CN103205894B - Finished and brightened polyurethane leather surface treatment agent with real-feather feel and preparation method thereof - Google Patents
Finished and brightened polyurethane leather surface treatment agent with real-feather feel and preparation method thereof Download PDFInfo
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- CN103205894B CN103205894B CN201310112748.6A CN201310112748A CN103205894B CN 103205894 B CN103205894 B CN 103205894B CN 201310112748 A CN201310112748 A CN 201310112748A CN 103205894 B CN103205894 B CN 103205894B
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Abstract
The invention relates to a finished and brightened polyurethane leather surface treatment agent with a real-feather feel. The finished and brightened polyurethane leather surface treatment agent is prepared by mixing 100 parts of solvent-based PU (Polyurethane), 3-9 parts of matting powder, 4-12 parts of organosilicone additives and 60-100 parts of a solvent, wherein the solvent-based PU is prepared by reacting diisocyanate, polyhydric alcohol, a chain extender, reactive organosilicone, an antioxidant, a dehydrating agent and catalysts in the presence of an organic solvent; and the molar ratio of the diisocyanate to the polyhydric alcohol to the chain extender to the reactive organosilicone is equal to (3.5-4.5):(2-3.5):1:(0.2-0.3). The finished and brightened polyurethane leather surface treatment agent has the advantages that the real-leather feel and the layering feel of a coating are obviously improved, so that the coating is very like real leather; and the water rubbing resistance, the wearing resistance and the scratch resistance of the coating are improved.
Description
Technical field
The present invention relates to polyurethane surface treating agent technical field, be specifically related to a kind of hot fog light kishke feel polyurethane leather surface finishing agent and preparation method thereof.
Background technology
Along with living standard constantly improves, people can constantly increase the demand of corium, and natural leather resource meeting day is inadequate.Polyurethane imitation corium has substituted the use of corium to a certain extent.The anti-corium of polyurethane is exactly to use special polyurethane finishing agent on polyurethane leather surface, after specific processes, makes its surface have sense of touch, the luminosity of corium and the characteristic of corium of corium, thereby reaches the effect of anti-corium.
At present, polyurethane finishing agent is on the market various in style, but has the finishing agent of kishke feel to have no report, for example, in hot light series, after scalding, substantially there is no sense of touch, is difficult to meet the demand of client to kishke feel.Therefore, need to prepare a kind of leather surface treatment agent of hot fog light kishke feel.
Summary of the invention:
The present invention is intended to propose a kind of hot fog light kishke feel polyurethane leather surface finishing agent and preparation method thereof, is used in after leather and fur products surface treatment, scalds after bright, water rubs through uniform temperature, and leather surface has luminosity and the sense of touch of corium, and can give leather stereovision.
This hot fog light kishke feel polyurethane leather surface finishing agent, by solvent-borne type PU(polyurethane resin), flatting silica, organosilicon auxiliary agent and solvent composition, its proportioning is by weight:
Solvent-borne type PU:100 part,
Flatting silica: 3～9 parts,
Organosilicon auxiliary agent: 4～12 parts,
Solvent: 60～100 parts;
Under the condition that wherein solvent-borne type PU is existed at organic solvent by vulcabond, polyalcohol, chain extender, response type organosilicon, antioxidant, dehydrating agent and catalyst, react and make.The described organosilyl mol ratio of vulcabond, polyalcohol, chain extender, response type is: (3.5～4.5) ︰ (2～3.5) ︰ 1 ︰ (0.2～0.3).
The preparation method of this hot fog light kishke feel polyurethane leather surface finishing agent comprises the following steps:
(1) in container, add flatting silica, organosilicon auxiliary agent and solvent by proportioning, high-speed stirred 20～40min;
(2) add 40% solvent-borne type PU of total amount, high-speed stirred 40～80min;
(3) add again remaining solvent-borne type PU, high-speed stirred 40～80min;
(4) grind after 15～30min, with 120 order polypropylene nets filtrations, obtain finished product;
The synthesis technique of wherein said solvent-borne type PU is:
(a) polyalcohol, antioxidant, dehydrating agent and partial solvent are joined in reactor, be warming up to 50 DEG C, stir 20～40min;
(b) add 70% vulcabond of total amount by proportioning, 70～95 DEG C of reactions 1.5～2.5 hours;
(c) add chain extender and response type organosilicon, 70～95 DEG C are reacted 1～1.5 hour;
(d) add catalyst, 65～80 DEG C are reacted 1.5～2.5 hours;
(e) add remaining vulcabond, regulate the viscosity of resin by vulcabond, add solvent, make viscosity reach 5000～7000cps/25 DEG C.
This hot fog light kishke feel polyurethane leather surface finishing agent has the following advantages:
1. after using this hot fog light kishke feel polyurethane leather surface finishing agent to process, imitation polyurethane epidermis face through scalding bright after, obviously increased kishke feel and the stereovision of coating, make it approach very much corium.Because organosilicon in solvent-borne type PU resin building-up process has been participated in reaction, make polyurethane resin with corium sense of touch.Meanwhile, preparing in finishing agent process, again add organosilicon auxiliary agent, finishing agent sense of touch is strengthened.Therefore, scald bright after, the sense of touch of coating is as corium.
2. the water-fast of coating rubs, anti-wear performance is improved: general hot fog light finishing agent, through scalding after leather water after bright rubs, brightness, gorgeous degree generally all can reduce, and after the product that use the present invention makes, water can maintain the original state after rubbing, and this is owing to adding organosilicon in course of reaction, has improved the anti-wear performance of leather surface.
Detailed description of the invention:
This hot fog light kishke feel polyurethane leather surface finishing agent is by solvent-borne type PU, flatting silica, organosilicon auxiliary agent and solvent composition, and its proportioning is by weight:
Solvent-borne type PU:100 part,
Flatting silica: 3～9 parts,
Organosilicon auxiliary agent: 4～12 parts,
Solvent: 60～100 parts;
Under the condition that wherein said solvent-borne type PU is existed at organic solvent by vulcabond, polyalcohol, chain extender, response type organosilicon, antioxidant, dehydrating agent and catalyst, react and make.The described organosilyl mol ratio of vulcabond, polyalcohol, chain extender, response type can be: the many first alcohol ︰ of two different cyanogen acid ester ︰ expand chain agent ︰ response type organosilicon=(3.5～4.5) ︰ (2～3.5) ︰ 1 ︰ (0.2～0.3).
In this hot fog light kishke feel polyurethane leather surface finishing agent, the described vulcabond of preparing solvent-borne type PU can be one or more the mixture in isophorone diisocyanate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hydrogenated diphenyl methane diisocyanate, hexamethylene diisocyanate; Described polyalcohol can be one or more the mixture in polyethylene glycol adipate glycol, poly-adipic acid-BDO esterdiol, polytetrahydrofuran diol, polyoxypropyleneglycol, polycaprolactone glycol; Described chain extender can be ethylene glycol, BDO, 1, the mixture of one or more in 6-hexylene glycol, neopentyl glycol, two adjacent chlorodiphenyl amine methane; Described response type organosilicon can be for end hydroxyl silicone oil, hold amido silicon oil, with one or more the mixture in chain reaction type silicone oil; Described catalyst can be one or more the mixture in stannous octoate, organo-bismuth, triethylamine.
In this hot fog light kishke feel polyurethane leather surface finishing agent, described flatting silica can be one or more the mixture in silica, calcium carbonate, organo montmorillonite; Described organosilicon auxiliary agent can be one or more the mixture in hydroxy silicon oil, polyether silicone oil, methyl-silicone oil.
The preparation method of this hot fog light kishke feel polyurethane leather surface finishing agent comprises the following steps:
(1) in container, add flatting silica, organosilicon auxiliary agent and solvent by proportioning, high-speed stirred 20～40min;
(2) add 40% solvent-borne type PU of total amount, high-speed stirred 40～80min;
(3) add again remaining solvent-borne type PU, high-speed stirred 40～80min;
(4) grind after 15～30min, with 120 order polypropylene nets filtrations, obtain finished product;
The synthesis technique of wherein said solvent-borne type PU is:
(a) by proportioning, polyalcohol, antioxidant, dehydrating agent and partial solvent are joined in reactor, be warming up to 50 DEG C, stir 20～40min;
(b) add 70% vulcabond of total amount, 70～95 DEG C of reactions 1.5～2.5 hours;
(c) add chain extender and response type organosilicon, 70～95 DEG C are reacted 1～1.5 hour;
(d) add catalyst, 65～80 DEG C are reacted 1.5～2.5 hours;
(e) add remaining vulcabond, regulate the viscosity of resin by vulcabond, add solvent, make viscosity reach 5000～7000cps/25 DEG C.
Introduce embodiment below:
Embodiment 1
(1) preparation of polyurethane resin: add polyalcohol 180g(polycaprolactone glycol in the reactor of 1L), solvent (dimethyl formamide) 250g, antioxidant (antioxidant 1010) 0.5g, dehydrating agent (2-amino-4-chloropyridine chloromethyl chlorosulfonic acid ester, be called for short TI) 0.5g, be warming up to 50 DEG C, stir 30min; Add vulcabond 129.1g('-diphenylmethane diisocyanate), react 2h at 75 DEG C; Add wherein ethylene glycol 60%, 1.4-butanediol 30%, neopentyl glycol 10% by weight of chain extender 40g() and organosilicon (two organic hydroxy silicate) 11g, 75 DEG C of reaction 1h; Add the sub-tin 0.1g of octoate catalyst, 70 DEG C of reaction 2h; Add gradually vulcabond ('-diphenylmethane diisocyanate) 55.3g to resin viscosity to 50000cps/25 DEG C, then add solvent (butanone) 165.4g.Final polyurethane resin 831.9g, solid content 50%, the viscosity 6000cps/25 DEG C of obtaining.
(2) preparation of surface conditioning agent: add flatting silica 10.5g(silica in container), wherein methyl-silicone oil 40% by weight of addition type organosilicon 12g(, polyether modified silicon oil 60%) and wherein dimethyl formamide 50%, toluene 50% by weight of solvent 120g(), high-speed stirred 30min; The solvent-borne type PU63g that adds (1) step to make, high-speed stirred 60min; The solvent-borne type PU94.5g that adds again (1) step to make, high-speed stirred 60min; Grind after 20min, with 120 order polypropylene nets filtrations, obtain hot fog light kishke feel polyurethane surface treating agent finished product 300g.
Embodiment 2
(1) preparation of polyurethane resin: add wherein polytetrahydrofuran diol 50%, poly-adipic acid-1 by weight of polyalcohol 180g(in the reactor of 1L, 4-butanediol ester glycol 25%, polycaprolactone glycol 25%), solvent (dimethyl formamide) 270g, antioxidant triphenyl phosphite 0.5g, dehydrating agent (TI) 0.5g, be warming up to 50 DEG C, stir 30min; Add vulcabond 129.1g('-diphenylmethane diisocyanate), react 2h at 75 DEG C; Add wherein ethylene glycol 50%, 1.6-hexylene glycol 30%, neopentyl glycol 20% by weight of chain extender 44.5g() and organosilicon (polyamino organosilicon) 11.5g, 75 DEG C of reaction 1h; Add catalyst (stannous octoate) 0.1g, 70 DEG C of reaction 2h; Add gradually vulcabond ('-diphenylmethane diisocyanate) 55.3g to resin viscosity to 55000cps/25 DEG C, then add solvent (toluene) 151.4g.Final polyurethane resin 842.9g, solid content 50%, the viscosity 5000cps/25 DEG C of obtaining.
(2) preparation of surface conditioning agent: add wherein calcium carbonate 40%, organo montmorillonite 60% by weight of flatting silica 3.6g(by proportioning in container), wherein methyl-silicone oil 30% by weight of addition type organosilicon 14.4g(, methoxyl group silicone oil 70%) and wherein butanone 50%, ethyl acetate 50% by weight of solvent 120g(), high-speed stirred 30min; The solvent-borne type PU48g that adds (1) step to make, high-speed stirred 60min; The solvent-borne type PU72g that adds again (1) step to make, high-speed stirred 60min; Grind after 20min, with 120 order polypropylene nets filtrations, obtain hot fog light kishke feel polyurethane surface treating agent finished product 258g.
Embodiment 3
(1) preparation of polyurethane resin: add wherein polyoxypropyleneglycol 20%, polyethylene glycol adipate glycol 20%, polycaprolactone glycol 60% by weight of polyalcohol 216g(in the reactor of 1L), solvent (dimethyl formamide) 264g, antioxidant triphenyl phosphite 0.5g, dehydrating agent (TI) 0.5g, be warming up to 50 DEG C, stir 30min; Add vulcabond 113.4g('-diphenylmethane diisocyanate), react 2h at 75 DEG C; Add wherein ethylene glycol 50%, two adjacent chlorodiphenyl amine methane 35%, methyl propanediol 15% by weight of chain extender 39.6g() and wherein polyhydroxy organosilicon 50%, polyamino organosilicon 50% by weight of organosilicon 11.5g(), 75 DEG C of reaction 1h; Add catalyst organo-bismuth 0.1g, 70 DEG C of reaction 2h; Add gradually vulcabond ('-diphenylmethane diisocyanate) 48.6g to resin viscosity to 65000cps/25 DEG C, then add wherein toluene 50%, isopropyl alcohol 50% by weight of solvent 165.1g().Final polyurethane resin 859.3g, solid content 50%, the viscosity 6000cps/25 DEG C of obtaining.
(2) preparation of surface conditioning agent: add wherein silica 70%, calcium carbonate 30% by weight of flatting silica 14.4g(in container), wherein methyl phenyl silicone oil 40% by weight of addition type organosilicon 6.4g(, polyether modified silicon oil 60%) and wherein isopropyl alcohol 50%, butyl acetate 50% by weight of solvent 96g(), high-speed stirred 30min; The solvent-borne type PU64g that adds (1) step to make, high-speed stirred 60min; The solvent-borne type PU96g that adds again (1) step to make, high-speed stirred 96min; Grind after 20min, with 120 order polypropylene nets filtrations, obtain hot fog light kishke feel polyurethane surface treating agent finished product 276.8g.
Embodiment 4
(1) preparation of polyurethane resin: add polyalcohol 162g(polycaprolactone glycol in the reactor of 1L), solvent (dimethyl formamide) 234g, antioxidant (antioxidant 1010) 0.5g, dehydrating agent (TI) 0.5g, be warming up to 50 DEG C, stir 30min; Add vulcabond 127.5g('-diphenylmethane diisocyanate), react 2h at 75 DEG C; Add wherein ethylene glycol 60%, 1.4-butanediol 30%, neopentyl glycol 10% by weight of chain extender 40.7g() and organosilicon (two organic hydroxy silicate) 10.4g, 75 DEG C of reaction 1h; Add catalyst 0.1g, 70 DEG C of reaction 2h; Add gradually vulcabond ('-diphenylmethane diisocyanate) 57.7g to resin viscosity to 70000cps/25 DEG C, then add solvent (butanone) 165.3g.Final polyurethane resin 798.7g, solid content 50%, the viscosity 6500cps/25 DEG C of obtaining.
(2) preparation of surface conditioning agent: add flatting silica 9g(silica by proportioning in container), wherein methyl-silicone oil 40% of addition type organosilicon 15g(, methyl phenyl silicone oil 60%) and wherein dimethyl formamide 50%, toluene 50% of solvent 120g(), high-speed stirred 30min; The solvent-borne type PU60g that adds (1) step to make, high-speed stirred 60min; The solvent-borne type PU90g that adds again (1) step to make, high-speed stirred 60min; Grind after 20min, with 120 order polypropylene nets filtrations, obtain hot fog light kishke feel polyurethane surface treating agent finished product 294g.
In embodiment, gained hot fog light kishke feel polyurethane leather surface finishing agent and the film performance on synthetic leather are as following table.
Claims (2)
1. a hot fog light kishke feel polyurethane leather surface finishing agent, by solvent-borne type PU, flatting silica, organosilicon auxiliary agent and solvent composition, its proportioning is by weight:
Solvent-borne type PU:100 part,
Flatting silica: 3～9 parts,
Organosilicon auxiliary agent: 4～12 parts,
Solvent: 60～100 parts;
It is characterized in that described solvent-borne type PU is reacted and makes under the condition of organic solvent existence by vulcabond, polyalcohol, chain extender, response type organosilicon, antioxidant, dehydrating agent and catalyst; The described organosilyl mol ratio of vulcabond, polyalcohol, chain extender, response type is: (3.5～4.5): (2～3.5): 1:(0.2～0.3); The described vulcabond of preparing solvent-borne type PU is one or more the mixture in isophorone diisocyanate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hydrogenated diphenyl methane diisocyanate, hexamethylene diisocyanate; Described polyalcohol is one or more the mixture in polyethylene glycol adipate glycol, poly-adipic acid-BDO esterdiol, polytetrahydrofuran diol, polyoxypropyleneglycol, polycaprolactone glycol; Described chain extender is ethylene glycol, BDO, 1, the mixture of one or more in 6-hexylene glycol, neopentyl glycol, two adjacent chlorodiphenyl amine methane; Described response type organosilicon is end hydroxyl silicone oil, hold amido silicon oil, with one or more the mixture in chain reaction type silicone oil; Described catalyst is one or more mixtures in stannous octoate, organo-bismuth, triethylamine; Described flatting silica is one or more the mixture in silica, calcium carbonate, organo montmorillonite; Described organosilicon auxiliary agent is one or more the mixture in hydroxy silicon oil, polyether silicone oil, methyl-silicone oil.
2. a preparation method for hot fog light kishke feel polyurethane leather surface finishing agent, is characterized in that comprising the following steps:
(1) in container, add flatting silica, organosilicon auxiliary agent and solvent by proportioning claimed in claim 1, high-speed stirred 20～40min;
(2) add 40% solvent-borne type PU of total amount, high-speed stirred 40～80min;
(3) add again remaining solvent-borne type PU, high-speed stirred 40～80min;
(4) grind after 15～30min, with 120 order polypropylene nets filtrations, obtain finished product;
Wherein said solvent-borne type PU synthesis technique is:
(a) polyalcohol, antioxidant, dehydrating agent and partial solvent are joined in reactor, be warming up to 50 DEG C, stir 20～40min;
(b) add 70% vulcabond of total amount by proportioning claimed in claim 1,70～95 DEG C of reactions 1.5～2.5 hours;
(c) add chain extender and response type organosilicon, 70～95 DEG C are reacted 1～1.5 hour;
(d) add catalyst, 65～80 DEG C are reacted 1.5～2.5 hours;
(e) add residue vulcabond, regulate the viscosity of resin by vulcabond, add solvent, make viscosity reach 5000～7000cps/25 DEG C.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757926A (en) * | 2014-01-21 | 2014-04-30 | 宜兴市东方皮塑化工有限公司 | Surface treating agent applied to luggage leather and preparation method thereof |
| CN104086740B (en) * | 2014-07-09 | 2016-05-04 | 温州柯莱恩科技有限公司 | The preparation method of the organosilicon grafted and modified polyurethane resin of a kind of use for synthetic leather |
| CN104131466A (en) * | 2014-07-22 | 2014-11-05 | 嘉兴禾大科技化学有限公司 | Velvet feeling polyurethane leather surface conditioning agent and preparation method thereof |
| CN105839424B (en) * | 2016-05-19 | 2018-11-02 | 福建宝利特科技股份有限公司 | A kind of artificial leather and preparation method thereof that surface is added lustre to |
| CN107325258A (en) * | 2017-08-18 | 2017-11-07 | 江苏宝泽高分子材料股份有限公司 | A kind of use for synthetic leather xanthochromia type outermost layer of skin resin and preparation method thereof |
| CN113105821A (en) * | 2020-01-13 | 2021-07-13 | 浙江诚迅新材料有限公司 | High-waterproofness nubuck treating agent and preparation method thereof |
| CN111254719B (en) * | 2020-01-16 | 2022-09-09 | 上海汇得科技股份有限公司 | Fluoride-free water repellent agent for polyurethane synthetic leather and preparation method thereof |
| CN113429539A (en) * | 2021-05-31 | 2021-09-24 | 成都玉瓶科技有限公司 | Hydroxyl polysiloxane modified waterborne polyurethane emulsion, super-smooth surface coating and preparation method thereof |
| CN115537111B (en) * | 2022-10-20 | 2023-12-05 | 东莞市卓琦电子科技有限公司 | Polyurethane leather hand feeling oil and preparation method thereof |
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| CN102040719A (en) * | 2010-11-23 | 2011-05-04 | 淮安凯悦科技开发有限公司 | Organosilicon modified water-based polyurethane resin and washing treating agent for synthetic leather |
| CN102533079A (en) * | 2011-12-08 | 2012-07-04 | 浙江深蓝轻纺科技有限公司 | Extinction-type water-based polyurethane finishing agent used for synthetic leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102040719A (en) * | 2010-11-23 | 2011-05-04 | 淮安凯悦科技开发有限公司 | Organosilicon modified water-based polyurethane resin and washing treating agent for synthetic leather |
| CN102533079A (en) * | 2011-12-08 | 2012-07-04 | 浙江深蓝轻纺科技有限公司 | Extinction-type water-based polyurethane finishing agent used for synthetic leather |
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