4 to 4, in 20 ° C. and 40 ° C. atmospheres, the interface of the FRP bonding surface was peeled off, resulting in poor adhesion.

[0055]

According to the present invention, there is no need for a sanding step or a primer coating step when bonding FRP,
Because direct bonding between FRPs is possible, productivity,
Provided is a curable resin composition for adhesion having excellent workability and thermal stability, and having good adhesiveness particularly leading to FRP material destruction even in a high-temperature atmosphere, and a method for producing the same.
Further, according to the present invention, dust is not generated due to sanding, and the working environment is greatly improved.

Claims (5)

[Claims] 1. A resin composition (C) comprising a radical polymerizable composition (A) containing a (meth) acryloyl group and a butadiene-acrylonitrile copolymer in a molecule and a radical polymerizable unsaturated monomer (B). ), And an isocyanate compound (D), a curing agent (E) and a curing accelerator (F). 2. The resin composition (C) is prepared by mixing 40 to 180 parts by weight of the radically polymerizable unsaturated monomer (B) with respect to 100 parts by weight of the radically polymerizable composition (A). The curable resin composition for adhesion according to claim 1. 3. A resin composition (C) based on 100 parts by weight,
The adhesive according to claim 2, wherein the isocyanate compound (D) is 1 to 50 parts by weight, the curing agent (E) is 0.1 to 20 parts by weight, and the curing accelerator (F) is 0.1 to 10 parts by weight. Curable resin composition. 4. The adhesive curable resin composition according to claim 1, further comprising a thixotropic agent. 5. A resin composition comprising a radical polymerizable composition (A) containing a (meth) acryloyl group and a butadiene-acrylonitrile copolymer in a molecule and a radical polymerizable unsaturated monomer (B). (C), and subsequently, an isocyanate compound (D), a curing agent (E) and a curing accelerator (F) are blended with the resin composition (C). Manufacturing method.