JPH0681828B2 - Pinyl pyridine adhesive - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinylpyridine-based adhesive.

Conventional technology General formula (1) [In the formula, R ₁ represents a hydrogen atom or an alkyl group. ] The homopolymer of vinyl pyridine represented by the following has a drawback that it has a high glass transition point (Tg) and is hard and brittle. Therefore, it is necessary to use the polymer alone as an active ingredient of an adhesive. It is difficult. Therefore, the vinyl pyridines of the above general formula (1) have been used for adhesives as copolymers with butadiene or as terpolymers with butadiene and styrene (Japanese Patent Publication No. 36-20584). (See Japanese Patent Publication No. 35-5195). However, these adhesives are mainly based on the adhesion between rubber and rubber or the adhesion between rubber and metal.

Objects and Structures of the Invention The inventors of the present invention not only bond rubber and rubber or rubber and metal, but also metal and metal, metal and composite, and composite and composite. As a result of intensive studies to develop an adhesive effective for adhesion, it was found that the copolymer shown below can achieve the intended purpose of the present invention, and the present invention has been completed here. .

That is, the present invention has the general formula (1) [In the formula, R ₁ represents a hydrogen atom or an alkyl group. ] And vinyl pyridines represented by the general formula (2) [In the formula, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents an alkyl group. ] A vinylpyridine-based adhesive characterized by containing a copolymer with an acrylate compound represented by the following.

The adhesive of the present invention contains, as a main component, a copolymer of the vinylpyridines represented by the general formula (1) and the acrylate compound represented by the general formula (2).

In the general formula (1), examples of the alkyl group represented by R ₁ include an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. In the general formula (2), examples of the alkyl group represented by R ₃ include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms.

As the vinyl pyridines of the general formula (1), conventionally known ones can be widely used.
Vinyl pyridine, 2-methyl-5-vinyl pyridine, 2
-Methyl-6-vinyl pyridine, 5-ethyl-2-vinyl pyridine, etc. can be mentioned. In the present invention, these may be used alone or in combination of two or more.

Also, as the acrylate compound of the general formula (2), conventionally known compounds can be widely used, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyre methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl. Methacrylate, propyl acrylate, propyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate and the like can be mentioned. In the present invention, these may be used alone or in combination of two or more.

The copolymer used in the present invention is obtained by copolymerizing the vinylpyridines represented by the general formula (1) and the acrylate compound represented by the general formula (2). The copolymer can be easily produced by a conventionally known polymerization method such as radical polymerization or ionic polymerization. A preferred embodiment for producing the copolymer will be described. For example, vinyl pyridines of the general formula (1) and an acrylate compound of the general formula (2) are mixed in a predetermined amount, and azobisisobutyronitrile (AIBN) is added. Azobiscyano compounds such as, peroxides such as benzoyl peroxide, alkyllithium, organometallic compounds such as ethyl aluminum dichloride, in the presence of a polymerization initiator such as an inorganic halogen compound such as boron fluoride, solution polymerization, suspension polymerization, Emulsion polymerization or bulk polymerization may be performed. Solvents used for solution polymerization include methanol, dimethylformamide,
Examples thereof include N-methylpyrrolidone and dimethyl sulfoxide. These polymerization reactions are usually carried out at -80 to 120 ° C, and the reaction time is generally 0.5 to 10 hours. The copolymer of the present invention thus obtained has a composition of 10 to 90 mol% of vinyl pyridines and 90 to 90% of an acrylate compound.
10 mol%, preferably vinyl pyridines 30
˜70 mol% and 70 to 30 mol% of an acrylate compound. If the composition of the copolymer deviates from the above range, the intended effect of the present invention cannot be exhibited. The average molecular weight of the copolymer is usually about 500 to 500000, preferably 1000 to 100000.

The adhesive of the present invention contains additives commonly used in this type of adhesive, such as solvents (for example, ketones such as methyl ethyl ketone, esters such as ethyl acetate, alcohols such as methanol, aromatic carbonization such as toluene). Hydrogen, etc.), antioxidants, elastomers, plasticizers, pigments, fillers and the like can be appropriately added.

When the adhesive of the present invention is used, the adhesive of the present invention is applied to a substrate to be adhered, for example, a metal such as rubber, aluminum or iron, a composite such as fiber reinforced plastic (FRP and FRTP), and dried. Post-heating and pressurization may be performed to bond the base materials to each other. The amount of the present invention the adhesive should be applied to the substrate, but it may vary depends on the type or the like of the substrate to be coated, may be coated at a ratio of 100 to 500 g / m ^2. As a coating method, any conventionally known method can be adopted, and examples thereof include a dipping method, a brush coating method, a roll coating method, and a spray method. As a drying method, for example, room temperature drying, heat drying, or the like can be adopted. The conditions of heat and pressure treatment after drying are preferably 100 to 250 ° C. and about 0.1 to 10 kg / cm ² .

EFFECTS OF THE INVENTION The adhesive of the present invention is not limited to adhesion between rubber and rubber and adhesion between metal and rubber, but also adhesion between metal and metal, adhesion between metal and composite, and adhesion between composite and composite. It is also very suitable.

Examples Example 1 4-vinylpyridine (hereinafter referred to as "monomer A"), 2-ethylhexyl methacrylate (hereinafter referred to as "monomer B") and AIBN 0.005 in the blending amounts shown in Table 1 below.
5 mol at a reaction temperature of 68 ° C. in 200 g of methanol
The polymerization reaction was carried out for a time. After completion of the reaction, the produced copolymer was precipitated in a hexane solvent and dried.

The monomer composition ratio of the copolymer obtained according to the formulation of the formulation 1 was monomer A: monomer B = 3: 1, and the average molecular weight of the copolymer was about 70,000. The monomer composition ratio of the copolymer obtained according to the formulation of the formulation 2 was monomer A: monomer B = 1: 1, and the average molecular weight of the copolymer was about 60,000. The monomer composition ratio of the copolymer obtained according to the formulation of the formulation 3 was monomer A: monomer B = 1: 3, and the average molecular weight of the copolymer was about 70,000.

Each of the copolymers obtained above was dissolved in methyl ethyl ketone to prepare a 20 wt% solution adhesive. The adhesive containing the copolymer obtained according to the formulation of formulation 1 is referred to as “adhesive A”, and the adhesive containing the copolymer obtained according to the formulation of formulation 2 is referred to as “adhesive B”. The adhesive containing the copolymer obtained according to the composition of the composition 3 was referred to as “adhesive C”.

Al / Al, steel / steel, FRP / Al and FRP / FRP are used as the base material, and adhesive A, adhesive B or adhesive C of 150 g / m ² is applied to these base materials (25 mm x 12.5 mm). Apply at a rate of 175 ℃, 3K
It was crimped at g / cm ² for 15 minutes. The tensile shear adhesive strength was determined according to the tensile shear adhesive strength test method for adhesives (JIS K-6850), and the results are shown in Table 2.

Example 2 0.4 mol of monomer A, 0.4 mol of monomer B and 0.05 mol of AIBN were used, and a polymerization reaction was carried out in 400 g of methanol at a reaction temperature of 68 ° C. for 5 hours. After completion of the reaction, the produced copolymer was precipitated in a hexane solvent and dried. The monomer composition ratio of the obtained copolymer was monomer A: monomer B = 1: 1, and the average molecular weight of the copolymer was about 5,000.

The copolymer obtained above was dissolved in methyl ethyl ketone to prepare a 20 wt% solution adhesive. This adhesive was designated as "Adhesive D".

Using Al / Al and FRP / Al as the base material, these base materials (2
Adhesive D is applied at a rate of 150 g / m ² to 5 mm x 125 mm), and 175
It was pressure-bonded at 3 Kg / cm ² for 15 minutes. The peel adhesion strength was determined according to the peel adhesion strength test method for adhesives (JIS K-6854), and the results are shown in Table 3.

Example 3 Using 0.25 mol of monomer A, 0.25 mol of monomer B, 0.25 mol of n-butyl methacrylate (hereinafter referred to as “monomer C”) and 0.01 mol of AIBN, polymerization was carried out in 200 g of methanol at a reaction temperature of 68 ° C. for 5 hours. The reaction was carried out. After the reaction was completed, a terpolymer produced in a hexane solvent was precipitated and dried. The monomer composition ratio of the obtained terpolymer was monomer A: monomer B: monomer C = 1: 1: 1, and the average molecular weight of the copolymer was about 40,000.

The terpolymer obtained above was dissolved in methyl ethyl ketone to prepare a 20 wt% solution adhesive. This adhesive was designated as "Adhesive E".

Using Al / Al, steel / steel and FRP / Al as the base material, apply adhesive E to these base materials (25 mm x 12.5 mm) at a rate of 150 g / m ² , and then apply 175 ° C, 3 Kg / cm ² And crimped for 15 minutes. The tensile shear adhesive strength was determined according to the tensile shear adhesive strength test method for adhesives (JIS K-6850), and the results are shown in Table 4.

Using Al / Al and FRP / Al as the base material, these base materials (2
Adhesive E is applied at a rate of 150 g / m ² to 5 mm x 125 mm), and 175
It was pressure-bonded at 3 Kg / cm ² for 15 minutes. The peel adhesive strength was determined according to the peel adhesive strength test method for adhesives (JIS K-6854), and the results are shown in Table 5.

Example 4 2-Vinylpyridine (hereinafter referred to as "monomer D") 0.4
A polymerization reaction was carried out in 200 g of methanol at a reaction temperature of 68 ° C. for 5 hours using 100 mol of the monomer, 0.4 mol of the monomer B and 0.005 mol of AIBN. After completion of the reaction, the produced copolymer was precipitated in a hexane solvent and dried. The monomer composition ratio of the obtained copolymer was Monomer D: Monomer B = 1: 1, and the average molecular weight of the copolymer was about 80,000.

The copolymer obtained above was dissolved in methyl ethyl ketone to prepare a 20 wt% solution adhesive. This adhesive was designated as "adhesive F".

Using Al / Al and steel / steel as the base material, apply adhesive F to these base materials (25 mm x 12.5 mm) at a rate of 150 g / m ² , and press-bond at 175 ° C, 3 Kg / cm ² for 15 minutes. did. The tensile shear adhesive strength was determined according to the tensile shear adhesive strength test method for adhesives (JIS K-6850), and the results are shown in Table 6.

 ─────────────────────────────────────────────────── --Continued from the front page Judgment panel for referee Judge Yasuda Wada Judge Norio Kakizawa Judge Shigeki Takagi (56) Reference JP 56-11915 (JP, A) JP 54-126027 (JP, JP, A) JP-B-46-9837 (JP, B1) JP-B-59-14505 (JP, B2)

Claims (5)

[Claims] 1. A general formula (1) [In the formula, R ₁ represents a hydrogen atom or an alkyl group. ] And vinyl pyridines represented by the general formula (2) [In the formula, R ₂ represents a hydrogen atom or a methyl group, and R ₃ represents an alkyl group. ] A vinyl pyridine type adhesive characterized by containing a copolymer with an acrylate compound represented by the following. 2. The composition of the copolymer is 10 to 90 vinyl pyridines.
The adhesive according to claim 1, which comprises mol% and 90 to 10 mol% of an acrylate compound. 3. The vinylpyridines are 2-vinylpyridine,
4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine and 5-ethyl-
The adhesive according to claim 1, which is at least one selected from the group consisting of 2-vinylpyridine. 4. The acrylate compound is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, propyl acrylate, propyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate. The adhesive according to claim 1, which is at least one selected from the group consisting of lauryl methacrylate, stearyl acrylate, and stearyl methacrylate. 5. The adhesive according to claim 1, wherein the average molecular weight of the copolymer is 500 to 500,000.