CN1063207C - Light-color grifted neoprene adhesive and its prodn - Google Patents
Light-color grifted neoprene adhesive and its prodn Download PDFInfo
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- CN1063207C CN1063207C CN96120201A CN96120201A CN1063207C CN 1063207 C CN1063207 C CN 1063207C CN 96120201 A CN96120201 A CN 96120201A CN 96120201 A CN96120201 A CN 96120201A CN 1063207 C CN1063207 C CN 1063207C
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- chloroprene rubber
- ultraviolet absorbers
- adhesive
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Abstract
The present invention relates to a graft polychloroprene adhesive containing polychloroprene, a solvent, methyl methacrylate, benzoperoxide, hydroquinone, 2, 6-ditert-butyl p-cresol, a tert-butyl phenolic resin and an ultraviolet light absorbent. The present invention which adopts a nitrogen introducing protection technology and is additionally provided with the ultraviolet light absorbent in the process of manufacturing and packaging the adhesive effectively prevents the adhesive from being oxidized by the oxygen of air as well as prevents the adhesive from ageing and color change phenomena caused by ultraviolet light, and thus, the graft polychloroprene adhesive with light color and anti-yellowing property can be obtained.
Description
The present invention relates to a kind of graft type neoprene adhesive.
Be used for polyvinyl chloride (PVC) leatheroid, urethane (PU) synthetic leather, rubber, leather, the bonding tackiness agent of multiple synthetic materials such as simulated leather mainly obtains by chloroprene rubber and methyl methacrylate (MMA) graft copolymerization.
Along with the trend of material for shoes, more and more higher to the requirement of tackiness agent color and luster to the light color development.Tackiness agent on the present market, production initial stage color is still shallow, but after storing for some time, color and luster is just handed over dark hastily, thereby cause the problem of two aspects: one influences the attractive in appearance of product shoes, the friendship of its two color and luster is a kind of superpolymer aged performance deeply, thereby causes the deterioration of tackiness agent adhesiveproperties.Therefore, the anti-xanthochromia problem of graft neoprene adhesive is that tackiness agent manufacturer and footwear industry manufacturers extremely pay close attention to and insurmountable always problem always.
Ma Xingfa etc. (discussion of graft neoprene adhesive color and luster problem, Chinese tackiness agent, 1994,3 (1), 22-24) inquired into the color and luster problem of graft neoprene adhesive and proposed some innovative approachs.Promptly when colloidal sol, adopt high-speed stirring, make the bigger neoprene latex molecule of molecular weight distribution issue the first portion fracture, but after adding polymerization single polymerization monomer and initiator, transfer slow stirring velocity as far as possible,, influence the glue color and luster in order to avoid be involved in a large amount of air in high shear.When the solid content of chloroprene rubber is 10～13%, initiator amount is 1.5phr, temperature of reaction is 90 ± 1 ℃, reaction times should be controlled in the 3h, except the first monomer M MA, also add the vinyl acetate of 5phr or vinylformic acid isoreactivity monomer and 10～20phr chlorinity and be 35～45% chlorination EVA, help obtaining the more shallow graft neoprene adhesive of color and luster.This article is from the preparation process of tackiness agent, inquired into obtain light tackiness agent the measure that should take, but the anti-xanthochromia problem after tackiness agent stored and use does not relate to.
Li Yaan (development of graft type chloroprene rubber adhesive agent, bonding, 1994,15 (6), 28～29) has proposed a kind of graft neoprene adhesive manufacturing process of laboratory condition.Be about to chloroprene rubber and place beaker; under stirring at normal temperature, be dissolved in the toluene; add initiator and methyl methacrylate again; under nitrogen protection, glue is heated to certain temperature; insulated and stirred is after a few hours; add the hydroquinone of polymerization retarder termination reaction; and add other auxiliary such as antioxidant 264 etc., and stop heating, continue to stir; under vacuum, concentrate glue simultaneously; when treating that temperature is reduced to 40 ℃ of left and right sides, stop to vacuumize, add toluene; glue is transferred to original content, reclaim the toluene and the MMA mixed solution that steam.And in the proposition reaction process nitrogen protection should be arranged; but can not in reaction vessel, charge into nitrogen simply,, must vacuumize inflated with nitrogen again because there is part oxygen to be dissolved in toluene or the reaction solution; just can reach the deoxygenation purpose after 2～3 times so repeatedly, technology is complicated.And think that tackifier such as terpine resin do not have obvious improvement to the performance of grafting tackiness agent, and can deepen the color and luster of glue.
Dai Lizong discloses in the CN96102957.9 patent application a kind of " tool is covered with paint, lacquer, colour wash, etc. and covered the high-adhesive-strength of anti-xanthochromia graft neoprene adhesive and production technique thereof ", this technology has been added white weighting agents such as titanium dioxide and light calcium carbonate, magnesium oxide, zinc oxide in composition, light is had refraction action, weakened the absorption of tackiness agent light.What obtain is an oyster white thickness glue, thereby has covering with paint, covering and anti-yellowing function, again because the strengthening action of weighting agent, thereby has produced adhesive effect preferably.
Purpose of the present invention is intended to develop the New Graft Chloroprene Rubber Adhesive of the light high-adhesive-strength of a kind of ultraviolet resistance and anti-variable color.
The anti-yellow handing-over branch chloroprene rubber adhesive agent of the said light color of the present invention comprises chloroprene rubber, solvent, methyl methacrylate, benzoyl peroxide, Resorcinol, 2,6 ditertiary butyl p cresol, tertiary butyl phenolic aldehyde resin and ultraviolet absorbers.The structural formula of said ultraviolet absorbers is
-dihydroxy benaophenonel or neighbour-(2-hydroxybenzoyl) ferrocene.
Solvent, methyl methacrylate, benzoyl peroxide, Resorcinol, 2, the add-on of 6-ditertbutylparacresol, tert butyl phenolic resin and ultraviolet absorbers is respectively 680～700% of the chloroprene rubber weight that feeds intake, 40～100%, 0.7～1.2%, 0.4～0.6%, 0.4～0.7%, 15～2% and 0.5～1.2%.The add-on of ultraviolet absorbers is preferably: 0.6～1.0%.Solvent for use and proportioning thereof are as follows:
Vinyl acetic monomer: hexanaphthene: 120# gasoline: butanone=50: 20: 20: 10 or
Vinyl acetic monomer: acetone: 120# gasoline: butanone=30: 20: 35: 15 or
Vinyl acetic monomer: toluene: 120# gasoline=25: 30: 45 or
Toluene: butanone=90: 10
The manufacturing process of the anti-yellow handing-over branch nitrogen fourth tackiness agent of the said light color of the present invention is as follows: by proportioning chloroprene rubber and solvent input band are stirred, condensation, nitrogen conduit, in the reactor of temperature regulating device, under the condition of logical nitrogen, continue to stir colloidal sol down in 60～70 ℃, after must dissolving fully, add methymethacrylate and benzoyl peroxide and carry out graft copolymerization, be reflected under 75～90C and carry out, preferably 85～88 ℃, react after 3.5 hours, cooling is cooled to 40～50 ℃, adds terminator Resorcinol and anti-aging agent 2, the 6-ditertbutylparacresol, the tackifier tert butyl phenolic resin.After treating that temperature is reduced to room temperature (about 30 ℃), add ultraviolet absorbers, continue again to stir 3 hours, close nitrogen and get final product discharging.At last tackiness agent is injected behind the pail pack to charge into again and pack with nitrogen.
Gained adhesive quality technical indicator:
Outward appearance: faint yellow transparent viscous fluid, not stratified, there is not precipitation, colourity: YO3 (pressing the GB-3181-82 duplicate carries out).
Solids content (%): 20 ± 2
Viscosity (mPa.s, 25 ℃): 1800～3000
Stripping strength (N/cm) (being undertaken) by the GB532-82 regulation:
PVC leather～PVC leather 〉=30
PU leather～PU leather 〉=32
PVC leather～PU leather 〉=32
Storage period: sealing, lucifuge, shady and cool place 10 months.
The present invention has adopted logical nitrogen technology and added ultraviolet absorbers to reach two purposes in the preparation of graft neoprene adhesive and wrapping process: one has prevented that in high-temperature reaction process airborne oxygen from causing macromolecular chain to rupture to the oxygenizement of chloroprene rubber and making glue thinning and aging (causing the color and luster intensification) phenomenon under oxygenant (initiator).Also prevented air residual in pail pack oxygenizement to tackiness agent in the long-term storage process.Its two, ultraviolet absorbers
There is following quick tautomerism,
After absorption agent had absorbed UV-light, luminous energy was opened chelate ring (six membered ring), and when chelate ring closed loop again, the energy that is absorbed discharges with other harmless form again, thereby had prevented the ultraviolet light and aging variable color of polymkeric substance.It is YO4 that this tackiness agent is stored 10 months colourity through sealing, lucifuge, shady and cool place.In addition, manufacturing process of the present invention is simple, needn't carry out loaded down with trivial details vacuum, has reduced production cost.
Grafting neoprene chamber stick through anti-yellow mating side, technology are made and common graft neoprene adhesive (with this manufacture method difference: 1. logical nitrogen technology; 2. not adding structure is
Ultraviolet absorbers) seal, see 10 months test of light, the former color is slightly handed over Huang, and the latter has become purple brown, colourity is respectively: YO5 and YRO3.
The invention will be further described with embodiment below.
Embodiment 1: (a day electrification is produced with 20g chloroprene rubber A-90, polymerization-grade) drops into 250ml electric mixer is housed, reflux condensing tube, thermometer, in the four-necked bottle of nitrogen conduit, add 138g solvent (toluene: butanone=90: 10) again, logical nitrogen (flow velocity: 0.2L/min), carrying out colloidal sol to chloroprene rubber in 65 ℃ of following stirrings dissolves fully, 85 ℃ add 9.0g methyl methacrylate and 0.18g benzoyl peroxide down, reacted 3.5 hours, after being cooled to 50 ℃, add the 0.1g Resorcinol, 0.12g 2, the 6-ditertbutylparacresol, 3.6g tertiary butyl phenolic aldehyde resin treats that temperature adds ultraviolet absorbers neighbour-dihydroxy benaophenonel 0.18g when reducing to about 30 ℃, continue again to stir after 3 hours to close nitrogen, discharging.The gained tackiness agent is removed from office sticking the bonding strength of material: PVC: 31.5N/cm, the PU leather is to sticking: 32.0N/cm, PVC leather～PU leather: 32.6N/cm.
Embodiment 2: (a day electrification is produced with 20g chloroprene rubber A-90, polymerization-grade) drops into 250ml electric mixer is housed, reflux condensing tube, thermometer, in the four-necked bottle of nitrogen conduit, add 140g solvent (vinyl acetic monomer: toluene: 120# gasoline=25: 30: 45) again, logical nitrogen (flow velocity: 0.2L/min), 60 ℃ of following stirrings are carried out colloidal sol to chloroprene rubber and are dissolved fully, 80 ℃ add 9.5g methyl two olefin(e) acid methyl esters down, when rising to 86 ℃, temperature adds the 0.2g benzoyl peroxide, reacted 3.5 hours, add the 0.1g Resorcinol after being cooled to 50 ℃, 0.12g 2, the 6-ditertbutylparacresol, 3.8g tertiary butyl phenolic aldehyde resin treats that temperature adds ultraviolet absorbers neighbour-(2-hydroxybenzoyl) ferrocene 0.20g when reducing to 30 ℃, continue again to stir after 3 hours to close nitrogen, discharging.The gained tackiness agent is removed from office sticking the bonding strength of material: PVC: 32.2N/cm, the PU leather is to sticking: 33.8N/cm, PVC leather～PU.Leather: 32.6N/cm.
Embodiment 3～5: the preparation method changes the consumption of methyl methacrylate, benzoyl peroxide, tertiary butyl phenolic aldehyde resin and ultraviolet absorbers with embodiment 1, the results are shown in following table.
Embodiment 6 (expanding tests, condition by embodiment 2 is carried out, in 200 liters of reactors, carry out): with 20kg chloroprene rubber A-90, the 140kg solvent drops into reactor, logical nitrogen (flow velocity 2L/min), 60 ℃ of following stirrings are carried out colloidal sol to chloroprene rubber and are dissolved fully, heat up 80 ℃ and add the 9.5kg methyl methacrylate down, add the 200g benzoyl peroxide when temperature rises to 86 ℃, react adding 100g Resorcinol behind 3.5 hours fast coolings to 50 ℃, 120g2, the 6-ditertbutylparacresol, 3.8kg tertiary butyl phenolic aldehyde resin adds neighbour-(2-hydroxybenzoyl) ferrocene 200g when equitemperature is reduced to 30 ℃, continue to stir discharging after 3 hours again.The gained tackiness agent is removed from office sticking the bonding result of material: PVC: 33.8N/cm, the PU leather is to sticking: 34.8N/cm, PVC leather～PU leather: 33.6N/cm.
Claims (4)
1. the light color graft type of anti-xanthochromia chloroprene rubber adhesive agent, contain neoprene rubber, solvent, methyl methacrylate, benzoyl peroxide, Resorcinol, 2, the 6-ditertbutylparacresol, tertiary butyl phenolic aldehyde resin, it is characterized in that also containing ultraviolet absorbers, solvent, methyl methacrylate, benzoyl peroxide, Resorcinol, 2,6 ditertiary butyl p cresol, the content of tert butyl phenolic resin and ultraviolet absorbers is respectively 680%～700% of the chloroprene rubber weight that feeds intake, 40%～100%, 0.7%～1.2%, 0.4%～0.6%, 0.4%～0.7%, 15%～22% and 0.5%～1.2%.
2. the light color graft type of anti-xanthochromia chloroprene rubber adhesive agent as claimed in claim 1 is characterized in that the general structure of said ultraviolet absorbers is
3. the light color graft type of anti-xanthochromia chloroprene rubber adhesive agent as claimed in claim 1, the content that it is characterized in that ultraviolet absorbers is 0.6%～1.0% of the neoprene latex weight that feeds intake.
4. the manufacturing process of the light color graft type of anti-xanthochromia chloroprene rubber adhesive agent according to claim 1, it is characterized in that at first chloroprene rubber and solvent input band being stirred by proportioning, condensation, nitrogen conduit, in the reactor of temperature regulating device, under the condition of logical nitrogen, in 60～70 ℃ of following colloidal sols, add methyl methacrylate and benzoyl peroxide then and carry out graft copolymerization, be reflected under 75～90 ℃ and carry out, react 3.5 hours postcooling, add terminator Resorcinol and anti-aging agent 2 when being cooled to 40～50 ℃, the 6-ditertbutylparacresol, the tackifier tert butyl phenolic resin, after treating that temperature is reduced to room temperature, add ultraviolet absorbers, restir 3 hours, close nitrogen, pack again with the nitrogen filling after tackiness agent being injected pail pack at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120201A CN1063207C (en) | 1996-10-21 | 1996-10-21 | Light-color grifted neoprene adhesive and its prodn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120201A CN1063207C (en) | 1996-10-21 | 1996-10-21 | Light-color grifted neoprene adhesive and its prodn |
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| Publication Number | Publication Date |
|---|---|
| CN1153804A CN1153804A (en) | 1997-07-09 |
| CN1063207C true CN1063207C (en) | 2001-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120201A Expired - Fee Related CN1063207C (en) | 1996-10-21 | 1996-10-21 | Light-color grifted neoprene adhesive and its prodn |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665464A (en) * | 2013-12-02 | 2014-03-26 | 珠海经济特区科茂橡塑材料有限公司 | Application of rubber thiocarbamate accelerant and yellowing-resistant rubber combined formula |
| CN104212388A (en) * | 2014-09-05 | 2014-12-17 | 无锡欧易博阀业科技有限公司 | Modified neoprene |
| CN105870273B (en) * | 2016-06-02 | 2018-10-30 | 厦门市三安光电科技有限公司 | A kind of iii-nitride light emitting devices |
| CN106366954A (en) * | 2016-08-30 | 2017-02-01 | 无锡万能胶粘剂有限公司 | Tasteless all-purpose adhesive |
| CN113061412B (en) * | 2021-03-23 | 2022-10-04 | 广东多正树脂科技有限公司 | Yellow glue capable of resisting plasticizer migration and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065082A (en) * | 1991-03-15 | 1992-10-07 | 辛辉 | A kind of modified version neoprene graft binding agent and manufacture method thereof |
| JPH0586347A (en) * | 1991-09-28 | 1993-04-06 | Aica Kogyo Co Ltd | Adhesive |
-
1996
- 1996-10-21 CN CN96120201A patent/CN1063207C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065082A (en) * | 1991-03-15 | 1992-10-07 | 辛辉 | A kind of modified version neoprene graft binding agent and manufacture method thereof |
| JPH0586347A (en) * | 1991-09-28 | 1993-04-06 | Aica Kogyo Co Ltd | Adhesive |
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| CN1153804A (en) | 1997-07-09 |
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