CN103468084A - Polyacrylate modified casein leather finishing agent and preparation method thereof - Google Patents
Polyacrylate modified casein leather finishing agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyacrylate modified casein leather finishing agent and a preparation method thereof. The polyacrylate modified casein leather finishing agent comprises the following raw materials in parts by weight: 45-100 parts of an acrylate mixed monomer, 3-10 parts of methacrylic acid, 5-8 parts of acetoacetic ethyl methacrylate, 100-150 parts of casein, 20-30 parts of triethylamine, 450-850 parts of deionized water, 5-10 parts of lauryl sodium sulfate, 10-20 parts of an emulsifier and 0.1-1 part of lauryl sodium sulfate. The polyacrylate modified casein leather finishing agent is prepared by monomer emulsification, proteolysis and polymerization reaction. The polyacrylate modified casein leather finishing agent is used for leather finish, and the product is flexible in feel, good in plating release, excellent in fastness, high in gloss and good in permeability.
Description
Technical field
The present invention relates to a kind of polyacrylate modified casein finishing agent and preparation method for corium, for improving the corium feel, from the hide finishes of plate, fastness, gloss, permeability.
Background technology
The casein finishing agent is widely used in leather finish, effectively improves leather hand feeling, from performances such as plate, fastness, gloss, permeabilities.
The CN201110057116.5 patent discloses " a kind of original position soapless seed emulsion polymerization polymerization prepares the method for modified Casein/nano silicon compound film former ", this technology is the multipolymer with hexanolactam grafting casein, simultaneously, introduce proper amount of nano silicon-dioxide, for leather finish, give the glossiness of leather nature, higher anti-xerotripsis fastness and dry and comfortable feel.But it can reach the high request of high gloss, high-permeability.
The CN201110427243.X patent discloses " modified Casein, hide finishes and preparation method thereof ", this technology provides under the organic acid condition and has obtained the modified Casein finishing agent with hexanolactam generation grafting polycondensation, it shows cationic, and to improve, the casein material filming is hard, the shortcoming of inextensibility, easy fracture.But its cationic has limited its application, positively charged ion is substantially used in back cover in finishing agent, and the product appearance does not reach the effect requirements of Gao Guang, high-clarity.
The CN200910036061.2 patent discloses " a kind of preparation method of modified casein used in leather finishing ", the just independent hexanolactam modified product that uses that it provides, select NP-10 as emulsifying agent, it is a kind of polyoxyethylene nonylphenol ether, contains APEO, to the objectionable impurities of human body, it is also the kind that European Union forbids strongly, and make softening agent with glycerine, feel is hardening gradually, is difficult to reach the requirement of Gao Guang, the performance index such as penetrating, soft.
The above prior art modified Casein Leather finishing agent product is the hexanolactam modified product, and each product has characteristics separately, but all must possess that feel is soft, gloss is high, permeability is good simultaneously, the good characteristics from plate.
Summary of the invention
The purpose of this invention is to provide modification of acrylic resin casein finishing agent and preparation method for a kind of leather finish, that product has is soft, from advantages such as plate are good, fastness is good, gloss is high, permeability is good.
the polyacrylate modified Casein Leather finishing agent of the present invention:
The raw material weight proportioning:
A, acrylate mixing monomer 45-100
B, methacrylic acid 3-10
C, AAEM 5-8
D, casein 100-150
E, triethylamine 20-30
F, deionized water 450-850
G, sodium lauryl sulphate 5-10
H, Emulsifier O N-50 10-20
I, initiator 0.1-1
Through monomer emulsification, proteolysis, polyreaction, make;
The product chemical index; Outward appearance: faint yellow translucent emulsion
Ionic: the moon
PH value: 8 ± 1
Solid content: 25 ± 1%;
?acrylate mixing monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide wherein to be mixed and uses more than three kinds or three kinds;
Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds mix and use;
Emulsifier O N-50 is BASF AG's product, the agency and sales of Shanghai Suo Kai trade Co., Ltd.
the polyacrylate modified Casein Leather finishing agent of the present invention preparation method:
Raw material is by weight ratio:
(1) monomer emulsification, the pre-emulsion preparation:
By acrylate mixing monomer 45-100, Emulsifier O N-50, be that 10-20, sodium lauryl sulphate 5-10, methacrylic acid 3-10, AAEM 5-8 join in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 110-210, make pre-emulsion;
(2) proteolysis, the preparation of hydrolyzed casein liquid:
Deionized water 340--640 is added to reactor, add casein 100-150 under stirring, 75-80 ℃ then heats up, stir 0.5-1 hour, casein is fully dissolved, add triethylamine 20-30, stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3) polyreaction:
During the initiator solution that initiator 0.1-1 and deionized water 25-50 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product;
Acrylate mixing monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide wherein to be mixed and uses more than three kinds or three kinds;
Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds mix and use;
Emulsifier O N-50 is BASF AG's product, the agency and sales of Shanghai Suo Kai trade Co., Ltd.
The polyacrylate modified Casein Leather finishing agent that the inventive method obtains: ionic: the moon, the pH value: 8 ± 1, solid content: 25 ± 1%.
The inventive method producing and manufacturing technique is simple and convenient, easily realizes, has good process implementing, and aqueous, environmental protective is pollution-free simultaneously.Product is soft, good from plate, good heat resistance, fastness is good, gloss is high, permeability is good, aqueous, environmental protective.
Hydroxyl, amino and the carboxyl and the multiple acrylate monomer that after casein hydrolysis of the present invention, produce produce copolymerization, the present invention has selected methacrylic acid, AAEM and has produced copolyreaction by butyl acrylate, ethyl propenoate, vinylbenzene, the fine acrylate mixing monomer formed of propylene, various active group synergy, adjust proportional quantity, can meet soft, good from plate, good heat resistance, fastness is good, gloss is high, permeability is good feature performance benefit.Because methacrylic acid contains methyl, methyl can produce steric hindrance, can increase repulsion between products molecule, has improved water-fast, anti-solvent, wear resisting property, thereby improves dry, wet rubbing fastness after leather finish; AAEM contains active group, provides crosslinked, forms reticulated structure in cross-linking process, effectively improves the anti-boiling hot property of adhesive fastness, Bearable dry and wet wipe and high temperature, and transparency, luminance brightness strengthen.The wherein hydroxyl of hydrolyzed casein liquid, amino and carboxyl and acrylate mixing monomer polymerization reactions, itself and butyl acrylate, ethyl propenoate polymerization after product are because butyl acrylate, ethyl propenoate second-order transition temperature are low, pliability is had to obvious contribution, form product soft; Vinylbenzene, vinyl cyanide belong to hard monomer, second-order transition temperature is high, from plate, heat-resisting enhancing, fastness can effectively improve, and hard monomer can improve water-repellancy simultaneously, water repellency is had to obvious contribution, thereby anti-dry, wet rubbing fastness excellence, in addition because vinyl cyanide contains specific groups-itrile group, vinyl cyanide increases tenacity, improve fastness, transparency after above monomer synergy, brightness spy are good.
Select anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent ON-50 synergy, the pre-emulsion stable performance, make each monomer fully fused, and product film forming transparency is good, obtains modification finishing agent product stable; The ON-50 good penetrability, increase and the leather binding strength, and emulsifier is few, and good with the binding strength of leather, washing fastness is good.
Adopt multiple initiator synergy, the residual ionization monomer is few, and reaction yield is high, even molecular weight distribution, and product is stable.
Embodiment
The raw material weight proportioning.
embodiment 1,
(1), monomer emulsification, pre-emulsion preparation:
Butyl acrylate 22.5, ethyl propenoate 15, vinylbenzene 7.5, Emulsifier O N-50 10, sodium lauryl sulphate 5, methacrylic acid 3, AAEM 5 are joined in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 111, make pre-emulsion;
(2), proteolysis, hydrolyzed casein liquid preparation:
Deionized water 350 is added to reactor, add casein 100 under stirring, the 75-80 ℃ that then heats up, stir 0.5-1 hour, and casein is fully dissolved, and adds triethylamine 20, and stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3), polyreaction:
During the initiator solution that initiator ammonium persulfate 0.4, Potassium Persulphate 0.4 and deionized water 25 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product.
The present embodiment product is due to butyl acrylate, ethyl propenoate large usage quantity in the selection of vinylformic acid mix monomer raw material, and feel is the most soft, adopts two kinds of initiator synergies, reacting balance, even molecular weight distribution simultaneously.
embodiment 2
raw material is by weight ratio:
(1), monomer emulsification, pre-emulsion preparation:
Butyl acrylate 20, vinylbenzene 15, vinyl cyanide 25, Emulsifier O N-50 15, sodium lauryl sulphate 6, methacrylic acid 4, AAEM 6 are joined in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 143, make pre-emulsion;
(2), proteolysis, hydrolyzed casein liquid preparation:
deionized water 460 is added to reactor, add casein 130 under stirring, the 75-80 ℃ that then heats up, stir 0.5-1 hour, and casein is fully dissolved, and adds triethylamine 26, and stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3), polyreaction:
During the initiator solution that initiator potassium persulfate 0.4, Sodium Persulfate 0.1 and deionized water 35 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product.
This embodiment product is owing to selecting butyl acrylate, vinylbenzene and vinyl cyanide in proportioning raw materials, and in the time of soft, transparency is good, and luminance brightness is best, and anti-xerotripsis fastness is best, heat-resisting, good from plate.
embodiment 3
Raw material is by weight ratio:
(1), monomer emulsification, pre-emulsion preparation:
Butyl acrylate 30, ethyl propenoate 30, benzene alkene nitrile 30, Emulsifier O N-50 17, sodium lauryl sulphate 10, methacrylic acid 8, AAEM 5 are joined in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 163, make pre-emulsion;
(2), proteolysis, hydrolyzed casein liquid preparation:
Deionized water 487 is added to reactor, add casein 110 under stirring, the 75-80 ℃ that then heats up, stir 0.5-1 hour, and casein is fully dissolved, and adds triethylamine 22, and stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3), polyreaction:
During the initiator solution that initiator potassium persulfate 0.2, Sodium Persulfate 0.3 and deionized water 45 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product;
this embodiment product is due to sodium lauryl sulphate, Emulsifier O N-50 large usage quantity in material component, and the product wetting ability is stronger, and emulsion state is good, good stability; Select butyl acrylate, ethyl propenoate amount larger, pleasant softness is good.
embodiment 4
Raw material is by weight ratio:
(1), monomer emulsification, pre-emulsion preparation:
Butyl acrylate 10, ethyl propenoate 10, vinyl cyanide 20, vinylbenzene 20, Emulsifier O N-50 20, sodium lauryl sulphate 5, methacrylic acid 7, AAEM 8 are joined in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 148, make pre-emulsion;
(2), proteolysis, hydrolyzed casein liquid preparation:
Deionized water 445 is added to reactor, add casein 120 under stirring, the 75-80 ℃ that then heats up, stir 0.5-1 hour, and casein is fully dissolved, and adds triethylamine 24, and stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3), polyreaction:
During the initiator solution that initiator ammonium persulfate 0.5, Sodium Persulfate 0.3 and deionized water 40 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product;
this embodiment product is due to material component kind ON-50 large usage quantity, and emulsion particle is special thin, and good penetrability is good with the bottom binding strength; The AAEM large usage quantity, provide cross-linked network, and dry wet rubbing fastness is best, heat-resisting, good from plate, and after synergy, luminance brightness, transparency are good.
embodiment 5
Raw material is by weight ratio:
(1), monomer emulsification, pre-emulsion preparation:
Ethyl propenoate 20, vinyl cyanide 20, vinylbenzene 10, Emulsifier O N-50 16, sodium lauryl sulphate 7, methacrylic acid 4, AAEM 6 are joined in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 155, make pre-emulsion;
(2), proteolysis, hydrolyzed casein liquid preparation:
Deionized water 465 is added to reactor, add casein 150 under stirring, the 75-80 ℃ that then heats up, stir 0.5-1 hour, and casein is fully dissolved, and adds triethylamine 30, and stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3), polyreaction:
During the initiator solution that initiator ammonium persulfate 0.3, Sodium Persulfate 0.3 and deionized water 35 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product;
This embodiment product is because material component is selected ethyl propenoate, vinylbenzene, vinyl cyanide, and the casein large usage quantity, and after modification, the product Bearable dry and wet wipe is good, and brightness reaches DE Specular Lighting, and hair side is clear, good from plate.
In above-described embodiment, Emulsifier O N-50 is BASF AG's product, the agency and sales of Shanghai Suo Kai trade Co., Ltd.
the application experiment contrast:
Hide finishes coating (weight ratio):
Modified Casein Leather finishing agent 100
Feel wax 100
Aqueous polyurethane emulsion 200
Dyestuff 20
Deionized water 400.
Use respectively the embodiment of the present invention 1,2,3,4,5 products, hide finishes BI-372 product, hide finishes CREX AN32 product, by said ratio, make hide finishes coating.
Feel wax is the FS-0536 that Liaoning Sunichem Co., Ltd. produces.Aqueous polyurethane emulsion is the FS-701C that Liaoning Sunichem Co., Ltd. produces.Dyestuff is that Huzhou Nan Xun is with the black dyes water of producing along Dye Co., Ltd.
Using spray gun evenly to spray on lamb skin twice, 90 ℃ dries 2 minutes; 110 ℃ of 5 seconds of boiling hot light.
Performance is compared as follows table:
Anti-dry, wet rubbing fastness: press the dry wet rubbing test of QB/T1327 leather surface color fastness, use the test of XK-3078 leather surface color fastness trier.
Feel, brightness, from plate, thermotolerance: by sense organ, touch judgement.
Transparency: by the whether clear judgement of visual observations graining.
From above test result, can find out, product of the present invention is soft, transparency, brightness fastness good, anti-dry, wet rubbing is excellent, from plate, good heat resistance.
Claims (3)
1. polyacrylate modified Casein Leather finishing agent is characterized in that:
The raw material weight proportioning
A, acrylate mixing monomer 45-100
B, methacrylic acid 3-10
C, AAEM 5-8
D, casein 100-150
E, triethylamine 20-30
F, deionized water 450-850
G, sodium lauryl sulphate 5-10
H, Emulsifier O N-50 10-20
I, initiator 0.1-1
Through monomer emulsification, proteolysis, polyreaction, make;
The product chemical index; Outward appearance: faint yellow translucent emulsion
Ionic: the moon
PH value: 8 ± 1
Solid content: 25 ± 1%;
Acrylate mixing monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide wherein to be mixed and uses more than three kinds or three kinds;
Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds mix and use.
2. polyacrylate modified Casein Leather finishing agent preparation method is characterized in that:
Raw material is by weight ratio:
(1) monomer emulsification, the pre-emulsion preparation:
By acrylate mixing monomer 45-100, Emulsifier O N-50, be that 10-20, sodium lauryl sulphate 5-10, methacrylic acid 3-10, AAEM 5-8 join in pre-newborn still, rapid stirring, at the uniform velocity add deionized water 110-210, make pre-emulsion;
(2) proteolysis, the preparation of hydrolyzed casein liquid:
Deionized water 340--640 is added to reactor, add casein 100-150 under stirring, 75-80 ℃ then heats up, stir 0.5-1 hour, casein is fully dissolved, add triethylamine 20-30, stirring reaction 1.5-2.5 hour, make the casein complete hydrolysis, obtains hydrolyzed casein liquid;
(3) polyreaction:
During the initiator solution that initiator 0.1-1 and deionized water 25-50 are mixed and step (1) pre-emulsion are added drop-wise to reactor at 75-80 ℃ of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 ℃ of reaction 0.5-1 hour, 40 ± 5 ℃ of blowings of lowering the temperature obtain product;
Acrylate mixing monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide wherein to be mixed and uses more than three kinds or three kinds;
Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds mix and use.
3. the polyacrylate modified Casein Leather finishing agent that claim 3 method obtains.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104530330A (en) * | 2014-12-24 | 2015-04-22 | 四川达威科技股份有限公司 | Leather finishing agent and preparation method thereof |
| CN109371661A (en) * | 2018-10-26 | 2019-02-22 | 含山县领创新材料科技有限公司 | A kind of sieve anti-static and abrasion-resistant aftertreatment technology |
| CN109705640A (en) * | 2018-11-29 | 2019-05-03 | 安徽开林新材料股份有限公司 | A kind of dope for inner wall of architecture |
| CN111304383A (en) * | 2020-04-08 | 2020-06-19 | 桐乡市迪诺纺织股份有限公司 | Manufacturing method of sofa leather coating process |
| CN115815094A (en) * | 2022-12-10 | 2023-03-21 | 浙江南龙皮业有限公司 | Anti-cracking coating agent for leather and leather coating method |
| IT202200010043A1 (en) * | 2022-05-16 | 2023-11-16 | Fgl Int S P A | FORMULATION FOR COATING PRODUCT |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530330A (en) * | 2014-12-24 | 2015-04-22 | 四川达威科技股份有限公司 | Leather finishing agent and preparation method thereof |
| CN104530330B (en) * | 2014-12-24 | 2017-09-26 | 四川达威科技股份有限公司 | A kind of leather finishing agent and preparation method thereof |
| CN109371661A (en) * | 2018-10-26 | 2019-02-22 | 含山县领创新材料科技有限公司 | A kind of sieve anti-static and abrasion-resistant aftertreatment technology |
| CN109705640A (en) * | 2018-11-29 | 2019-05-03 | 安徽开林新材料股份有限公司 | A kind of dope for inner wall of architecture |
| CN111304383A (en) * | 2020-04-08 | 2020-06-19 | 桐乡市迪诺纺织股份有限公司 | Manufacturing method of sofa leather coating process |
| IT202200010043A1 (en) * | 2022-05-16 | 2023-11-16 | Fgl Int S P A | FORMULATION FOR COATING PRODUCT |
| CN115815094A (en) * | 2022-12-10 | 2023-03-21 | 浙江南龙皮业有限公司 | Anti-cracking coating agent for leather and leather coating method |
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