JPS59221367A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide a composition for the bonding of rubber in water, etc., having excellent adhesivity and flexibility, and obtained by adding specific amounts of a hardly water-soluble amine and amide to an epoxy resin containing >=50wt% of an epoxy resin prepared by the reaction of a specific long-chain dibasic acid with an epoxy resin. CONSTITUTION:The objective composition is composed of (A) 100pts.wt. of epoxy resin composition containing >=50wt% of an epoxy resin obtained by reacting a long-chain dibasic acid of formula (R is alkyl or alkenyl wherein the C number of the straight chain is 2-8) with an epoxy resin having two or more epoxy groups in the molecule and (B) 4-430pts.wt. of a hardly water-soluble amine and/or amide (e.g. m-phenylenediamine, a polyamide derived from the dimer of linoleic acid and ethylenediamine, etc.). USE:It exhibits especially excellent adhesivity to chloroprene rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition, and more particularly to an adhesive composition that is used for adhesion to rubber in water or on wet surfaces, and particularly has excellent adhesive properties and flexibility.

Conventionally, epoxy resins have been widely used in various fields such as various paints and adhesives because of their excellent chemical resistance, adhesive properties, and electrical properties. However, adhesives that cure in water or on wet surfaces and have sufficient adhesive strength have only been used for bonding concrete in civil engineering fields, such as adhesives made of polybutadiene epoxy resin and polyamide amine. , Epoxy resin has high hardness (poor adhesive properties and lacks flexibility,
There has been no material that can be used practically in underwater or wet surfaces, especially as a repair material for marine rubber products such as fenders, marine hoses, rubber bags for oil recovery, and rubber water storage tanks.

In view of these problems, the present invention aims to improve the adhesion and flexibility of adhesion to rubber underwater or on wet surfaces. It is used as a repair material for repair work.

The present inventors have conducted extensive research in order to achieve the above objective, and as a result, the epoxy resin (8) containing the epoxy resin (A') obtained by reacting a long chain dibasic acid with an epoxy resin,
It has been discovered that an adhesive composition containing a specific amount of poorly water-soluble amine and/or amide (C) improves adhesion and flexibility when adhering rubber in water or on wet surfaces.The present invention reached.

In other words, the present invention has the following general formula: HOOC-(CH'2'> 5-R-(CI-12)
5-〇〇0I-1 (However, R is an alkyl group or alkenyl group having 2 to 8 carbon atoms in the straight chain portion) and has a long chain dibasic acid and at least two epoxy groups in the molecule. Epoxy resin (B) containing at least 50% by weight of epoxy resin (A) obtained by reacting with epoxy resin
The adhesive composition is characterized by containing 4 to 430 Φω parts of a poorly water-soluble amine and/or tsunomide (C).

The long-chain dibasic acids used in a3 in the present invention have the general formula, 1100C-(Ct12) 5-R-(CH
2) 5 -COO1-1 (wherein R is an alkyl group or an alkenyl group having 2 to 8 carbon atoms in the straight chain portion);
Specifically, as a saturated linear dibasic acid, for example, R is -(CH2)4-1-(Ct-L)a-1 As a saturated branched dibasic acid, for example, R is =CH-CH2-Ct-12 -C13, CH(CH2)a-CH2-C1j3 As an unsaturated linear dibasic acid, for example, R is -C1''2-Ctoj=CI''-CI-
12-1, CH2Cto1=, CH(CH2) 2-C
H=CH-CH2-1 =CH2C=CH(CH2)2 CH31 CHa CH=,, CC)-L -1 Unsaturated branched dibasic acid -C1 For example, R is =CH(CH2)
2 Ct(= CH2CH= CHCH2-1CH, CH2
-CH=CH2, etc. can be mentioned. These dibasic acids may be used alone or in combination of two or more.

In the present invention, the epoxy resins to be reacted with two t'A groups include those having at least two epoxy groups in the molecule, such as bisphenol fragments (epoxy resins and their hydrogenated products, cycloaliphatic epoxy resins, Examples include general-purpose epoxy resins such as phenol or cresol novolac type epoxy resin, -notalic acid glycidyl ester type, poxy resin, dimer acid type epoxy resin, and polyglycol type epoxy resin.
: Only one type of poxy resin may be used alone, or two types of poxy resin may be used alone.
You may use more than one species together. An epoxy resin having at least two epoxy groups (A'
) and the chemical formulas of compounds which are examples of epoxy resin (A) (epoxy resins (A)-1 to 6) are shown in Table 2 below.

In the present invention, an epoxy resin (△) having at least 21 [1i1 epoxy groups in the molecule obtained by reacting the long-chain dibasic acid with an epoxy resin] is used as an epoxy resin in the adhesive silk composition. It is contained in an amount of at least 50% by weight of the resin (B) component. This epoxy resin (B) component is
Epoxy resin (A> may be used alone or in combination of two or more types, and epoxy resin (A) may be used in combination with general-purpose epoxy resins such as those listed above. In any case, C and epoxy resin (A) are , 5 in the epoxy resin (B) component
0% by weight or less” - Must contain epoxy resin (
If the content m of A) is less than 50% by weight, high adhesion and flexibility in water or on wet surfaces cannot be obtained.

The adhesive composition of the present invention is obtained by blending a specific amount of poorly water-soluble amine and/or amide (C) into the epoxy resin (B). The blending amount of poorly water-soluble amine and/or amide (C) is epoxy resin (B) 1
It is mixed at a ratio of 4 to 430 parts by weight per 0.00 parts by weight. If the amount is less than 4 parts by weight, curing will be insufficient, and if more than 430 parts by weight is added, unreacted curing agent will remain, and in both cases the cohesive force of the adhesive will be low.
As a result, the adhesive strength is low and the water resistance is also reduced, which is not preferable.

In the present invention, water soluble amine and/or amide (
C) refers to the use of one or more curing agents for epoxy resins, such as aromatic amines, polyalkylene polyamines, polyamides, amide polyamines, and NBR-modified amines that are poorly soluble in water and have the ability to replace water molecules. . in particular,
m-phenylenediamine, 4,4' as aromatic amine
- Methylene dianiline, etc., polyamides made from lyluic acid 2-diamine and diethylene triamine as polyamides, polyamides made from lyluic acid m-form and diethylenetriamine, etc., amide polyamines made from tall oil and triethylenetetramine as amide polyamines. , amide polyamines from ricinoleic acid, triethylenetetramine, etc.
Dibutylaminoprobylamine, bis(hexamethylene)triamine, etc. as polyalkyl polyamines, NBR
Examples of modified amines include reactants with carboxylperazine.

In the present invention, a conventional 'FWI curing agent can be used in combination with the water-soluble amine and/or amide (C). These room temperature curing agents include aliphatic polyamines, amine adducts, tertiary amines,
Examples include modified polymercaptan. For example, aliphatic polyamines such as i-lyethylenetetramine, dimethylamitube [1-pyramine, etc.], amine adducts such as diethylenetriamine and bisphenol A epoxy resin adducts, triethylenetetramine and ethylene oxide adducts, etc., and tertiary amines such as 2,
4,6,-tris(dimethylaminomethyl)phenol, benzyldimethylamine, etc., trimercaptomethyltrioxane as a modified polymercaptan, rubber as an adherend of the adhesive composition in the present invention,
Natural rubber, butadiene rubber, styrene-butadiene rubber
Examples include ethylene propylene rubber, ethylene propylene rubber, nitrile butadiene rubber, epichlorohydrin rubber, acrylic rubber, and chlorinated polyethylene, among which chlorobrane rubber shows good adhesion.

In the adhesive composition of the present invention, an extender, a reinforcing agent, a filler, a face r1, and the like may be mixed in appropriate amounts as necessary. These include, for example] - Lutal, glass illt, asbeth 1~mif, carbon fiber, cellulose, polyethylene powder, quartz powder, mica, activated alumina, phosphorus, bentone, silica titanium dioxide, carbon black, Examples include iron oxide and aluminum powder, all of which can be used effectively depending on the purpose.

Furthermore, the adhesive composition of the present invention may contain a silane coupling agent in order to improve its adhesiveness. For example, vinyl 1-lye 1-xysilane, γ-methacrylooxypropyl]-rimethoxysilane, γ-amitub[1-pyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl 1-rimethoxysilane, γ
- Glycidoxypropyl 1 to 1 to 4 rainbow searan,
Examples include γ-mercap] to gD pyrutrimethoxysilane.

Next, the present invention will be explained in detail based on Examples and Comparative Examples. All formulations in Tables 1, J, and 3 are parts by weight.

Examples 1 to 9 and Comparative Examples 1 to 2 The compositions J shown in the main component column of Table 1 were mixed on a paint mill to prepare a main component. Similarly, a curing agent was prepared by mixing on a paint mill according to the formulation specified in the column of curing agent components in Table 1. An adhesive composition was obtained by mixing this base agent and a curing agent. In addition, the general formula of 1 Bogishi resin (A) obtained by reacting a long-chain dibasic acid and an epoxy resin and the epoxy resin (Ah-1 to 6 chemical formulas listed in Table 1 used in the examples) are It is shown in Table 2.

On the other hand, JI obtained by the formulation and vulcanization conditions shown in Table 3
3mm x 25. Vulcanized chloroprene rubber with S hardness 45.
A test piece with a thickness of 4 mm x 150 mm was prepared, and after being puffed with sandpaper (AA-120 manufactured by Riken Corundum) in seawater, the above adhesive composition was applied to a thickness of 3 mm.
Apply with Il, layer a plain weave cloth on top, and apply η for adhesion test.
I made it a sample. This sample for adhesion test was placed in seawater for 20 minutes.
C. for one week and the adhesive strength was measured. Adhesive strength was measured at 20℃ using Shimoka Δ-1~Graph 5500!
A tensile speed of iomm/min was measured.

In addition, in order to measure the hardness of the adhesive composition, the above adhesive composition 11 was placed on a pattern of 3n+m x 50mm x 5
Cast with a dimension of 0+nm and store in seawater at 20°C.
After being cured for 1 week, the hardness was measured using a JIS hardness meter.

The results are shown in Table 1.

*1: Bisphenol type epoxy resin, trade name Sumiepoxy FIA-128P, manufactured by Sumitomo Chemical Co., Ltd., ball boxy equivalent: approximately 185, *2: 1. ．． 6 hexanediol diglycidyl ether, trade name Koborite 1600, Kyoeisha oil and fat products, epoxy equivalent 150, *3: modified amine, trade name Sanmide #P~117, manufactured by Yowa Kagaku Kogyo Co., Ltd.
Active hydrogen amine equivalent ω approximately 97, *4: Polyamide, trade name Sanmide # 310P, manufactured by Sansho Kagaku Kogyo Co., Ltd., active hydrogen amine equivalent ω 110, *5: Modified aromatic polyamine, trade name Sanmide # M 1001, three-phase Chemical industry"11
manufactured by Kadenka Kogyo Co., Ltd., active hydrogen amine equivalent G approximately 95, Nido 6: Modified aliphatic amine, trade name ADEKA HARDNER EH-220, manufactured by Kadenka Kogyo Co., Ltd., active hydrogen amine equivalent G 89, * 7: NBR modified polyamine, trade name Hycar AT B N 1
300X 16, B, manufactured by Gutdridge Chemical Co., Ltd.
Active hydrogen amine Totake approx. 900. ″4:8: tertiary amine,
Trade name: Adekaha-Donor El-IC-30, manufactured by Kadenka Kogyo Co., Ltd. *Exit Silane Coupling Agent, trade name: A189, manufactured by Nippon Konica Co., Ltd. 14-Table 6 *10: Trade name: Denka Chloroprene EM-40, Manufactured by Denki Kagaku Kogyo Co., Ltd., Mooney viscosity (MLH4, 100°C) 4
8 ±5, *11: Ethylene thiourea, trade name Tsukusela 22, Ohmukai Shinko M[i, *12: Aluminum silicate, RIT, manufactured by Vanderbilt.

As shown in Table 1, Examples 1 to 9 using the adhesive composition of the present invention were all adhesively treated in seawater, and had good adhesion to black 1" Blend rubber, and was even more flexible. It can be seen that the properties are also good.

On the other hand, Comparative Example 1 using a general-purpose poxy resin
It was found that No. 2 had low adhesion to Kuro[1 Brene rubber and lacked flexibility.

As explained above, the epoxy resin (B
) and a specific group of slightly water-soluble amine and/or amide (C), the adhesive composition of the present invention uses an amine and/or amide that is H-soluble in water and capable of converting water molecules. Because of this, it cures well in water or on a wet surface.
Furthermore, since it uses an epoxy resin (A) obtained by reacting a long-chain dibasic acid with an epoxy resin that has at least two epoxy groups in the molecule, it is flexible and flexible when adhering to rubber. As a result, it can be used as a repair material for rubber products used in the ocean, as well as as a coating material, lining material, and sealing material used underwater.

Patent applicant: Yokohama Rubber Co., Ltd. Agent: Patent attorney Tatsuo Ito Agent: Patent attorney Tetsuya Ito 18-

Claims (1)

[Scope of Claims] A long chain dibasic acid represented by the general formula % (where R is an alkyl group or alkenyl group having 2 to 8 carbon atoms in the straight chain portion),
Epoxy resin (B) containing at least 50% by weight of epoxy resin<A) obtained by reacting with an epoxy resin having at least two J-boxy groups in the molecule at °C
00 parts by weight and a poorly water-soluble amine and/or amide (
C) An adhesive composition containing 4 to 430 parts by weight.