JPS61231071A - Vinyulpyridine adhesive - Google Patents

Abstract

PURPOSE:To provide the titled adhesive which has an excelelnt effect of bonding rubbers to each other, rubber to metal CONSTITUTION:A vinylpyridine (A) of formula I (hwerein R1 is H, alkyl) such as 2-vinylpyridine or 2-methyl-5-vinylpyridine and.

Description

[Detailed description of the invention] 1 bundle, L plate Rikata 1 The present invention relates to vinylpyridine adhesives.

The vinylpyridine homopolymer represented by the general formula (1) (in which R1 represents a hydrogen atom or an alkyl group) has the drawbacks of having a high glass transition point (Tg>) and being hard and brittle. ,
Therefore, it is difficult to use this polymer alone as an active ingredient in adhesives.

Therefore, vinylpyridines of the above general formula (1) have been used for adhesives to date as a copolymer with butadiene or as a terpolymer with butadiene and styrene (Japanese Patent Publication No. 36-20584). Official Gazette, Special Publication 1977
(Refer to Publication No.-5195). However, all of these adhesives are mainly used for bonding rubber to rubber or bonding rubber to metal.

The present inventors have developed not only rubber-to-rubber adhesion and rubber-to-metal adhesion, but also metal-to-metal adhesion, metal-to-composite adhesion, and composite-to-composite bonding. As a result of intensive research to develop an adhesive that is also effective for adhesion to bodies, we have discovered that the copolymers shown below can achieve the intended purpose of the present invention, and we have hereby completed the present invention. reached.

That is, the present invention is directed to the general formula (1) [wherein R1 represents a hydrogen atom or an alkyl group]. ] and an acrylate compound represented by the general formula (2) (wherein R2 represents a hydrogen atom or a methyl group, and R3 represents an alkyl group). This relates to vinylpyridine-based adhesives.

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

In the above general formula (1), examples of the alkyl group represented by R1 include an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Further, in the general formula (2), examples of the alkyl group represented by R3 include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms.

As the vinylpyridine of general formula (1), a wide variety of conventionally known vinylpyridines can be used, such as 2-vinylpyridine, 4-vinylpyridine,
Vinylpyridine, 2-methyl-5-vinylpyridine, 2
-Methyl-6-vinylpyridine, 5-ethyl-2-vinylpyridine, and the like. In the present invention, these can be used alone or in combination of two or more.

Furthermore, as the acrylate compound of general formula (2), a wide variety of conventionally known compounds can be used, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2- Examples include ethylhexyl methacrylate, propyl acrylate, propyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, and stearyl methacrylate. In the present invention, these can be used alone or in combination of two or more.

The copolymer used in the present invention has the above general formula (1
) and the acrylate compound of general formula (2) are copolymerized. The copolymer can be easily produced by conventionally known polymerization methods, such as radical polymerization and ionic polymerization. Preferred embodiments for producing the copolymer include, for example, the general formula (
A predetermined amount of the vinyl pyridine of 1) and the acrylate compound of the general formula (2) are blended, and azohisisobutyronitrile (
Solution polymerization and suspension in the presence of polymerization initiators such as azobiscyano compounds such as AIBN>, peroxides such as benzoyl peroxide, organometallic compounds such as alkyl lithium and ethyl aluminum dichloride, and inorganic halogen compounds such as boron fluoride. What is necessary is just to carry out polymerization, emulsion polymerization, or bulk polymerization. Examples of the solvent used in solution polymerization include methanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and the like. These polymerization reactions are usually carried out at -80 to 120°C.
The reaction time is generally 0.5 to 10 hours. The copolymer of the present invention thus obtained has a composition consisting of 10 to 90 mol% of vinylpyridines and 90 to 10 mol% of acrylate compounds, preferably 30 to 70 mol% of vinylpyridines and acrylate compounds. It consists of 70 to 30 mol%. If the composition of the copolymer deviates from the above range, the desired effects of the present invention may not be exhibited. Further, the average molecular weight of the copolymer is usually about 500 to 500,000, preferably 1,000 to 100.
Within the range of 000.

The adhesive of the present invention may contain additives that are normally added to adhesives of this type, such as solvents (e.g., ketones such as methyl ethyl ketone, esters such as ethyl acetate, alcohols such as methanol, aromatic carbon dioxide such as toluene, etc.). Hydrogens, etc.), antioxidants, elastomers, plasticizers, pigments, fillers, etc. can be blended as appropriate.

When using the adhesive of the present invention, the adhesive of the present invention is applied to the base material to be bonded, such as rubber, metals such as aluminum, iron, composites such as fiber reinforced plastics (FRP and FRTP), etc., and dried. The above-mentioned base materials may be bonded together by post-heating and pressing. The amount of the adhesive of the present invention to be applied to the above-mentioned substrate varies depending on the type of substrate to be applied, etc., and cannot be determined unconditionally, but it may be applied generally at a rate of 100 to 500 q/m<2>. As the coating method, any conventionally known method can be employed, such as a dipping method, a spacing method, a roll coating method, a spraying method, and the like. Further, as a drying method, for example, normal temperature drying, heating drying, etc. can be adopted. The heating and pressing IJA processing conditions after drying are, for example, 100-250°C, 0.1-10
It is preferable to set it to about kg/Cm2.

The adhesive of the present invention can be applied not only to rubber-to-rubber adhesion and rubber-to-metal adhesion, but also to metal-to-metal adhesion, metal-to-composite adhesion, and composite-to-composite adhesion. It is also extremely suitable for bonding.

Jou-凰-1 Example 1 4-vinylpyridine (hereinafter referred to as "
Monomer A"), 2-ethylhexyl methacrylate (hereinafter referred to as "Nanatsumer B"), and AIBN O
,005 mol, and a polymerization reaction was carried out in 200Q methanol at a reaction temperature of 68° C. for 5 hours. After the reaction was completed, the copolymer produced was precipitated in a hexane solvent and dried.

Table 1 Formulation 1 (mol) 0.6 0.2 Formulation 2 (mol) 0.4 0.4 Mo3 Mol 0.2 0.6 The monomer composition ratio of the copolymer obtained according to the formulation of Formulation 1 is Monomer A: monomer 8-3:1, 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 Formulation 2 was Monomer A: Monomer B = 1:1, and the average molecular weight of the copolymer was about 60,000. The seven-mer composition ratio of the copolymer obtained according to the formulation of Formulation 3 was Monomer A: Monomer 8-1:3, and the average molecular weight of the copolymer was about 7.
It was 0000.

Each of the copolymers obtained above was dissolved in methyl ethyl ketone to prepare a 20% by weight solution of an adhesive. Formulation 1
An adhesive containing a copolymer obtained according to the formulation of
"Adhesive A", the adhesive containing the copolymer obtained according to the formulation of Formulation 2 was referred to as "Adhesive B", and the adhesive containing the copolymer obtained according to the formulation of Formulation 3 was referred to as "Adhesive C”.

AQ/AQSMA material/steel material, FRP/AQ and FRP/FRP are used as the base material, and these base materials (25mm x
12.5mm> of adhesive A, adhesive B, or adhesive C.
Coated at a rate of 50g/m2, 175℃, 3KQ/Cm
2 for 15 minutes.

Tensile shear adhesive strength test method for adhesives (JISK-6
The tensile shear adhesive strength was determined according to 850) and the results are shown in Table 2'.

Table 2 Tensile shear adhesive strength AQ/AQ 35.2 92.0 55
．． 1 steel material/steel material 136.0 FRP//l 60.0FRP/FRP
75.0 Example 2 0.4 mol of monomer A, 80.4 mol of heptamer and AI
A polymerization reaction was carried out in methanol 400Q using 05 mol of BNO at a reaction temperature of 68° C. for 5 hours. After the reaction is completed, the copolymer produced is precipitated in a hexane solvent,
Dry. 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% by weight solution of an adhesive. This adhesive was designated as "Adhesive D".

AQ/AQ and F RP/A Q were used as base materials, and adhesive was applied to these base materials (25 mm x 125 mm> at a rate of 150 g/m2, 175°C, 3KC)/
It was crimped with Cm2 for 15 minutes. The peel adhesion strength was determined according to the adhesive peel adhesion strength test method (JIS K-6854>), and the results are shown in Table 3.

Base material T-type peel strength 180 degree peel strength (of
/25mm) (Kc+f/25mm)AQ/AQ
8.8 10.9FRP/A9
3.2 Example 3 Monomer A 0.25 mol, monomer 80.25 mol, n
-Butyl methacrylate (hereinafter referred to as "monomer Cl")
Using 0.25 mol and AIBNo. 01 mol, a polymerization reaction was carried out in 20OC1 of methanol at a reaction temperature of 68° C. for 5 hours.

After the reaction was completed, the resulting terpolymer was precipitated in a hexane solvent 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% by weight solution of an adhesive.

This adhesive was designated as "Adhesive E".

AQ/AQ, m material/steel material, and FRP/AQ were used as base materials. Adhesive E was applied to these base materials (25 mm x 12.5 mm) at a rate of 150 g/m2, and the mixture was heated at 175°C for 3
KC]/Cm2 for 15 minutes. The tensile shear adhesive strength was determined according to the adhesive tensile shear joint strength test method (J Is K-6850), and the results are shown in Table 4.

Base material Tensile shear surface adhesion strength (K f/Cm2 AQ/A9 46.6 Steel material/Steel material 111.7 FRP/A9 63.6 AQ/AQ and FRP/AQ are used as the base material, and these base materials (25 mm x 125 mm ) to 150% adhesive E.
It was coated at a rate of g/m2 and pressed at 175°C and 3Kg/cm2 for 15 minutes. Peel adhesion strength testing method for adhesives (J
Determine the peel adhesion strength according to IS K-6854>,
The results are shown in Table 5.

Table 5 Base material T-type peel strength 180 degree peel strength (gf
/25mm) (at f/25mm)AQ/AQ
10.6 13.0FRP/AQ
9.2 Example 4 2-vinylpyridine (hereinafter referred to as "monomer D") 0.
4 moles, 80.4 moles of monomer and AIBN O,0
A polymerization reaction was carried out in methanol 20OCJ at a reaction temperature of 68° C. for 5 hours using 0.05 mol. After the reaction was completed, the copolymer produced was precipitated in a hexane solvent and dried. The monomer composition ratio of the obtained copolymer was Monomer D: Monomer 8=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% by weight solution of an adhesive. This adhesive was designated as "Adhesive F".

AQ/AQ and steel/steel materials were used as base materials, and 150% of adhesive F was applied to these base materials (25 mm x 12.5 mm).
It was coated at a rate of g/m2 and pressed at 175°C and 3Kg/cm2 for 15 minutes. The tensile shear adhesive strength was determined according to the adhesive tensile shear joint strength test method (JIS K-6850>), and the results are shown in Table 6.

Table 6 Base material Tensile shear adhesive strength (Kqf/cm2) AQ/A9 35.0 Steel/Material 52. O (that's all)

Claims (5)

[Claims] (1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, R_1 represents a hydrogen atom or an alkyl group. ] Vinylpyridines represented by the general formula (2) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (2) [In the formula, R_2 represents a hydrogen atom or a methyl group, and R_3 represents an alkyl group. ] A vinylpyridine adhesive characterized by containing a copolymer with an acrylate compound represented by the following. (2) The adhesive according to claim 1, wherein the composition of the copolymer is 10 to 90 mol% of a vinylpyridine and 90 to 10 mol% of an acrylate compound. (3) Vinylpyridines include 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-vinylpyridine,
The adhesive according to claim 1, which is at least one selected from the group consisting of methyl-6-vinylpyridine and 5-ethyl-2-vinylpyridine. (4) Acrylate compounds include 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, lauryl The adhesive according to claim 1, which is at least one selected from the group consisting of methacrylate, stearyl acrylate, and stearyl methacrylate. (5) The adhesive according to claim 1, wherein the copolymer has an average molecular weight of 500 to 500,000.