CN100999868A - Improved impregnation formula for adhesion of terylene tyre cord and rubber and preparation method thereof - Google Patents
Improved impregnation formula for adhesion of terylene tyre cord and rubber and preparation method thereof Download PDFInfo
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- CN100999868A CN100999868A CN 200610148313 CN200610148313A CN100999868A CN 100999868 A CN100999868 A CN 100999868A CN 200610148313 CN200610148313 CN 200610148313 CN 200610148313 A CN200610148313 A CN 200610148313A CN 100999868 A CN100999868 A CN 100999868A
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Abstract
The present invention relates to recipe and preparation process of improved glue for adhering dacron fabric cord to rubber. The improved glue consists of water soluble polyurethane with carboxyl group or sulfonyl group containing chain expander, acrylate emulsion and butyronitrile latex. It can raise the adhesion strength of the dacron/rubber interface and improve the heat performance of the interface greatly. Its preparation process includes the steps of: preparing water soluble polyurethane, preparing acrylate emulsion, and adding water soluble polyurethane and preparing acrylate emulsion into butyronitrile latex. The present invention has environment friendship, low cost and convenient use.
Description
Technical field
The invention belongs to chemical field, particularly a kind of impregnation formula and preparation method who improves terylene tyre cord and rubber adhesion.
Background technology
Terylene tyre cord strengthens the body material by fields such as extensive radial, rubber hose, rotary hoses as rubber tyre, in China still is that nylon cord is as leading position, but nylon cord can not will progressively be replaced by polyester cord, steel cord as the enhancing body of radial.Because the low activity on polyester cord surface, the compound dipping solution of traditional resorcinol-formaldehyde-latex (RFL) can not make the interface produce good bond effect, thereby be necessary to develop the reasonable dipping solution prescription of combination property, satisfy growing polyester cord market
Improve terylene cord/rubber surface adhesive property, mainly contain that alkaline solution is handled, method such as post processing is handled when two step impregnations, a step impregnation, spinning, but all have its limitation.Although adhesion strength is improved, increase rate is not clearly, and the cord mechanical mechanics property also can descend in Ger.2114749 alkali treatment (alkalescent materials such as ammoniacal liquor, polymine); US2003198794 two steps impregnation is owing to complex process, and the big shortcoming of activator blocked isocyanate toxicity of usefulness, and pre-dipping solution is more crisp with epoxy resin, causes the interface shock resistance low; CA1242042, JP2229273 one-step method impregnation remove to add isocyanates and chlorophenol resin improved RFL dipping solution, isocyanates high toxicity own, and the chlorophenol resin is expensive, causes and uses certain limitation; It is coated that US4933236 adopts the spinning post processing to carry out with poly epoxy resin etc., causes the cord hardening difficulty of reeling, and preservation and final adhesion strength increase rate are not very big.
Summary of the invention
Technical problem to be solved by this invention provides a kind of impregnation formula and preparation method who improves terylene tyre cord and rubber adhesion, improve the performance of terylene/rubber interface adhesion strength, solve the environmental problem that the blocked isocyanate high toxicity brings, simplify technological process, reduce production costs.
A kind of impregnation formula that improves terylene tyre cord and rubber adhesion of the present invention: comprise aqueous polyurethane, polyacrylate dispersion, NBR latex, will activate with bonding and unite two into one,
Terylene tyre cord behind the impregnation controlled by gum dipping process, heat treatment, sulfuration process continue to improve terylene cord/rubber composite interface binding intensity.The impregnation time is optimum value at 1min～5min, and the terylene tyre cord rubber absorption capacity is 2.0～6%.
Impregnation after-baking temperature and time influences the interaction between polyurethane, acrylate, the NBR latex, and verified heat treatment time is 120～150 ℃, and terylene cord/rubber interface adhesion strength reached maximum when the time was 1min～4min
Cure time, temperature cause the incomplete adhesion strength of sulfuration to descend inadequately, cord physical and mechanical properties under long-time high temperature descends behind the over cure, select suitable time and temperature, verified curing temperature is at 130～160 ℃, when cure time was 50min～150min, can reach the best point of sulfuration this moment.
Sulfide stress influences state of cure (vulcanization) equally, and also used time and temperature are vulcanized in influence greatly, and when sulfide stress generally was controlled at 5～15MP, cord can produce good the contact with rubber, makes sulfuration fully.
A kind of preparation method who improves the impregnation formula of terylene tyre cord and rubber adhesion of the present invention comprises step:
(1) water-soluble anionic polyurethane preparation
With excessive vulcabond or polyisocyanates and oligomer diol, add that the carboxylic acid chain extender at high temperature reacts the generation performed polymer, be 10～30% performed polymers by being prepared into solid content under emulsifying agent, the mechanism again;
(2) polyacrylate dispersion is that main body and methacrylate, vinylacetate, third rare nitrile copolymerization make solid content 30～60% by acrylic acid first (second, fourth) ester;
(3) with above-mentioned both join in the NBR latex, formation dipping solution prescription, with NBR latex be polyurethane by mass ratio: acrylate: NBR latex is 1～10: 0.5～8: 5～40, add a small amount of shellac, plasticizer, bleeding agent, terylene tyre cord is controlled by gum dipping process, heat treatment, sulfuration process continued to improve terylene cord/rubber composite interface binding intensity.
Described step 2 stirs 4～6h with the mol ratio 10～15: 5～10: 0.5～4: 0.1～3: 6～10 of N hydroxymethyl acrylamide, third rare nitrile, Ammonium Persulfate 98.5, alkyd sodium, ethyl acrylate, water at 70 ℃, obtains about 10～50% acrylic acid ester emulsions of solid content.
Beneficial effect
A kind of impregnation formula that improves terylene tyre cord and rubber adhesion of the present invention has been simplified technological process, has reduced cost, has been avoided the high toxicity because of using blocked isocyanate to bring, and can increase substantially the adhesion strength at interface.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 71 gram polyoxyethylene enediols and 5 gram dihydroxypropionic acid mixture heated to 140 ℃, be cooled to 60 ℃ then and add 24gTDI in batches, stir 3～6h at 80 ℃, prepolymer NCO content is about 6% (quality).0.9 gram triethylamine is melted in 42 gram water, and, form solid content 37% left and right sides emulsion by strong agitation.Get 19 gram above-mentioned emulsion and add 0.1ml ammoniacal liquor (28%), 5 gram water and 1.3 gram methacrylic acid thickeners, stir, get solid content 30% left and right sides water-soluble resin; With N hydroxymethyl acrylamide 9 gram, alkyd sodium 1.35 grams, water 141 grams and 10% Ammonium Persulfate 98.5 70 ℃ stir polymerization down after, add 126 again and restrain ethyl acrylates, 4.5 gram acrylic acid, 4.5 gram N hydroxymethyl acrylamides, 15 gram third rare nitriles and 4.5 gram 10% Ammonium Persulfate 98.5s and 70 ℃ of stirring 4～6h, obtain about 50% acrylic acid ester emulsion of solid content; Adopt quality than polyurethane: acrylate: NBR latex (solid content) is 2: 1.5: 12, add a small amount of plasticizer, bleeding agent etc. of getting in addition, then the terylene cord dipping is handled, rubber absorption capacity is 3.7%, 140 ℃ of heat treatment temperatures, time 200s, 140 ℃ of curing temperatures, time 60min, sulfide stress are 5MP, final resultant interface binding intensity is 102N/cm
Embodiment 2
With 71 gram polyoxyethylene enediols and 5 gram dihydroxypropionic acid mixture heated to 140 ℃, be cooled to 60 ℃ then and add 24gTDI in batches, stir 3～6h at 80 ℃, prepolymer NCO content is about 6% (quality).0.9 gram triethylamine is melted in 42 gram water, and, form solid content 37% left and right sides emulsion by strong agitation.Get 19 gram above-mentioned emulsion and add 0.1ml ammoniacal liquor (28%), 5 gram water and 1.3 gram methacrylic acid thickeners, stir, get solid content 30% left and right sides water-soluble resin; With N hydroxymethyl acrylamide 9 gram, alkyd sodium 1.35 grams, water 141 grams and 10% Ammonium Persulfate 98.5 70 ℃ stir polymerization down after, add 126 again and restrain ethyl acrylates, 4.5 gram acrylic acid, 4.5 gram N hydroxymethyl acrylamides, 15 gram third rare nitriles and 4.5 gram 10% Ammonium Persulfate 98.5s and 70 ℃ of stirring 4～6h, obtain about 50% acrylic acid ester emulsion of solid content; Adopt quality than polyurethane: acrylate: NBR latex (solid content) is 2: 2.5: 11, add a small amount of plasticizer, bleeding agent etc. of getting in addition, then the terylene cord dipping is handled, rubber absorption capacity is 3.4%, 150 ℃ of heat treatment temperatures, time 120s, 150 ℃ of curing temperatures, time 60min, sulfide stress are 5MP, final resultant interface binding intensity is 110N/cm
Embodiment 3
With 71 gram polyoxyethylene enediols and 5 gram dihydroxypropionic acid mixture heated to 140 ℃, be cooled to 60 ℃ then and add 24gTDI in batches, stir 3～6h at 80 ℃, prepolymer NCO content is about 6% (quality).0.9 gram triethylamine is melted in 42 gram water, and, form solid content 37% left and right sides emulsion by strong agitation.Get 19 gram above-mentioned emulsion and add 0.1ml ammoniacal liquor (28%), 5 gram water and 1.3 gram methacrylic acid thickeners, stir, get solid content 30% left and right sides water-soluble resin; With N hydroxymethyl acrylamide 9 gram, alkyd sodium 1.35 grams, water 141 grams and 10% Ammonium Persulfate 98.5 70 ℃ stir polymerization down after, add 126 again and restrain ethyl acrylates, 4.5 gram acrylic acid, 4.5 gram N hydroxymethyl acrylamides, 15 gram third rare nitriles and 4.5 gram 10% Ammonium Persulfate 98.5s and 70 ℃ of stirring 4～6h, obtain about 50% acrylic acid ester emulsion of solid content; Adopt quality than polyurethane: acrylate: NBR latex (solid content) is 2: 1: 14, add a small amount of plasticizer, bleeding agent etc. of getting in addition, then the terylene cord dipping is handled, rubber absorption capacity is 4.1%, 140 ℃ of heat treatment temperatures, time 150s, 140 ℃ of curing temperatures, time 60min, sulfide stress are 5MP, final resultant interface binding intensity is 110N/cm.
Claims (7)
1. impregnation formula that improves terylene tyre cord and rubber adhesion: it is characterized in that: comprise aqueous polyurethane, polyacrylate dispersion, NBR latex, will activate with bonding and unite two into one.
2. a kind of impregnation formula that improves terylene tyre cord and rubber adhesion according to claim 1: it is characterized in that:, the impregnation time, the terylene tyre cord rubber absorption capacity was 2.0～6% at 1min～5min.
3. a kind of impregnation formula that improves terylene tyre cord and rubber adhesion according to claim 1 and 2 is characterized in that: heat treatment time is 120～150 ℃, and the time is 1min～4min.
4. according to claim 1 or 2 or 3 described a kind of impregnation formulas that improve terylene tyre cord and rubber adhesion, it is characterized in that: curing temperature is at 130～160 ℃, when cure time is 50min～150min.
5. according to claim 1,2,3,4 described a kind of impregnation formulas that improve terylene tyre cord and rubber adhesion, it is characterized in that: sulfide stress is at 5～15MP.
6. preparation method who improves the impregnation formula of terylene tyre cord and rubber adhesion is characterized in that: comprise step:
(1) water-soluble anionic polyurethane preparation
With excessive vulcabond or polyisocyanates and oligomer diol, add that the carboxylic acid chain extender at high temperature reacts the generation performed polymer, be 10～30% performed polymers by being prepared into solid content under emulsifying agent, the mechanism again;
(2) polyacrylate dispersion is that main body and methacrylate, vinylacetate, third rare nitrile copolymerization make solid content 30～60% by acrylic acid first (second, fourth) ester;
(3) with above-mentioned both join in the NBR latex, formation dipping solution prescription, with NBR latex be polyurethane by mass ratio: acrylate: NBR latex is 1～10: 0.5～8: 5～40, add a small amount of shellac, plasticizer, bleeding agent, terylene tyre cord is controlled by gum dipping process, heat treatment, sulfuration process continued to improve terylene cord/rubber composite interface binding intensity.
7. a kind of preparation method who improves the impregnation formula of terylene tyre cord and rubber adhesion according to claim 2, it is characterized in that: described step 2 stirs 4～6h with the mol ratio 10～15: 5～10: 0.5～4: 0.1～3: 6～10 of N hydroxymethyl acrylamide, third rare nitrile, Ammonium Persulfate 98.5, alkyd sodium, ethyl acrylate, water at 70 ℃, obtains about 10～50% acrylic acid ester emulsions of solid content.
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| CN 200610148313 CN100999868A (en) | 2006-12-29 | 2006-12-29 | Improved impregnation formula for adhesion of terylene tyre cord and rubber and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011320A (en) * | 2010-10-14 | 2011-04-13 | 芜湖华烨工业用布有限公司 | Polyester impregnation technology |
| CN104389168A (en) * | 2014-12-18 | 2015-03-04 | 湖北久瑞核技术股份有限公司 | Tyre cord fabric dipping glue, preparation method and dipped tyre cord fabric |
| CN104532565A (en) * | 2014-12-18 | 2015-04-22 | 湖北久瑞核技术股份有限公司 | Polyester cord fabric impregnating adhesive, preparation method and impregnated polyester cord fabric |
| CN104594036A (en) * | 2014-12-18 | 2015-05-06 | 湖北久瑞核技术股份有限公司 | Method for bonding fibers or fiber fabrics |
| CN106087433A (en) * | 2016-07-29 | 2016-11-09 | 芜湖华烨工业用布有限公司 | A kind of polyester canvas heat-resisting impregnation process liquid and preparation method |
| CN107236494A (en) * | 2017-07-17 | 2017-10-10 | 山东奥固特化工有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
| CN108864515A (en) * | 2018-07-13 | 2018-11-23 | 无锡宝强工业织造有限公司 | For the high temperature-resistance conveyor belt dipping solution of resistance to aminolysis and preparation method thereof of polyester dipped canvas |
| CN109097993A (en) * | 2018-09-10 | 2018-12-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
| CN110295497A (en) * | 2019-05-29 | 2019-10-01 | 安徽华烨特种材料有限公司 | A kind of aging-resistant flame-proof type canvas maceration extract |
| CN115506155A (en) * | 2021-06-22 | 2022-12-23 | 北京化工大学 | Impregnation system for fiber surface treatment and preparation method thereof |
-
2006
- 2006-12-29 CN CN 200610148313 patent/CN100999868A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011320A (en) * | 2010-10-14 | 2011-04-13 | 芜湖华烨工业用布有限公司 | Polyester impregnation technology |
| CN104389168A (en) * | 2014-12-18 | 2015-03-04 | 湖北久瑞核技术股份有限公司 | Tyre cord fabric dipping glue, preparation method and dipped tyre cord fabric |
| CN104532565A (en) * | 2014-12-18 | 2015-04-22 | 湖北久瑞核技术股份有限公司 | Polyester cord fabric impregnating adhesive, preparation method and impregnated polyester cord fabric |
| CN104594036A (en) * | 2014-12-18 | 2015-05-06 | 湖北久瑞核技术股份有限公司 | Method for bonding fibers or fiber fabrics |
| CN106087433A (en) * | 2016-07-29 | 2016-11-09 | 芜湖华烨工业用布有限公司 | A kind of polyester canvas heat-resisting impregnation process liquid and preparation method |
| CN107236494A (en) * | 2017-07-17 | 2017-10-10 | 山东奥固特化工有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
| CN107236494B (en) * | 2017-07-17 | 2019-01-29 | 山东奥固特化工科技有限公司 | A kind of organic fiber cord dip adhesive composition and preparation method thereof |
| CN108864515A (en) * | 2018-07-13 | 2018-11-23 | 无锡宝强工业织造有限公司 | For the high temperature-resistance conveyor belt dipping solution of resistance to aminolysis and preparation method thereof of polyester dipped canvas |
| CN109097993A (en) * | 2018-09-10 | 2018-12-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
| CN110295497A (en) * | 2019-05-29 | 2019-10-01 | 安徽华烨特种材料有限公司 | A kind of aging-resistant flame-proof type canvas maceration extract |
| CN115506155A (en) * | 2021-06-22 | 2022-12-23 | 北京化工大学 | Impregnation system for fiber surface treatment and preparation method thereof |
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