CN101691476B - Binding agent, preparation method and application thereof - Google Patents
Binding agent, preparation method and application thereof Download PDFInfo
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- CN101691476B CN101691476B CN2009101708416A CN200910170841A CN101691476B CN 101691476 B CN101691476 B CN 101691476B CN 2009101708416 A CN2009101708416 A CN 2009101708416A CN 200910170841 A CN200910170841 A CN 200910170841A CN 101691476 B CN101691476 B CN 101691476B
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- Prior art keywords
- tackiness agent
- polyurethane prepolymer
- base polyurethane
- tree elastomer
- weight
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011230 binding agent Substances 0.000 title abstract description 5
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 239000000806 elastomer Substances 0.000 claims description 31
- 239000004814 polyurethane Substances 0.000 claims description 20
- 229920005906 polyester polyol Polymers 0.000 claims description 18
- 229920002635 polyurethane Polymers 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims description 13
- 229920003052 natural elastomer Polymers 0.000 claims description 13
- 229920001194 natural rubber Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical class OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002649 leather substitute Substances 0.000 abstract description 2
- 238000004026 adhesive bonding Methods 0.000 abstract 1
- 208000018747 cerebellar ataxia with neuropathy and bilateral vestibular areflexia syndrome Diseases 0.000 abstract 1
- 239000010985 leather Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 46
- 239000000126 substance Substances 0.000 description 15
- 238000010559 graft polymerization reaction Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 244000286663 Ficus elastica Species 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229920001195 polyisoprene Polymers 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical class CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XFEWMFDVBLLXFE-UHFFFAOYSA-N 1-isocyanatodecane Chemical compound CCCCCCCCCCN=C=O XFEWMFDVBLLXFE-UHFFFAOYSA-N 0.000 description 1
- VRVUKQWNRPNACD-UHFFFAOYSA-N 1-isocyanatopentane Chemical class CCCCCN=C=O VRVUKQWNRPNACD-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a binding agent, which can be used in the process of manufacturing vulcanized shoes. The binding agent is used for gluing upper materials (such as true leather, artificial leather, canvases and the like) to rubber or crude rubber. The invention also provides a preparation method and application of the binding agent.
Description
Technical field
The present invention relates to tackiness agent, be specifically related to a kind of tackiness agent organic solvent, environmental protection, that bonding effect is good that do not contain, be particularly suitable for the tackiness agent of vulcanized shoes.
Background technology
China is shoemaking big country, also is the major country of production of vulcanized shoes, and for example, the liberation footwear are exactly a kind of vulcanized shoes.The vulcanized shoes good permeability, low price, pattern is changeable, generally receives liking of young consumers.In recent years, along with vamp material is superior gradually, tradition such as corium, synthetic leather were used in the material on the sports shoes, also were used to make vulcanized shoes, and vulcanized shoes is also developing towards high extreme direction, and the customer group of vulcanized shoes enlarges day by day, the demand cumulative year after year.
The demand of sulfuration adhesive for shoes is annual at home also to be increased along with the rising of vulcanized shoes sales volume.Domestic sulfuration adhesive for shoes is mainly the solvent-borne type product, uses the solvent borne product in a large number, has polluted environment, has wasted resource, has influenced the healthy of the workman of Shoes Factory, even some tackiness agent contains " triphen " type material, directly influences HUMAN HEALTH.Though some producer has adopted natural emulsion to cooperate the bonding vulcanized shoes of vulcanization accelerator, because it is few to follow stability vamp material kind poor, can be bonding, both can't large-scale production and application, also limited the application of high-grade fabric in vulcanized shoes.
Therefore, need a kind of tackiness agent that is used for vulcanized shoes of invention to address the above problem.
Summary of the invention
The purpose of this invention is to provide a kind of tackiness agent organic solvent, environmental protection, that bonding effect is good that do not contain, be particularly suitable for the tackiness agent of vulcanized shoes.Other goals of the invention of the present invention have provided a kind of preparation method and application of tackiness agent.
The invention provides a kind of tackiness agent, comprise the water of 100-200 weight part, the modified natural rubber of 100-200 weight part; Described modified natural rubber is polymerized by the tree elastomer and the Polyurethane performed polymer of graft polymerization preformer; Described graft polymerization preformer tree elastomer has methylacrylic acid and tree elastomer to be polymerized; Described Polyurethane is polymerized by vulcabond and polyester polyol; Described Polyurethane segment accounts for 40～60% of final total polymer weight.
The staple of tackiness agent of the present invention is polyurethane-modified tree elastomer, contains two kinds of functional groups in the molecule: the segment of tree elastomer structure can react with rubber, rubber; The urethane segment can react with the urethane in material and the tackiness agent.Adopt tackiness agent of the present invention, its bonding effect is good, and does not contain organic solvent, meets the theory of modern industry environmental protection.
As the preferred implementation of tackiness agent of the present invention, the tree elastomer of described methylacrylic acid graft modification, wherein the methylacrylic acid segment accounts for 2～10 weight % of modified natural rubber.
As the preferred implementation of tackiness agent of the present invention, the NCO mass contg in the described polymeric polyisocyanate, with NCO, calculate molecular weight=42, is 2.0 to 6.0 weight % of urethane.
As the preferred implementation of tackiness agent of the present invention, described Polyurethane performed polymer is synthetic by aliphatic diisocyanate and polyester polyol, and molecular weight is 8000～12000.
As the preferred implementation of tackiness agent of the present invention, described polyester polyol is formed by di-carboxylic acid and divalent alcohol polycondensation, and described di-carboxylic acid comprises: hexanodioic acid, Succinic Acid and pentanedioic acid; Described divalent alcohol comprises: 1,4 butyleneglycols, 1,5 pentanediols, 1,6 pinakons.
As the preferred implementation of tackiness agent of the present invention, in the described polyester polyol polycondensation process, add caprolactone.The polyester polyol for preparing can obtain solvability preferably.
As the preferred implementation of tackiness agent of the present invention, described tree elastomer STR-3L level tree elastomer.
As the preferred implementation of tackiness agent of the present invention, said graft polymerization preformer tree elastomer is a methylacrylic acid graft polymerization preformer tree elastomer.
As the preferred implementation of tackiness agent of the present invention, described Polyurethane performed polymer is vulcabond and polyester polyol synthetic Polyurethane.
As the preferred implementation of tackiness agent of the present invention, described polyester polyol is an aliphatic polyester; Described vulcabond is an aliphatic diisocyanate.
As the preferred implementation of tackiness agent of the present invention, described tackiness agent comprises the water of 130-180 weight part, the modified natural rubber of 130-180 weight part.As the more preferably embodiment of tackiness agent of the present invention, described tackiness agent comprises the water of 150 weight parts, the modified natural rubber of 140 weight parts.
The present invention also provides a kind of method for preparing tackiness agent, and it comprises the steps:
1), obtains methylacrylic acid grafted tree elastomer with tree elastomer and methylacrylic acid polymerization;
2) with vulcabond and polyester polyol reaction, obtain the Polyurethane performed polymer, the molecular weight of said Polyurethane performed polymer is 8000～12000;
3) with above-mentioned 1) plant grafted tree elastomer and 2) in the Polyurethane prepolymer reaction, make the tree elastomer of Polyurethane modification;
4) with above-mentioned 3) in the 100-200 weight part modified natural rubber, be scattered in the water of 100-200 weight part, obtain product.
As the preferred implementation of adhesive preparation method of the present invention, described Polyurethane is the aliphatic poly ammoniacum; Described vulcabond is for also being aliphatic diisocyanate; Described tree elastomer is earlier through the methylacrylic acid grafting; Described tackiness agent is a water miscible liquid.
The present invention provides a kind of aqueous binder, can be used as the tackiness agent of vamp material in the vulcanized shoes making processes.
Description of drawings
Fig. 1 is for using the operational flowchart of the embodiment of the invention 1 tackiness agent.
Embodiment
For making the present invention be more prone to understand,, further set forth the present invention below in conjunction with specific embodiment.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.
Tackiness agent of the present invention, it is suitable for the Application Areas of all water dispersible glue, and does not have those shortcomings of prior art.
Embodiment 1
The whole world has larger vulcanized shoes enterprise of family more than 3000 approximately at present.The vulcanized shoes good permeability, low price, very near vast middle-grade consumer group, volume of production and marketing is stable always over past ten years rises, and China is the maximum vulcanized shoes producing country in the whole world.Market also increases the demand of vulcanized shoes, has had many Shoes Factories to begin to increase the production line of building vulcanized shoes.Vulcanized shoes earlier period be the footwear that belong to low-grade, but along with producer in style and technical raising, began on market, to appear ascendant trend in recent years.Vulcanized shoes popular in 2003 forms one pseudo-classic wind in young consumers, for follow the fashion, colorful human consumer provides various selection.Along with the further segmentation in market, the young consumer group will pursue various, individual character more in the selection of CRUX product, and the vulcanized shoes of a new generation, the variation of its product is more and more liked for campus student and younger generation's human consumer.So in following several years, vulcanized shoes market still can continue to increase.
At present, China's footwear are looked forward to when the preparation vulcanized shoes, tackiness agent major part or the organic solvent adhesive used, and the organic solvent more than 85% evaporate in the air, and environment has been caused serious pollution, has also wasted resource simultaneously.In China, shoe industry is a labour intensive profession, and most of flow process all is manual operations, and the on-the-spot density of population is big, and the evaporable organic solvent is very big to the potential hazard of human body; When especially having used " triphen " material in the tackiness agent, endanger bigger.Organic solvent adhesive all has potential safety hazard in construction and storage process.
Formally vote through through parliament of European Union and EU Council in December, 2006, and in formally effective enforcement on June 1 " chemical registration, assessment, permission and statute of limitation " in 2007.The REACH rules are rules of a supervision chemical substance, and incidence has comprised Chemicals and the derived product that contains chemical substance.Its object of standardization not only comprises 30,000 number of chemical article, also comprises 5,000,000 kinds of derived product that chemical substance is made, and relates to industries such as oil, chemical industry, medicine, agricultural chemicals, weaving, clothes, toy, footwear, furniture, electromechanics.About 30,000 kinds of chemical substances are detected, in the REACH rules, need detailed title and hazardness, guarantee the public's health and environment protection.The REACH rules have forwarded more responsibilities of controlling the chemical risks to enterprise from administrative authority more.The security feature of chemical substance need be understood by the enterprise of production, operation, use chemical, understands it and whether human body and environment is produced harm.And the security feature that will understand chemical substance will have the support of experimental data, in this sense, get into European Union market, not have the market access without data.European Union is the main exit object of China footwear enterprise, and the threshold of " healthy, environmental protection " has been set in the enforcement of REACH rules undoubtedly to the outlet of footwear.
So; In the making processes of vulcanized shoes, use aqueous adhesive; Not only meet " China is to the limits of harmful substances standard in the indoor decorating adhesive " of Chinese Government, and can help footwear enterprise to stride across the environmental requirement threshold of REACH rules tackiness agent.
A kind of tackiness agent of present embodiment comprises the water of 150 weight parts, the modified natural rubber of 140 weight parts; Described modified natural rubber is polymerized by the tree elastomer and the Polyurethane performed polymer of graft polymerization preformer; Described graft polymerization preformer tree elastomer is a methylacrylic acid grafted tree elastomer, and described Polyurethane is the aliphatic poly ammoniacum; The sticking section of described Polyurethane accounts for 40～60% of total polymer weight.
The synthetic primitive reaction of vinylformic acid graft polymerization preformer tree elastomer is (wherein R is H) as follows:
The building-up reactions of Polyurethane performed polymer is following:
Graft polymerization preformer tree elastomer and base polyurethane prepolymer for use as synthetic primitive reaction are following:
Be used to prepare vinylformic acid of the present invention and can be aliphatic alkyl vinylformic acid, preferred: methylacrylic acid.
Being used to prepare tree elastomer of the present invention is common tree elastomer, preferred: STR3L one-level smoked sheet.
The Polyurethane performed polymer can be any aliphatic poly ammoniacum, and its raw material vulcabond is an aliphatic diisocyanate, for example 1, and 4-two isocyanato-butane, 1; 6-two isocyanato-hexanes (HDI), 2-methyl isophthalic acid, 5-two isocyanato-pentanes, 1,5-two isocyanato-s-2; 2-dimethylpentane, 2,2,4-and 2,4; 4-trimethylammonium-1,6-two isocyanato-hexanes, 1,10-two isocyanato-decane, preferred vulcabond is HDI;
Polyester polyol also is an aliphatic polyester polyols, and its molecular weight is between 1000～1500.Preferential polyester polyol is hexanodioic acid and 1,4 butyleneglycol synthetic polyester polyols.
The tackiness agent of embodiment 1 can adopt following preparation method to prepare, and its preparation method comprises the steps:
1. the tree elastomer with 100 parts of quality is dissolved among the mixed solvent A of 500 parts of quality, adds the methylacrylic acid of 20 parts of quality, stirs.Add the Lucidol of 2～5 parts of quality, under 60～90 ℃ of conditions, stirred 4～5 hours, stop heating, cooling reaction system is to room temperature; The Resorcinol that adds 1 part of quality.Extracting and separating goes out copolymer mixture solution.
2. the vulcabond of the pure and mild 35 parts of quality of polyester polyols of 100 parts of quality is dropped into methylethylketone (the methyl ethyl ketone of 200 parts of mass parts; MEK): toluene (TOL): in the mixed solvent of pimelinketone (CYC)=40: 30: 30; The auxiliary agent that adding needs; Be heated to solvent and begin to reflux, stir end in 4 hours, process the Polyurethane performed polymer.
3. the graft polymerization preformer tree elastomer solution in above-mentioned 1 is heated to 90 ℃, begins to drip 100 parts of Polyurethane performed polymers, after dropwising, insulation is also stirred, and reacts 3 hours.
4. in above-mentioned system, add 500 parts of quality zero(ppm) water, vibration 10min isolates oil phase.Repetitive operation three times.
With 1～2% X 2073 be dissolved in 190 parts of quality zero(ppm) water in, stir the above-mentioned oil phase system of adding down in brute force, stirred 30 minutes.Organic solvent is extracted in decompression out.
6. composite is the natural rubber latex of the PU modification of 50% solid content, and interim PU segment accounts for about 40% of polymer weight.
The raw material that adopts:
1) tree elastomer: one-level smoked sheet, limited-liability company of Hainan tree elastomer industrial group.
2) mixed solvent A: hexanaphthene: MIBK: sherwood oil: DMF=20: 20: 30: 30, ratio can suitably be adjusted, but should guarantee that whole process does not have polymkeric substance to separate out.
3) all solvents are commercially available AR level.
4) vulcabond: Huntsman Shanghai ltd.
5) polyester polyol: Jiangsu Chinese commerce-change worker ltd.
6) TEB 3K: Dutch Akzo Nobel N.V..
7) Lucidol: Dutch Akzo Nobel N.V..
8) Resorcinol: French sieve ground is inferior.
9) X 2073: revive like chemical industry ltd in Nanjing.
With the tackiness agent called after NR-040 of embodiment 1, adopt the method shown in Fig. 1 schema, rubber is binded with corium and anti-fur respectively, sulfuration then, the sulfurized condition can be 110 ± 5 ℃, 0.3 ± 0.02Mpa, 75 ± 15min.The adherent effect adopts following method test: it all is Chubu Resin Chemicals Co., Ltd.'s production and selling that other in Fig. 1 flow process are followed material.
One, tensile test
Prepare 3 test pieces, supply the test and the amount of commenting to use.Specimen will be placed 24 hours ability and cut out that to cut be the test strip after sulfuration, and before test, will be placed in the laboratory environment more than 2 hours.
The setting of testing tool and adjustment: one side with the last anchor clamps that are sandwiched in puller system of tested object, the other side is sandwiched in lower clamp.When test piece places on the test fixture, guarantee to have and place appropriately, must guarantee that test piece is clipped on the anchor clamps always very securely when surveying pulling force, if will clamp again when bending is arranged.
Begin test, separately (in the zone that is difficult to draw back, speed can come down to 50mm/min with the both sides material with speed 200mm/min.Test is when carrying out, sticking together that defiber must be known and obviously, if do not have, can use pocket knife to make this defiber between this two block of material, and data logging is got off between two block of material.When puller system has been moved the summit of machine soon to, stop to test and again test piece being clipped, to heavily press from both sides once between per at least 5 test zones.Repeat above action till whole pulling force test piece all tests.
Two, creep test
Each direction be used for fixing static load then the minimal sample amount of test be 3.
2. be equipped with appearance:
2.1 size cross cutting 6 slat gum bars with 2.54cm * 15cm * 4mm.Adopt O/RS 017 or O/RS 031 low-elongation rubber compounding.
2.2 respectively on long and wide direction, with 3 plane materiel bars of size cross cutting of 2.54cm * 15cm, totally 6.
2.3 (the 1st: terminal 1.5 inches places the end at India-rubber strip and plane materiel bar indicates 3 lines; Second: terminal 2.0 inches places; Article three: terminal 2.5 inches places).
2.4 locate to bore the aperture that a diameter is about 4-5mm for terminal 1.5 inches at India-rubber strip and vamp material bar.
2.5 any treatment agent and glue are not brushed by the terminal 2.0 inches places of reserved materials, authentic treatment agent of brushing and glue on India-rubber strip and plane materiel bar.
2.6 the test strip behind the brushing glue is placed 3-5min in 50-60 ℃ baking oven, or makes thorough drying according to the guide of BPFC.Material is fitted India-rubber strip and plane materiel bar rapidly after going out baking oven, and fully pressing is fitted to accomplish.
2.7 will accomplish the test sample book of fitting placed 24 hours in the laboratory.
2.8, the laminated material bar is torn to the 3rd line place (terminal 2.5 inches places) with hand for guaranteeing before the test consistent then edge is arranged.
3. the foundation of testing apparatus and debugging:
3.1 baking oven is preheated to 41 ℃ (105F).
3.2 the test strip after all applyings was worn out 3 days in baking oven.
3.3 take out sample and adjust temperature to 80 ℃ preheating.
4. data gathering and analysis
After 4.1 test strip is cooled to room temperature, will be the fit area separately, hitch and belt hung on the baking oven top from the drill hole of India-rubber strip with belt.Tie up to the drill hole of upper layer of material with a 1kg SW.
Be used for about 180 ° of angles to guarantee that plane materiel is adhered 4.2 adhesion is stable.
Place 30min in the baking oven 4.3 will follow bar.
4.4 take out test strip and check then bar rapidly in period Mo.
4.5 measure by following the length that the line end tears apart, in mm.
4.6 the length of splitting of arbitrary test strip (length direction or width) is " PASS " less than 1/2 inch (1.27cm).If arbitrary test sample book (length direction or width) is regarded as " FAIL ", this treatment agent/glue need be reappraised by CE.
| With the footwear material of rubber to pasting | Later stage pulling force (kg/cm) | MV (kg/cm) | Destroy type | Creep (cm) | Pulling force standard (kg/cm) | Creep standard (cm) |
| Corium | 8.0，7.7，8.4 | 8.0 | Rubber destroys | 0.0 | 2.7 | 1.27 |
| Anti-fur | 7.4，7.5，7.7 | 7.5 | Rubber destroys | 0.0 | 2.7 | 1.27 |
Three, burn-in test
1, test piece is prepared: before test, sulfuration back test piece must be placed 24 hours or the more time at normal temperatures.
2, testing tool is set and adjustment:
2.1. open baking box then design temperature at 70 ℃.
2.2. stablize constantly 70 ± 2 ℃ the time Deng baking box, baking box put in ready test piece.
2.3. after 120 hours that test piece is placed in baking box, from baking box, take out.
2.4. after test piece placed 48hrs at normal temperatures, the test pulling force.
| With the footwear material of rubber to pasting | Later stage pulling force (kg/cm) | MV (kg/cm) | Destroy type | Aging back tension (kg/cm) | MV (kg/cm) | Destroy type | Pulling force standard (kg/cm) |
| Corium | 5.3，5.3，5.3 | 5.3 | Rubber destroys | 5.3，5.4，5.4 | 5.4 | Rubber destroys | 2.7 |
| Anti-fur | 5.0，5.0，5.0 | 5.0 | Rubber destroys | 5.1，5.2，5.1 | 5.1 | Rubber destroys | 2.7 |
Four, hydrolysis test
1, test piece is prepared: before test, sulfuration back test piece must be placed 24 hours or the more time at normal temperatures.
2, testing tool is set and adjustment:
2.1. open the hydrolysis case, design temperature is at 70 ℃, relative humidity is 95%RH.
2.2. 70 ± 2 ℃ the time, moisture stable is put into the hydrolysis case with ready test piece when 90 ± 5RH Deng the homo(io)thermism of hydrolysis case.
2.3. take out after 120 hours that test piece is placed in the hydrolysis case.
2.4. after test piece placed 48hrs at normal temperatures, the test pulling force.
| With the footwear material of rubber to pasting | Later stage pulling force (kg/cm) | MV (kg/cm) | Destroy type | Hydrolysis back tension (kg/cm) | MV (kg/cm) | Destroy type | Pulling force standard (kg/cm) |
| Corium | 6.4，6.5， 6.9 | 6.6 | Corium destroys | 5.7，6.3，5.7 | 5.7 | Cohesion destroys | 2.7 |
Five, volatile organic solvent gas (VOC) test
Because the glue among the embodiment 1 is aqueous product, itself does not contain VOC, thereby, adopt this glue to make vulcanized shoes, will reduce glue part of V OC, thereby realize that VOC reduces discharging,
Should be noted that at last; Above embodiment is only in order to technical scheme of the present invention to be described but not to the restriction of protection domain of the present invention; Although the present invention has been done detailed description with reference to preferred embodiment; Those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention, and do not break away from the essence and the scope of technical scheme of the present invention.
Claims (9)
1. a tackiness agent comprises the water of 100-200 weight part, the modified natural rubber of 100-200 weight part; Described modified natural rubber forms through twice graft modification, uses the methylacrylic acid graft modification earlier, and then is polymerized with base polyurethane prepolymer for use as; Described base polyurethane prepolymer for use as is polymerized by vulcabond and polyester polyol, and described urethane segment accounts for 40～60% of final total polymer weight; The tree elastomer of described methylacrylic acid graft modification, wherein the methylacrylic acid segment accounts for 2～10 weight % of modified natural rubber.
2. tackiness agent according to claim 1 is characterized in that, the NCO mass contg in the described base polyurethane prepolymer for use as, and with NCO, calculate molecular weight=42, is 2.0 to 6.0 weight % of base polyurethane prepolymer for use as.
3. tackiness agent according to claim 1 is characterized in that, described base polyurethane prepolymer for use as is synthetic by aliphatic diisocyanate and polyester polyol, and molecular weight is 8000～12000.
4. tackiness agent according to claim 1 is characterized in that, described polyester polyol is formed by di-carboxylic acid and divalent alcohol polycondensation, and described di-carboxylic acid comprises: hexanodioic acid, Succinic Acid and pentanedioic acid; Described divalent alcohol comprises: 1,4 butyleneglycols, 1,5 pentanediols, 1,6 pinakons.
5. tackiness agent according to claim 4 is characterized in that, in the described polyester polyol polycondensation process, adds caprolactone.
6. tackiness agent according to claim 1 is characterized in that, described tackiness agent comprises the water of 130-180 weight part, the modified natural rubber of 130-180 weight part.
7. method for preparing the described tackiness agent of claim 1, it comprises the steps:
1), obtains methylacrylic acid grafted tree elastomer with tree elastomer and methylacrylic acid polymerization;
2) with vulcabond and polyester polyol reaction, obtain base polyurethane prepolymer for use as, the molecular weight of said base polyurethane prepolymer for use as is 8000～12000;
3) with above-mentioned 1) in grafted tree elastomer and 2) in base polyurethane prepolymer for use as reaction, make polyurethane-modified tree elastomer;
4) with above-mentioned 3) in the 100-200 weight part modified natural rubber, be scattered in the water of 100-200 weight part, obtain product.
8. the method for preparing tackiness agent according to claim 7 is characterized in that, described urethane is aliphatic polyurethane; Described vulcabond is an aliphatic diisocyanate; Described tackiness agent is a water miscible liquid.
9. the arbitrary described tackiness agent of claim 1 to 6 is as the purposes of vamp material tackiness agent in the vulcanized shoes manufacturing processed.
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| CN102898984B (en) * | 2012-09-11 | 2014-04-02 | 苏州市胶粘剂厂有限公司 | Preparation method for aqueous adhesive for vulcanized shoes |
| CN105017993B (en) * | 2015-08-10 | 2017-09-19 | 万华化学（广东）有限公司 | A kind of vulcanized shoes aqueous binder and preparation method thereof |
| CN106010365B (en) * | 2016-07-07 | 2018-06-26 | 芜湖风雪橡胶有限公司 | Rubber adhesive and preparation method thereof |
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| CN1995258A (en) * | 2006-11-17 | 2007-07-11 | 广州市化学工业研究所 | Aqueous adhesive for shoes and its production method |
| CN101173031A (en) * | 2006-11-01 | 2008-05-07 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| CN101508879A (en) * | 2009-03-17 | 2009-08-19 | 陕西科技大学 | Method of preparing watersoluble polyurethane adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101173031A (en) * | 2006-11-01 | 2008-05-07 | 北京林氏精化新材料有限公司 | Polyurethane prepolymer, aquosity polyurethane binder and uses thereof |
| CN1995258A (en) * | 2006-11-17 | 2007-07-11 | 广州市化学工业研究所 | Aqueous adhesive for shoes and its production method |
| CN101508879A (en) * | 2009-03-17 | 2009-08-19 | 陕西科技大学 | Method of preparing watersoluble polyurethane adhesive |
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| JP特开2002-188071A 2002.07.05 |
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