RU2315796C1 - Composition used as adhesive underlayer for attaching rubber to metal at vulcanization or as adhesive for hot attaching of rubber on base of fluorine-containing rubber and acrylic rubber - Google Patents

Abstract

FIELD: production of adhesive underlayers (adhesive primers) from compositions on base of organo-silosilanes used for attaching of rubber on base of natural, isoprene, butadiene, butadiene-nitrile, butadiene-styrene, chloroprene and butyl rubber.

SUBSTANCE: proposed composition is single-layer adhesive for hot attaching of rubber on base of fluorine-containing and acrylic rubber to metal in the course of vulcanization. This composition may be used for manufacture of rubber-metal articles in automobile industry, mechanical engineering and other industries. Proposed composition contains 3-aminopropyl-triethyl ethoxy-silane, dimethyl ether of triethylene glycol, paraform solution in mono-ethanol amine, ethyl alcohol, glycerin and distilled water.

EFFECT: high strength of attaching rubber mixes to metals at vulcanization; enhanced corrosion resistance, heat resistance and ecological safety; low cost of product.

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Description

The invention relates to the production of adhesive sublayers (adhesive primers) based on organosilanes used for fastening rubbers based on natural, isoprene, butadiene, butadiene-nitrile, butadiene-styrene, chloroprene and butyl rubber. It is also a single-layer adhesive for fastening rubbers based on fluororubber and acrylate rubbers to metal during vulcanization and can be used in the manufacture of rubber-metal products for the automotive, engineering and other industries.

Known universal adhesive undercoat Chemosil 211 manufactured by Henkel, used with various Chemosil adhesives for bonding rubber compounds with reinforcement during vulcanization. It has high technical characteristics, but contains toxic volatile organic solvents.

Known adhesive sublayer (KP) (RU 2266940) for fixing rubber compounds to metal during vulcanization, including chlorinated natural rubber, fillers, stabilizer, phenolic resin, phenol-formaldehyde resin, wetting agent, urotropin and organic solvents. However, it also contains volatile organic solvents.

Both primers contain chlorinated rubbers which, when aged, emit hydrogen chloride, which leads to sub-film corrosion.

The universal water-based primer Chemosil XW 1200 manufactured by Henkel, which in combination with a suitable adhesive, for example Chemosil XW 7600, combines raw rubber compounds with metals during vulcanization, is known. However, it contains (28-32) wt.% Solids and requires regular mixing, application on a surface heated to (40-90) ° C and is expensive.

The prototype of this invention is an adhesive composition (RU 2180675), which can be used as a primer, including: 3-aminopropyltriethoxysilane, a solution of paraform in monoethanolamine, ethyl alcohol and water. The water content is more than 50%. This adhesive is mainly used for attaching fluororubber based rubber compounds to metal fittings and is expensive.

The technical result of the invention is the achievement of high strength fastening of rubber compounds to metal during vulcanization, giving the adhesive underlayer universality, corrosion resistance, heat resistance, environmental cleanliness, cheaper product.

The technical result is achieved by the fact that the adhesive sublayer for attaching rubber compounds to the metal during vulcanization includes 3-aminopropyltriethoxysilane, triethylene glycol dimethacrylic ester, paraform, monoethanolamine, glycerin, ethyl alcohol and water in the following ratio of components, wt.%:

3-aminopropyltriethoxysilane 3,5-5,5 triethylene glycol dimethacrylic ester 2.5-4.5 paraform 0.2-0.4 monoethanolamine 0.2-0.4 glycerol 0.2-0.4 ethanol 3,5-5,5 distilled water rest.

A comparable analysis allows us to conclude that the claimed composition differs from the known content of triethylene glycol dimethacrylate. Thus, the claimed technical solution meets the criterion of "novelty."

The proposed composition does not contain harmful organic solvents and heavy metals, gives high strength fastening rubber to metals. This allows us to conclude that the proposed solution meets the criterion of "inventive step".

An adhesive sublayer is prepared as follows: a solution of paraform in monoethanolamine is prepared with stirring in a three-necked flask with a reflux condenser (solution 1).

Dissolve 3-aminopropyltriethoxysilane (AGM-9), triethylene glycol dimethacrylic ester (TGM-3) and glycerol in ethanol (solution 2).

With stirring, solution 1 is dissolved in water, solution 2 is added and left to mature for 24 hours.

The proposed adhesive sublayer (primer) is a universal adhesive sublayer for Henkel’s Chemosil adhesives, adhesive composition (CC) for fixing rubber to metal during vulcanization, including chlorinated natural rubber, a copolymer of 2,3-dichlorobutadiene-1,3 with chloroprene, aromatic dinitroso compound, fillers, stabilizers and organic solvents (RU 2266943). During the vulcanization process, it fixes rubber mixtures based on natural, isoprene, styrene butadiene, chloroprene and butyl rubber to the metal and is a single-layer adhesive for rubbers based on fluorine rubber and acrylate rubbers.

Table 1 shows examples of compositions of the invention.

Tests of the adhesive sublayer for the strength of the rubber and metal fastening (steel 3) under laboratory conditions on fungi were carried out as follows: one layer of soil was applied to the sampled, degreased and dried for 20 min metal surface and dried at (20 ± 5) ° С within 30 minutes Then glue was applied and dried under the same regime. The surface of the rubber blank was refreshed with gasoline. Samples were vulcanized in accordance with the vulcanization mode of the tested rubber compounds. The bond strength of rubber with metal with a uniform separation was determined according to GOST 209-75, method B. The speed of the movable mechanism of the tensile testing machine is (100 ± 10) mm / min.

Technical characteristics of the obtained compositions are shown in table 2.

Table 1 Name of ingredient The recipe in wt.% one 2 3 four AGM-9 2,5 four 5 5.5 TGM-3 2,5 3 four 4,5 Paraform 0.2 0.25 0.35 0.4 Monoethanolamine 0.2 0.25 0.35 0.4 Distilled glycerin 0.2 0.25 0.35 0.4 Ethanol 3,5 four 5 5 Distilled water rest

table 2 Name of indicator Test results Suggested Examples one 2 3 four Appearance White to Light Yellow Dispersion Viscosity VZ-246 viscometer (nozzle diameter 4 mm) at 20 ° C, s 10.0 10,2 10.3 10,4 Density, g / cm ³ 0,993 0,993 0,994 0,994 The bond strength of rubber with metal with a uniform separation of kgf / cm ² in the system: 1. - the first layer, the proposed sublayer; - the second layer of Chemosil 222, - p / cm IRP 1347-2 at a rate of at least 40 kg / cm ² 61.5 63,2 65,4 62.7 2. - the first layer, the proposed sublayer; - second layer of QC Rubber grade Norm kg / cm ^2, not less than IRP 1347-2 40 69.7 72.7 77.8 73.3 7-57-1003 25 48.6 57.4 71.3 66.8 7-57-3060 thirty 57.2 61,4 67.2 58.6 7-57-1008 25 51.7 57.8 73.1 62.8 7-57-1016 25 50.1 57.0 64.1 57.8 7-57-2012 25 56.4 59,4 61.3 60,4 7-57-545-81 25 50,5 52,2 54,2 52,2

The nature of the gap in all tests on rubber.

7-51-420 bond strength rubber based fluororubber and 7-57-2801 acrylate rubber with the metal underlayer using the present as a single layer of adhesive (50-55) kg / cm ² (45-50) kg / cm ² accordingly, at a rate of 25 kgf / cm ² .

Industrial tests of the adhesive layer in the production of rubber-metal products for the automotive industry have been carried out.

The adhesive sub-layer homogenized by vigorous stirring was applied onto the cleaned and dried surface of the steel reinforcement by immersion. On a strong and non-sticky film formed after drying for 30 minutes at a temperature of (23 ± 5) ° С and thermostating for 20 minutes at a temperature of (170 ± 5) ° С, after cooling, KK glue was applied, which was dried at that same mode. The vulcanization mode of the parts corresponded to the vulcanization mode of the rubber compound used. Technical difficulties in applying the undercoat and glue, as well as during the vulcanization of parts, were not observed. The results of industrial tests using the known and proposed sublayers are shown in table 3.

Table 3 Detail number Rubber grade Destructive load of adhesion of rubber with metal, kgf, not less Value Test results The first layer, known sublayer KP; The second layer of adhesive KK The first layer is the proposed sublayer; The second layer of adhesive KK 2108-1001033-10 7-57-1008 400 > 800> 800> 800 > 800; > 800; > 800 2108-1001020-10 7-57-1008 350 > 800> 800> 800 > 1000; > 1000; > 1000 2101-2202120 7-57-1016 420 566-570-512 640-608-584 594-606-608 618-602-732 550-590-512 653-620-615 2123-2202120 7-57-1016 525 770-708-642 810-850-860 762-634-682 980-968-900 990-990-776 1010-1005-1000 2110-1001242 7-57-1022 400 820-750-700 900-800-850 2123-100175 7-57-2014 1000 3575; 2350, 3750 4000; 3,500; 3800 2110-1005058 7-57-9024 4000 5700; 5150 5800; 6000 2108-2904064 7-51-3060 350 > 800; > 800; > 800 > 800; > 800; > 800 2121-1001020 7-57-1003 650 > 800> 800> 800 > 1000> 1000> 1000 2110-2904070 7-57-9003 fifty 90; 97; 103 120; 110; 120 2112-1001310 7-57-1023 204 640; 680; 700 680; 740; 720

As can be seen from the data in table 3, the use of an aqueous sublayer gives high strength to the fastening of rubbers based on various rubbers to steel reinforcement.

Tests were also carried out on brass fungi with a rubber compound 7-B-14-81 (7-57-545-81) using an aqueous sublayer and adhesive KK. The vulcanization mode (180 ° C × 4 min). The bond strength of rubber with brass at a rate of at least 25 kgf / cm ² was (50.9-54.2) kgf / cm ² (the nature of the gap in rubber).

Industrial tests of the adhesive sublayer for attaching 5-57-545-81 rubber to brass fittings were carried out in the manufacture of parts 100-3515225 and 199-3522060. The processing of the reinforcement, the application of the adhesive sublayer and Chemosil 222 adhesives and KK were carried out according to the above method. The manufacturing technology of parts and the vulcanization mode corresponded to established standards. During development, micro-peeling was not observed on the parts.

Claims (1)

Composition as an adhesive sublayer for attaching rubbers to metal during vulcanization or as an adhesive for hot-bonding rubbers based on fluoroelastomers and acrylate rubbers, including 3-aminopropyltriethoxysilane, triethylene glycol dimethyl ether, a solution of paraform in monoethanolamine, ethyl alcohol and glycerol in the following the ratio of components, wt.%: 3-aminopropyltriethoxysilane 3,5-5,5 triethylene glycol dimethyl ether 2.5-4.5 paraform 0.2-0.4 monoethanolamine 0.2-0.4 glycerol 0.2-0.4 ethanol 3,5-5,5 distilled water rest