CN1134965A - High adhesion strength graft chlorobutyl rubber adhesive with changing-to-yellow resistant of coatings thereof, and process for prodn. of same - Google Patents
High adhesion strength graft chlorobutyl rubber adhesive with changing-to-yellow resistant of coatings thereof, and process for prodn. of same Download PDFInfo
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- CN1134965A CN1134965A CN 96102957 CN96102957A CN1134965A CN 1134965 A CN1134965 A CN 1134965A CN 96102957 CN96102957 CN 96102957 CN 96102957 A CN96102957 A CN 96102957A CN 1134965 A CN1134965 A CN 1134965A
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Abstract
Graft chloroprene adhesive is produced from chloroprene rubber and a coating function possessing filler (10%-20% titanium dioxide, 5%-10% light calcium carbonate, 3%-6% magnesium oxide, 3%-6% zinc oxide). with the aid of 0.15%-0.3% aluminium acid esters coupling agent, it is mixed with solvent. Add in 35%-60% methyl propylene formate and 0.7%-1.0% benzoyl peroxide to graft copolymerize. The reaction taking place at 80-90 deg.C for 4 h., then add in 0.4-0.6% hydroquinone, 0.4-0.7% 2.6-ditertiary butyl para cresol and 15%-20% tertiary butyl phenolic resin. The adhesive agent obtd. possesses high adhesion strength and can resist aging.
Description
The present invention relates to a kind of graft neoprene adhesive and production technique thereof.
Being used for material adherent tackiness agent such as polyvinyl chloride (PVC) leatheroid, urethane (PU) synthetic leather, corium, TPR ground and EVA foam material mainly carries out graft copolymerization by chloroprene rubber and methyl methacrylate (MMA) and obtains.
Pan Ronghua, Dai Lizong once disclosed a kind of graft neoprene adhesive and manufacture method thereof that has the second reactive monomer component in Chinese patent CD87107257.2.Structure is
The second reactive monomer add-on be the 5～l5% of chloroprene rubber weight of feeding intake, the add-on of first monomers methyl methacrylate (MMA) and initiator benzoyl peroxide (BPO) is respectively 45%～60% and 0.7%～1.0% of the chloroprene rubber weight that feeds intake, and Synergist S-421 95 tert butyl phenolic resin (i.e. 2402 resins) in addition, Resorcinol (HQ) and anti-aging agent 26-ditertbutylparacresol (popular name antioxidant 264), add-on is respectively 15%～20% of the chloroprene rubber weight that feeds intake, 0.4%～0.6% and 0.4%～0.7%, be controlled at 80～86 ℃ of polyase 13 .5～4 hour.This patent has been applied to produce for many years.
People such as Li Kenong, Shao Guangda (Chengdu Univ. of Science ﹠ Technology's journal, 1982,4:13～22) discloses a kind of CAF type hide finishes, and it is a kind of latex that carries out copolymerization by chloroprene monomer and esters of acrylic acid, does not have to cover and binding function.
People's (vinylformic acid polyreactions in the presence of chloroprene rubber such as Wen Ziyi field, chemically industry (Osaka), 1966,40 (2): 574～582) disclose mainly with regard to Diisopropyl azodicarboxylate, the variation of the conditions such as add-on of these three kinds of initiators of lauroyl peroxide and benzoyl peroxide is to benzene being the research of the influence of the vinylformic acid of solvent and chloroprene rubber graft copolymerization.
Dai Lizong, Pan Ronghua (synthetic and the characterization technique polymer material science and the engineering of graft neoprene adhesive, 1993,9 (6): 126～131) provide the synthetic method of graft neoprene adhesive, polymerization conversion, the conclusive evidence method of the measuring method of percentage of grafting and graft copolymerization; Angle from matrix material, the relation of phase structure and tackiness agent performance has been discussed, thermal characteristics to grafting mechanism, tackiness agent is inquired into, and especially should be used as detailed narration with regard to modern analysis means such as IR, XPS, TEM, SEM, TGA aspect the graft neoprene adhesive sign.
The synthetic materials of reporting in the above-mentioned document has the function of tackiness agent or the function of finishing agent, still the report that no-trump is bonding and covering with paint, several functions of covering combine.
In recent years, along with the chemization of material for shoes and color and luster trend to the light color development, the processing of finishing agent is all passed through on footwear material surface, common adhesive for shoe use is in satisfying bonding process, often because gluing pollutes vamp accidentally, and need after being coated with glue bond, to increase cleaning, finishing process, or influence the attractive in appearance of footwear because of the aging xanthochromia of tackiness agent.
Purpose of the present invention is intended to develop a kind of high-adhesive-strength, possesses the novel adhesive of anti-xanthochromia the and the production technique thereof of covering with paint and covering function.
The said graft neoprene adhesive of the present invention comprises filler, coupling agent, solvent, methyl methacrylate, benzoyl peroxide, Resorcinol, 26-ditertbutylparacresol and the tertiary butyl phenolic aldehyde resin of chloroprene rubber, tool covering function; Said filler is titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide; Said coupling agent is an aluminate coupling agent, titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide, aluminate coupling agent, methyl methacrylate, benzoyl peroxide, Resorcinol, the 26-ditertbutylparacresol, the add-on of tertiary butyl phenolic aldehyde resin is respectively 10%～20% of the chloroprene rubber weight that feeds intake, 5%～10%, 3%～6%, 3%～6%, 0.15%～0.3%, 35%～60%, 0.7%～1.0%, 0.4%～0.6%, 0.4%～0.7%, 15%～20%, the feed ratio of chloroprene rubber and solvent is 1: 6.8～7.4 (weight ratios).Used solvent and proportioning thereof are as follows:
Vinyl acetic monomer: hexanaphthene: 120
#Gasoline=50: 20: 30, or vinyl acetic monomer: acetone: 120
#Gasoline=35: 20: 45, or vinyl acetic monomer: toluene: 120
#Gasoline=25: 30: 45 or vinyl acetic monomer: 120
#Gasoline=2: 1, or pure toluene.
The add-on of titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide, aluminate coupling agent (weight of the chloroprene rubber that feeds intake relatively) is preferably 14%～16%, 7%～8%, 4%～5%, 4%～5% and 0.20%～0.25%.
The production technique of the said graft neoprene adhesive of the present invention is as follows: at first press proportioning with chloroprene rubber and titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide under the cooperation of aluminate coupling agent with solvent evenly after, it is dropped into band stirs, condensation, in the reactor of temperature regulating device, continue to stir colloidal sol down in 60～80 ℃, after treating dissolving fully, add methyl methacrylate and benzoyl peroxide and carry out graft copolymerization, be reflected under 80～90 ℃ and carry out, preferably 83～86 ℃, react after 4 hours, add Resorcinol and 26-ditertbutylparacresol termination reaction, and add the tackifier tert butyl phenolic resin.The gained tackiness agent is the oyster white viscous solution, and is not stratified.Its each quality and technical index is as follows:
Solids content (%): 19.2 ± 0.5;
Kinetic viscosity (25 ℃, mpas): 1500～2000;
Bonding strength (N/mm measures next stripping strength by the GB532-82 measuring method):
The PVC leather is to gluing 〉=3.0, and the PU leather is to gluing 〉=3.0, PVC leather～PU leather 〉=3.0;
Storage period: sealing, the shady and cool place of lucifuge preservation period 6 months.
Chloroprene rubber adhesive agent provided by the invention has to be covered with paint, lacquer, colour wash, etc. and bonding dual-use function, and can ageing-resistant xanthochromia, to the bonding strength height of sticking material PVC of difficulty and PU, and adopts to hang down and poisons solvent formula; The production technique of tackiness agent is simple, easily control.This tackiness agent has solved the problem that runs in shoe-making industry and the evolution of footwear industry, its great advantage is not pollute vamp behind the gluing, and then simplified shoe-making process, only needed 1～2 time butanone to wipe examination by maxxaedium, carry out brush coating with regard to available this glue of being furnished with 5%～8% isocyanic ester behind the airing, can glue together through oven dry in 60 ℃, 4～6 minutes, after solidifying 72 hours, just can reach maximum bonding strength.
The invention will be further described with embodiment below.
Embodiment 1: (a day electrification is produced with 20g chloroprene rubber A-90, polymerization-grade), 3g titanium dioxide, 1.5g light calcium carbonate, 1.0g zinc oxide, 0.8g magnesium oxide, 0.05g aluminate coupling agent mix back input 250ml and are equipped with in the three-necked bottle of electric mixer, reflux condensing tube, thermometer, add 140g solvent (vinyl acetic monomer: toluene: 120 again
#Gasoline=25: 30: 45), carrying out colloidal sol to chloroprene rubber in 70 ℃ of following stirrings dissolves fully, 85 ℃ add 8.0g methyl methacrylate and 0.20g benzoyl peroxide down, reacted 4 hours, add the 0.11g Resorcinol, 0.12g oxidation inhibitor 26-ditertbutylparacresol, 4.0g tertiary butyl phenolic aldehyde resin, after the dissolving fully, stop stirring, discharging.The gained tackiness agent is removed from office sticking the bonding strength of material: PVC: 3.21N/mm, the PU leather is to sticking: 3.40N/mm, PVC leather～PU leather: 3.09N/mm.
Embodiment 2: with 20g chloroprene rubber A-90,3g titanium dioxide, 1.5g light calcium carbonate, 1.0g zinc oxide, 0.8g magnesium oxide, 0.05g aluminate coupling agent mix the back input and have in the three-necked bottle of stirring, condensation, temperature control, add 148ml solvent (vinyl acetic monomer: hexanaphthene: 120 again
#Gasoline=50: 20: 30), stir colloidal sol down in 80 ℃, 80 ℃ add 8g methyl methacrylate and 0.14g benzoyl peroxide down, reacted 4 hours, add 0.12g Resorcinol, 0.10g 26-ditertbutylparacresol, 3.0g tertiary butyl phenolic aldehyde resin, after the dissolving fully, stop stirring, discharging.The gained tackiness agent is removed from office sticking the bonding strength of material: PVC: 3.10N/mm, the PU leather is to sticking: 3.30N/mm, PVC leather～PU leather: 3.05N/mm.
Embodiment 3～5: preparation method, condition change the add-on of methyl methacrylate, coupling agent and filler with embodiment 1, the results are shown in following table.
| Group (g) part embodiment | Methyl methacrylate | Titanium dioxide | Light calcium carbonate | Zinc oxide | Magnesium oxide | Aluminate coupling agent | The PVC leather is to sticking (N/mm) | The PU leather is to sticking (N/mm) | PVC leather～PU removes from office (N/mm) |
| ????3 ????4 ????5 | ???7 ???10 ???12 | 4 3.5 2 | 1 1.6 2 | 1 0.6 1.2 | 1.2 0.6 1 | 0.06 0.04 0.03 | 3.01 3.30 3.02 | 3.20 3.08 3.04 | 3.07 3.03 3.22 |
Embodiment 6 (expanding tests, condition by embodiment 1 is carried out, in 200 liters of reactors, carry out): with 20Kg chloroprene rubber A-90, the 3Kg titanium dioxide, 1.5Kg light calcium carbonate, 1.0Kg zinc oxide, 0.8Kg magnesium oxide, the 50g coupling agent, colloidal sol after the 140Kg solvent is combined, add methyl methacrylate 8Kg, benzoyl peroxide 200g, behind the graft polymerization reaction 4 hours, add the 150g Resorcinol, 120g 26-ditertbutylparacresol and 4Kg tertiary butyl phenolic aldehyde resin, dissolving back gained tackiness agent is removed from office sticking the bonding result of material: PVC: 4.68N/mm (material partial rupture), the PU leather is to sticking: 4.50N/mm (material partial rupture), PVC leather～PU leather: 4.41N/mm (material partial rupture).
Claims (4)
1. a tool is covered with paint, lacquer, colour wash, etc. and is covered the high-adhesive-strength of anti-xanthochromia graft neoprene adhesive, contain neoprene rubber, solvent, methyl methacrylate, benzoyl peroxide, Resorcinol, 26-ditertbutylparacresol and tertiary butyl phenolic aldehyde resin, it is characterized in that also containing the filler and the coupling agent of tool covering function, said filler is a titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide, said coupling agent is an aluminate coupling agent, titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide, aluminate coupling agent, methyl methacrylate, benzoyl peroxide, Resorcinol, the 26-ditertbutylparacresol, the content of tertiary butyl phenolic aldehyde resin is respectively 10%～20% of the chloroprene rubber weight that feeds intake, 5%～10%, 3%～6%, 3%～6%, 0.15%～0.3%, 35%～60%, 0.7%～1.0%, 0.4%～0.6%, 0.4%～0.7%, 15%～20%, the feed ratio of chloroprene rubber and solvent is 1: 6.8～7.4 (weight ratios).
2. tool as claimed in claim 1 is covered with paint, lacquer, colour wash, etc. and is covered the high-adhesive-strength of anti-xanthochromia graft neoprene adhesive, it is characterized in that the content of titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide, aluminate coupling agent is respectively 14%～16%, 7%～8%, 4%～5%, 4%～5%, 0.20%～0.25% of the chloroprene rubber weight that feeds intake.
3. tool is covered with paint, lacquer, colour wash, etc. the production technique that covers the high-adhesive-strength of anti-xanthochromia graft neoprene adhesive, it is characterized in that at first by proportioning chloroprene rubber and titanium dioxide, light calcium carbonate, zinc oxide, magnesium oxide under the cooperation of aluminate coupling agent with solvent evenly after, it is dropped into band stirs, condensation, in the reactor of temperature regulating device, continue to stir colloidal sol down in 60～80 ℃, after treating dissolving fully, add methyl methacrylate and benzoyl peroxide and carry out graft copolymerization, be reflected under 80～90 ℃ and carry out, react after 4 hours, add Resorcinol and 26-ditertbutylparacresol termination reaction, and add the tackifier tert butyl phenolic resin, stop after the dissolving fully stirring, discharging.
4. tool as claimed in claim 3 is covered with paint, lacquer, colour wash, etc. the production technique that covers the high-adhesive-strength of anti-xanthochromia graft neoprene adhesive, and the graft copolymerization temperature that it is characterized in that adding methyl methacrylate and benzoyl peroxide is 83～86 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96102957A CN1052998C (en) | 1996-03-22 | 1996-03-22 | High adhesion strength graft chlorobutyl rubber adhesive with changing-to-yellow resistant of coatings thereof, and process for prodn. of same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96102957A CN1052998C (en) | 1996-03-22 | 1996-03-22 | High adhesion strength graft chlorobutyl rubber adhesive with changing-to-yellow resistant of coatings thereof, and process for prodn. of same |
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| Publication Number | Publication Date |
|---|---|
| CN1134965A true CN1134965A (en) | 1996-11-06 |
| CN1052998C CN1052998C (en) | 2000-05-31 |
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| CN96102957A Expired - Fee Related CN1052998C (en) | 1996-03-22 | 1996-03-22 | High adhesion strength graft chlorobutyl rubber adhesive with changing-to-yellow resistant of coatings thereof, and process for prodn. of same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023285A1 (en) * | 1998-10-22 | 2000-04-27 | H.B. Fuller Licensing & Financing, Inc. | Photo album page adhesive with color stability |
| CN101037577B (en) * | 2007-04-30 | 2010-12-22 | 湖南神力实业有限公司 | Nano chlorobutadiene rubber adhesive and preparation method thereof0} |
| CN101921563A (en) * | 2010-09-16 | 2010-12-22 | 武汉理工大学 | Adhesive for powder metallurgy-macromolecule self-lubricating composite and preparation method thereof |
| CN102702995A (en) * | 2012-05-28 | 2012-10-03 | 常州大学 | Preparation method of aqueous emulsion type neoprene antioxidant system product |
| CN103045134A (en) * | 2011-11-30 | 2013-04-17 | 成都盛尔嘉科技有限公司 | Chloroprene rubber adhesive agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1006708B (en) * | 1987-12-03 | 1990-02-07 | 厦门大学 | Graft duprene rubber adhesive with second active monomer composition |
-
1996
- 1996-03-22 CN CN96102957A patent/CN1052998C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023285A1 (en) * | 1998-10-22 | 2000-04-27 | H.B. Fuller Licensing & Financing, Inc. | Photo album page adhesive with color stability |
| CN101037577B (en) * | 2007-04-30 | 2010-12-22 | 湖南神力实业有限公司 | Nano chlorobutadiene rubber adhesive and preparation method thereof0} |
| CN101921563A (en) * | 2010-09-16 | 2010-12-22 | 武汉理工大学 | Adhesive for powder metallurgy-macromolecule self-lubricating composite and preparation method thereof |
| CN101921563B (en) * | 2010-09-16 | 2012-11-07 | 武汉理工大学 | Adhesive for powder metallurgy-macromolecule self-lubricating composite and preparation method thereof |
| CN103045134A (en) * | 2011-11-30 | 2013-04-17 | 成都盛尔嘉科技有限公司 | Chloroprene rubber adhesive agent and preparation method thereof |
| CN102702995A (en) * | 2012-05-28 | 2012-10-03 | 常州大学 | Preparation method of aqueous emulsion type neoprene antioxidant system product |
| CN102702995B (en) * | 2012-05-28 | 2014-04-30 | 常州大学 | Preparation method of aqueous emulsion type neoprene antioxidant system product |
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| CN1052998C (en) | 2000-05-31 |
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