JPS6099184A - Composition for bonding and method for bonding using the same - Google Patents

Abstract

PURPOSE:To provide a composition composed of an aqueous solution of a resorcinol.formaldehyde resin, a vulcanization controller for rubber and a sulfochlorinated polyolefin, and suitable for the firm bonding of a fiber material with rubber. CONSTITUTION:The objective composition is composed of (A) an aqueous solution of a resorcinol-formaldehyde resin, (B) a vulcanization controller for rubber (preferably tetramethylthiuram disulfide, mercaptobenzothiazole, nickel dibutyldithiocarbamate, etc.) and (C) a sulfochlorinated polyolefin (preferably sulfochlorinated polyethylene, etc.). The amount of the component B is preferably 0.3-30pts.wt. per 100pts.wt. of the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition for bonding textile materials and rubber, and a bonding method using the same.

Rubber is often used in tires, belts, hoses, waterproof sheets, etc. by bonding reinforcing fibers and rubber. Conventionally, resorcin formaldehyde resin aqueous liquid (hereinafter referred to as 1<RF liquid) and NR Radenotas have been used to bond natural rubber (hereinafter abbreviated as NR) and styrene-citadiene copolymer rubber (hereinafter abbreviated as SBR) to fibers. , SDR latex or styrene, getadiene,
Compositions with vinylpyridine terpolymer rubber latex and the like are used as so-called RFL adhesives. However, terpolymer rubber (hereinafter referred to as E
PDM (abbreviated as PDM) is far superior to highly unsaturated rubbers such as NR and SBR, which are conventionally used mainly in tires and belts, in terms of weather resistance, ozone reduction properties, heat resistance, etc. However, its use is limited because it has poor adhesion to fibers and sufficient adhesive strength cannot be obtained even when using the above-mentioned RF L adhesive. In addition, inbutylene isoprene copolymer rubber (butyl rubber hereinafter abbreviated as IIR)
etc. have similar circumstances.

Therefore, the present inventors have conducted extensive studies on bonding methods for EPDM etc. and fibers, and found that by using an organic solvent solution or aqueous dispersion of RF liquid and sulfohalogenated polymer (hereinafter abbreviated as SHP) together. After discovering that it had an excellent adhesive effect, the company applied for a patent. (Japanese Patent Application No. 55-180822) Furthermore, this adhesion method, especially SH
Continuing studies on bonding methods using P water dispersions and using polyvinyl alcohol in combination will significantly improve adhesive strength. (Patent No. 11556-62847) RF
A patent application was also filed for a method of adding zinc compounds and magnesium compounds to L. (Special application Sho 58-2024
6') As a result of further studies on a good composition for firmly adhering textile materials and rubber, the present inventors found that
We discovered that a composition made by adding sulfochlorinated polyolefin (hereinafter referred to as SCP) and a specific rubber vulcanization modifier to an RF liquid exhibits strong adhesive strength even during baking treatment at relatively high temperatures, leading to the present invention. did.

An adhesive composition for adhering rubber to a textile material made of Refine and Shibachi Fukai Kyouishi, and a textile material obtained by impregnating the textile material with this composition. This is an adhesion method that involves contact vulcanization with rubber.

The RF liquid as used in the present invention consists of 1 liquid and SCP latex. The RF liquid contains formaldehyde, a substance that easily generates formaldehyde such as formaldehyde, and a phenolic compound such as dihydroxybenzenes such as resorcinol by an appropriate known method, for example, in the presence of an alkali metal hydroxide. It is an aqueous liquid that has been reacted with 0.0% formaldehyde per mole of phenolic compound.
The resin concentration is generally 5 to 4 molar.
It has been adjusted to 0% focus. - SCP latex is an aqueous dispersion that generally contains about 5 to 70% by weight of a sulfochlorinated polymer.

An example of a sulfochlorinated polymer is ethylene.

Homopolymers such as propylene, n-butylene, inzotylene, polyester, and isoprene; non-conjugated dienes such as ethylidenenorbornene and dicyclopentadiene; or styrene, vinyl chloride, vinyl acetate, acrylic acid, and methacrylic acid. It is a polymer with a structure thought to be produced by treating a copolymer with ester etc. with chlorine and sulfur dioxide or sulfuryl chloride. Chlorine content in the polymer is 5-70% by weight
, the sulfur content is often between 0.1 and 10% by weight.

The RFL liquid is adjusted so that the sulfochlorinated polymer is 10 to 5000% by weight per solid content in the RF liquid. Viscosity modifier if necessary.

Antioxidants and the like may also be added.

The present invention provides a composition that can improve the adhesive strength between textile materials and rubbers using the above-mentioned RFL liquid, and its feature is that the addition of a rubber vulcanization modifier is effective. This is because we have discovered a formulation that exhibits poor adhesion even when subjected to high-temperature processing, which compensates for the drawback of reduced adhesion when the load is conventionally subjected to high-temperature and baking treatments. Vulcanization modifiers for rubber are broadly classified into chiclams and guanidines.

They can be classified into thiazoles, dithioates, and other chickens, but as a result of various studies on their addition and effects, we found that tetramethylthiclam disulfide (T
T), dipentamethylene tixin hexasulphy, de(
TRA), thiazoles such as mercaptobenzothiazole (M) and dibenzothiazyl disulfide (DM), and dithioic acid salts such as ninocrudiptyldithiocarpamate (
The present invention was completed based on the knowledge that N I3 C) can give good results in improving adhesive strength.

The vulcanization modifier is prepared by mixing in water or an alkaline aqueous solution, if necessary in the presence of a surfactant, in a ball mill overnight. The prepared aqueous dispersion is R
It is preferable to add it to the FL liquid. Of course, when the RFL liquid is forcibly stirred, the powdered vulcanization modifier can be added directly to the RFL liquid.
It can also be added to the liquid. These vulcanization modifiers are SC
0.1 to 50 parts by weight, more preferably 0.1 to 50 parts by weight, per 100 parts by weight of sulfochlorinated polymer in PC Terratex.
3 to 30 parts by weight is used. In addition, these vulcanization modifiers are
Although it can be added to an RF liquid or an aqueous dispersion of a sulfochlorinated polymer, it is most commonly added directly to an RFL liquid. Further, the combined use of zinc compounds and magnesium compounds has the effect of further improving adhesive strength. The zinc compound, magnesium compound, and aqueous dispersion can be prepared in the same manner as the vulcanization modifier, and the amount added is 0.1 to 50 parts by weight per 100 parts by weight of the sulfochlorinated polymer.
More preferably, 0.3 to 0 parts by weight are used. The method of addition is the same as that of the vulcanization regulating agent described above. .

The yJc-dispersion of SCP is prepared by a method such as sulfochlorination of an aqueous dispersion of a raw material polymer or a method of 5IIP hydrolysis, and the latter method is usually adopted. That is, it is better to mix the SC'P solution with water containing an appropriate emulsifier and stir it at high speed, to make a complete dispersion consisting of the SCP solution phase and the aqueous phase, and then under pressure.

Remove some or all of the solvent from the liquid phase by vaporizing and distilling it by heating at an appropriate pressure under normal pressure or reduced pressure, and if necessary, vaporizing and distilling some of the water, By using methods such as using centrifugal force to remove water,
7i: Adjust the 70 weight stone to an appropriate density of about 1 stone. Note that the SHP solvent in this case is benzene, toluene, and xylene.

Aromatic hydrocarbons such as ethylbenzene, carbon tetrachloride,
Solutions of halogenated hydrocarbons such as ethylene tetrachloride, ethane tetrachloride, and fluorinated chlorinated hydrocarbons are often used. In SCP aqueous dispersions, emulsifiers are usually used as fractional stabilizing aids, as shown in the above production method. As the emulsifier, fatty acid Eltl rosin acid stone M@, alkyl ether sulfonic acid ra, alkyl sulfonic acid salts,
Alkyl sulfates, alkenesulfonates, alkyl ether sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ethers,
Polyoxyethylene alkyl esters, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl allyl esters, fatty acid sucrose esters,
Various anionic surfactants, nonionic surfactants such as naphthalene sulfonic acid soda formalin condensate, tetraalkylammonicum salts, alkylpyridinicum salts, alkylbenzylammonicum salts, polyethylene polyamine tetraacetic acid salts, alkyl betaines, etc. , cationic surfactants, and amphoteric surfactants are used, but among these, anionic surfactants are generally preferred in terms of adhesive strength. ~2Oi amount%', preferably 0.1-10
% by weight used. If it is less than 0.01%, the dispersion stabilizing effect will not be sufficient, and even if it is used in excess of 20%, the effect will be almost the same as in the case of -20%. For this water dispersion, it is also possible to use a small amount of an emulsification aid such as Impropatol, which is soluble in both water and the solvent.

The decorations and textiles to which the present invention is applied include cotton and nylon.

Examples include natural fibers such as vinylon, polyester, and aromatic polyamide, as well as synthetic fibers.

The fibers subjected to the I<F L surface treatment of the present invention are belts.

Ethylene propylene diene copolymer rubber, ethylene propylene copolymer rubber, and inbutylene impurity diene copolymer rubber for applications such as drawing cloth and hoses.

In addition to sulfochlorinated polyethylene rubber, ethylene propylene lentene copolymer rubber, ethylene propylene gedene diene copolymer rubber, ethylene butene copolymer rubber, and ethylene butene diene copolymer rubber, natural rubber, butadiene rubber, and styrene butadiene rubber.

Used after bonding with rubbers such as acrylonitrile butadiene rubber and chloroprene rubber.

The shapes of the fibers vary widely depending on their use, such as cords, canvas, short fibers for reinforcement, and short fibers for flocking.

The method for bonding textile materials and rubber using the adhesive composition of the present invention is usually first by dipping.

The textile material is impregnated with RF liquid using an appropriate method such as coating, spraying, or roll treatment, and then immersed or applied to the textile material that has been treated as it is or has been subjected to drying, heat treatment, etc. as necessary. .

It is impregnated with an SCP dispersion containing a rubber vulcanization modifier using an appropriate method such as spraying or roll treatment, and then processed through processes such as drying and heat treatment to form rubbers such as EPDM containing various additives. Textile materials can be prepared by contact vulcanization, or by dipping, coating, spraying, or rolling a composition in which an aqueous dispersion of SCP and a rubber vulcanization modifier is mixed with an RF liquid. There are methods such as impregnation, drying, heat treatment, etc., and contact vulcanization with rubber such as EPDM containing various additives.As a result, the fiber material and the rubber are strongly bonded. can be done. Among these methods, RF fluid.

The method of treating textile materials using a composition in which the SCP aqueous dispersion and the vulcanization modifier aqueous waste liquid for rubber are mixed in advance is advantageous for the commercial industry, as the process is simplified. The composition used shows an excellent adhesive effect.

Regarding the case where the RF L liquid is used in the method of the present invention, the RF liquid can be immersed, applied, sprayed, etc.
Soak for 3 times using an appropriate method such as roll treatment, and heat from room temperature to 250℃.
Dry at an appropriate temperature such as ℃ 1: Limbs subjected to Kai heat treatment,
Rubber that has been appropriately vulcanized with a vulcanizing agent, Ic accelerator, anti-aging agent, reinforcing agent, etc. is mixed together, or when the rubber is sandwiched between the vulcanizing agent and the vulcanizing agent, the pressure of 1130~
160℃, &! The bond is completed by finishing the rubber, such as by vulcanizing it under normal vulcanization conditions, such as from 1 minute to 2 hours.

In the method and composition of the present invention, NR latex, SB
It is of course possible to use latices such as R latex or styrene butadiene vinyl pyridine terpolymer latex and conventional RFL adhesives in combination in any desired manner, often with good results.

Examples of the present invention will be shown below, but the present invention is not limited thereto. The reason why ethylene propylene diene copolymer rubber is used as the adherend to fibers is because, as mentioned above, ethylene propylene diene copolymer rubber is considered to be the most difficult to adhere to fibers.

Preparation of 0-sulbochlorinated polyolefin latex For example, polyethylene (density 0.96'I/at/I
) 12 kg of sulfochlorinated polyethylene (chlorine content: 35%, sulfur content: 1%), which had been produced previously, was dissolved in 68 hours of toluene. On the other hand, add polyoxyethylene (
E-0.4 mole addition), octyl enyl ether sulfate ester sodium salt (manufactured by Nihon Shin-A Co., Ltd., trade name Trax H-45) 1.2 KfI (purity 30%), polyoxyethylene (E,0 .30 mole addition), nonylphenyl ether sulfate ester salt (manufactured by NOF ■, product name Toranox N-300) 690 mol (purity 35%) and caustic potassium 84 y' were dissolved, and two solutions were prepared. The mixture was sufficiently emulsified with Emulsifier A (T, K, Homo Mixer, manufactured by Tokuhama Kaiichi Hiegyo Co., Ltd.). Thus obtained lζ emulsion r2U
Transfer to an OJ stainless steel container and boil for 150~'l O
The mixture was heated by circulating hot water at 70° C. under reduced pressure through the jacket of 11 g of Om, and toluene and the like were distilled off. After cooling, a product of 30 KfI was obtained. # Solid content of J product is 40%
Met.

In addition, sulfochlorinated polyzolopylene (chlorine content 26%) manufactured from polypropylene (density 0.901/7)
, sulfur content 1%), sulfochlorinated EPDM (chlorine content 23%,
sulfur content 1%), ethylene propylene rubber (density 0.8
7! ? /7) sulfochlorinated ethylene propylene rubber (chlorine-containing S, <28%).

The preparation of a latex of a sulfochlorinated polymer with a sulfur content of 1%) can be carried out in the same manner as described above.

Preparation of vulcanization modifier for 0 rubber Vulcanization accelerator 100 “Anionic surfactant (Note 1) 3 Ammonia casein 3 Pure water 144 0Adjustment of vulcanizing agent (Le!J adjustment of zinc oxide aqueous dispersion) ZnO (Note 2) 100 Anionic surfactant 3 Ammonia case °in 3 Sodium silicate 0.5 Pure water 143.5 (Adjustment due to magnesium oxide water dispersion) MgO (Note 3) 100 Anionic surfactant 3 Ammonia casein 3 Sodium silicate 0.5 Pure water 560.2 The above composition is solution-mixed using a ball mill.

(Note 1) Anionic surfactant [manufactured by Kao Atlas Co., Ltd.
Product Name: Demol N] (Note 2) ZnO [Seido Kagaku 14'A3'M, Product Name:
AZO:] (Note 3) MgO [manufactured by Kyowa Kagaku Kogyo 3, product name: Kyowa Mag 150] 01<F liquid preparation Add resorcinol 11y and 37% Polmarine aqueous solution to a solution of 0.47 ml of caustic soda dissolved in 242 ml of water. 16.2F and left to mature at room temperature for 5 hours.

Adjustment of 0RFL liquid CSM latte:yri7.27.5F' and RFg2op
, a vulcanization modifier for rubber, zinc oxide, and an aqueous dispersion of magnesium oxide were mixed together, and the mixture was left to mature at room temperature for 2 hours. RF
The ratio of solid content in the liquid/5CPE in C8M Radenox is 11
It is 5.

0 Mixture of adhered rubber * EPDM E502 70 parts * EPDM E 512F 30 parts Zinc white 5 parts Stearic acid 1 part MAF carbon 110 parts Diana Process NM280 70 parts N-cyclohexyl-2-benzothiazyl-sulfenamide 1.5
Part tetramethylthiclam disulfide 0.5 part Dipentamethylene lenticlam tetrasulfide 0.7 part Digtyldithiocarbamic acid! IF lead 1.5 parts Ij
f Yellow 1 part Prepare the above composition using a remixer or the like 4 times a month.

Kisumitomo Chemical Co., Ltd. Nisprene (Ethylene Propylene Ethylene Norbornene Sangenkyo City Co., Ltd.) 0 Measurement of Adhesion Strength After immersing a 1260 denier nylon cord in the above RFL solution, dry it in a constant temperature dryer at 220 ''C. After drying and baking for 3 minutes, the treated cord thus prepared was embedded in the above unvulcanized adhered rubber compound.
An H-test specimen was prepared by vulcanization at 50'C for 30 minutes, and the adhesive strength was measured using the "H-pull trial run" described in Indian Rubber World, Vol. 114, No. 213-217@ (1946).

Note: PE polyethylene, PP polypropylene.

Applicant: Hiroshi Sasaki, Representative of Steel Chemical Industry Co., Ltd. (Sponsored to write the amendment) Commissioner of the Patent Office, Kazuo Wakasugi1, Indication of the case, Patent Application No. 208048 of 1982, Title of the invention: Adhesive composition and its use (also Adhesion method 3, relationship with the case of the person making the amendment Patent applicant name Title Steel Chemical Industry Co., Ltd. 5 Contents of the amendment (1) Specification tube page 7 line 13 rRF liquid and” changed to “RFL
Correct with "liquid and".

(2) Lines 3 and 13 of page 11 of the specification rsHPj is r
Correct with SCPJ.

(3) "rRF liquid" on page 15 of the specification cylinder, line 12 "rRF liquid"
and correct it.

(4) Insert the following sentence after "ta." on page 17, line 16 of the specification. "(hereinafter abbreviated as 5CPE latex)" (5) rcsMJ on page 20, lines 3 and 6 of the specification is "5CPE latex".
CPE”.

that's all

Claims (1)

[Claims] (1) Resorcinol/formaldehyde resin aqueous liquid and -f
A one-wear composition for bonding a textile material and rubber, which comprises a vulcanization modifier for rubber and a sulfochlorinated polyolefin. (2) The composition according to claim (1), wherein 0.3 to 30 parts by weight of a rubber vulcanization modifier is added to 100 parts by weight of the sulfochlorinated polyolefin. Composition. (4) The composition according to claim (3), wherein the one selected from the chiclams is tetramethylthiuram disulfide. (5) Claim (3) in which one species selected from the chiclam family is dipentamethylene lenticlam hexasulfide.
Compositions as described. Composition of. (7) The composition according to claim (6), wherein the one selected from thiazoles is mercaptobenzothiazole. (8) The composition according to claim (6), wherein the one selected from thiazoles is dibenzothiazyl disulfide. (9) The rubber vulcanization modifier is a nick(t) of dithioate salts.
The composition according to claim (1), wherein the sulfochlorinated polyolefin is sulfochlorinated polyethylene. (9) Each of the compositions according to claim (1), wherein the rubber is an ethylene propylene diene copolymer rubber;
or a method for adhering a textile material and rubber, which comprises subjecting the textile material impregnated with a mixture thereof to contact vulcanization treatment. 03) The method according to claim 02), wherein the rubber vulcanization modifier is added in an amount of 3 to 30 parts by weight of So per 100 parts by weight of the sulfochlorinated polyolefin. Method. (5) The method according to claim (14), wherein the one selected from the thiurams is tetramethylthiclam disulfide.The one selected from the thiurams is tetramethylthiclam disulfide. Claims (1)
4) Method described Q7) The method described in patent claim tJζji, wherein the vulcanization modifier for com is at least one selected from thiazoles. (18) The method according to claim (I7), wherein the one selected from thiazoles is mercaptobenzothiazole; (19) The method according to claim (I7), wherein the one selected from thiazoles is dibenzothiazyl disulfide. Method described. (2) Patent claim in which the vulcanization modifier for rubber is nickel dibutyl dithiocarpamate, which is a dithioate salt]1
λn11-2;:ノJゝA1 "The method described by Kuredei. (5) The method according to claim Q2), in which the sulfochlorinated polyolefin is sulfochlorinated polyethylene (2)) The rubber is ethylene The method according to claims (to), which is a propylene diene copolymer rubber.