CN103468084B - Polyacrylate modified Casein Leather finishing agent and preparation method - Google Patents

Abstract

The polyacrylate modified Casein Leather finishing agent of the present invention and preparation method, raw material weight proportioning: crylic acid ester mixture monomer 45-100, methacrylic acid 3-10, AAEM 5-8, casein 100-150, triethylamine 20-30, deionized water 450-850, sodium lauryl sulphate 5-10, emulsifying agent 10-20, initiator 0.1-1, obtain through monomer emulsification, proteolysis, polyreaction.For leather finish, product is soft, from plate is good, fastness is good, gloss is high, permeability is good.

Description

Polyacrylate modified Casein Leather finishing agent and preparation method

Technical field

The present invention relates to a kind of polyacrylate modified casein finishing agent for corium and preparation method, for improving corium feel, hide finishes from plate, fastness, gloss, permeability.

Background technology

Casein finishing agent is widely used in leather finish, effectively improves leather hand feeling, from performances such as plate, fastness, gloss, permeabilities.

CN201110057116.5 patent discloses " a kind of original position Soap free cationic emulision legal system is for the method for modified Casein/nano silicon compound film former ", this technology is with the multipolymer of hexanolactam grafting casein, simultaneously, introduce proper amount of nano silicon-dioxide, give the natural glossiness of leather, higher resistance to xerotripsis fastness and dry and comfortable feel for leather finish.But it can reach the high request of high gloss, high-permeability.

CN201110427243.X patent discloses " modified Casein, hide finishes and preparation method thereof ", this technology provides and obtain modified Casein finishing agent with hexanolactam generation grafting polycondensation under organic acid condition, it shows cationic, and to improve, casein material filming is hard, the shortcoming of inextensibility, easy fracture.But its cationic limits its application, positively charged ion is substantially used in back cover in finishing agent, and product appearance does not reach the effect requirements of Gao Guang, high-clarity.

CN200910036061.2 patent discloses " a kind of preparation method of modified casein used in leather finishing ", what it provided is just used alone hexanolactam modified product, select NP-10 as emulsifying agent, it is a kind of polyoxyethylene nonylphenol ether, namely containing APEO, to the objectionable impurities of human body, the kind that Ye Shi European Union forbids strongly, and make softening agent with glycerine, feel can be hardening gradually, is difficult to reach the requirement of Gao Guang, the performance index such as penetrating, soft.

Upper described prior art modified Casein Leather finishing agent product is hexanolactam modified product, and each product has respective feature, but all must possess that feel is soft, gloss is high, permeability is good, from the good feature of plate simultaneously.

Summary of the invention

The object of this invention is to provide a kind of leather finish modification of acrylic resin casein finishing agent and preparation method, product have 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:

Raw material weight proportioning:

A, crylic acid ester mixture 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

Obtain through monomer emulsification, proteolysis, polyreaction;

Product chemical index; Outward appearance: faint yellow translucent emulsion

Ionic: cloudy

PH value: 8 ± 1

Solid content: 25 ± 1%;

crylic acid ester mixture monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide, and wherein three kinds or more is used in combination;

Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds are used in combination;

Emulsifier O N-50 is BASF AG's product, and Shanghai Suo Kai trade Co., Ltd acts as the agent of.

the present invention's polyacrylate modified Casein Leather finishing agent preparation method:

Raw material is by weight ratio:

(1) monomer emulsification, prepared by pre-emulsion:

Be 10-20, sodium lauryl sulphate 5-10 by crylic acid ester mixture monomer 45-100, Emulsifier O N-50, 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, prepared by hydrolyzed casein liquid:

Deionized water 340--640 is added reactor, under stirring, adds casein 100-150, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 20-30, stirring reaction 1.5-2.5 hour, makes casein complete hydrolysis, obtains hydrolyzed casein liquid;

(3) polyreaction:

The initiator solution be mixed initiator 0.1-1 and deionized water 25-50 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C of blowings of lowering the temperature obtain product;

Crylic acid ester mixture monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide, and wherein three kinds or more is used in combination;

Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds are used in combination;

Emulsifier O N-50 is BASF AG's product, and Shanghai Suo Kai trade Co., Ltd acts as the agent of.

The polyacrylate modified Casein Leather finishing agent that the inventive method obtains: ionic: cloudy, pH value: 8 ± 1, solid content: 25 ± 1%.

The inventive method producing and manufacturing technique is simple and convenient, easily realizes, and has good process implementing, and aqueous, environmental protective is pollution-free simultaneously.Product is soft, good from plate, good heat resistance, fastness are good, gloss is high, permeability is good, aqueous, environmental protective.

The hydroxyl, amino and the carboxyl that produce after casein hydrolysis of the present invention and multiple acrylate monomer produce copolymerization, the present invention have selected methacrylic acid, AAEM and produces copolyreaction by butyl acrylate, ethyl propenoate, vinylbenzene, the fine crylic acid ester mixture monomer formed of propylene, various active group acts synergistically, adjustment proportional quantity, can meet soft, good from plate, that good heat resistance, fastness are 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, improves water-fast, solvent resistant, wear resisting property, thus improves dry, the wet rubbing fastness after leather finish; AAEM contains active group, provides crosslinked, forms reticulated structure in cross-linking process, effectively improves the resistance to 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 crylic acid ester mixture monomer polyreaction, its be polymerized with butyl acrylate, ethyl propenoate after product due to butyl acrylate, ethyl propenoate second-order transition temperature low, there is obvious contribution to pliability, 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, obvious contribution is had to water repellency, thus resistance to 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 to act synergistically, pre-emulsion stable performance, make each monomer fully fused, product film clarity is good, obtains modification finishing agent product and stablizes; ON-50 good penetrability, increase and leather binding strength, and emulsifier is few, good with the binding strength of leather, washing fastness is good.

Adopt multiple initiator to act synergistically, residual ionization monomer is few, and reaction yield is high, even molecular weight distribution, and product is stablized.

Embodiment

Raw material weight proportioning.

embodiment 1,

(1), monomer emulsification, pre-emulsion prepare:

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 prepare:

Deionized water 350 is added reactor, under stirring, adds casein 100, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 20, stirring reaction 1.5-2.5 hour, make casein complete hydrolysis, obtain hydrolyzed casein liquid;

(3), polyreaction:

The initiator solution be mixed initiator ammonium persulfate 0.4, Potassium Persulphate 0.4 and deionized water 25 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C 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 prepare:

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 prepare:

deionized water 460 is added reactor, under stirring, adds casein 130, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 26, stirring reaction 1.5-2.5 hour, make casein complete hydrolysis, obtain hydrolyzed casein liquid;

(3), polyreaction:

The initiator solution be mixed initiator potassium persulfate 0.4, Sodium Persulfate 0.1 and deionized water 35 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C 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, while soft, transparency is good, and luminance brightness is best, and resistance to xerotripsis fastness is best, heat-resisting, good from plate.

embodiment 3

Raw material is by weight ratio:

(1), monomer emulsification, pre-emulsion prepare:

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 prepare:

Deionized water 487 is added reactor, under stirring, adds casein 110, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 22, stirring reaction 1.5-2.5 hour, make casein complete hydrolysis, obtain hydrolyzed casein liquid;

(3), polyreaction:

The initiator solution be mixed initiator potassium persulfate 0.2, Sodium Persulfate 0.3 and deionized water 45 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C 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 product wetting ability is comparatively strong, and emulsion state is good, good stability; Select butyl acrylate, ethyl propenoate amount comparatively large, pleasant softness is good.

embodiment 4

Raw material is by weight ratio:

(1), monomer emulsification, pre-emulsion prepare:

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 prepare:

Deionized water 445 is added reactor, under stirring, adds casein 120, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 24, stirring reaction 1.5-2.5 hour, make casein complete hydrolysis, obtain hydrolyzed casein liquid;

(3), polyreaction:

The initiator solution be mixed initiator ammonium persulfate 0.5, Sodium Persulfate 0.3 and deionized water 40 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C 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 bottom binding strength; AAEM large usage quantity, provides cross-linked network, and dry wet rubbing fastness is best, heat-resisting, good from plate, and the rear luminance brightness of synergy, transparency are good.

embodiment 5

Raw material is by weight ratio:

(1), monomer emulsification, pre-emulsion prepare:

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 prepare:

Deionized water 465 is added reactor, under stirring, adds casein 150, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 30, stirring reaction 1.5-2.5 hour, make casein complete hydrolysis, obtain hydrolyzed casein liquid;

(3), polyreaction:

The initiator solution be mixed initiator ammonium persulfate 0.3, Sodium Persulfate 0.3 and deionized water 35 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C of blowings of lowering the temperature obtain product;

This embodiment product selects ethyl propenoate, vinylbenzene, vinyl cyanide due to material component, and casein large usage quantity, modified 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, and Shanghai Suo Kai trade Co., Ltd acts as the agent of.

application experiment contrasts:

Hide finishes coating (weight ratio):

Modified Casein Leather finishing agent 100

Feel wax 100

Aqueous polyurethane emulsion 200

Dyestuff 20

Deionized water 400.

Use the embodiment of the present invention 1,2,3,4,5 product, hide finishes BI-372 product, hide finishes CREX AN32 product respectively, make hide finishes coating by said ratio.

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 produced along Dye Co., Ltd.

To use on spray gun even application to lamb skin twice, dry 2 minutes for 90 DEG C; 110 DEG C of hot light 5 seconds.

Performance comparision is as following table:

Resistance to dry, wet rubbing fastness: by the dry wet rubbing test of QB/T1327 leather surface color fastness, use XK-3078 leather surface color fastness trier test.

Feel, brightness, from plate, thermotolerance: by sense organ, touch judge.

Transparency: by the whether clear judgement of visual observations graining.

As can be seen from above test result, product of the present invention is soft, transparency, brightness fastness good, resistance to dry, wet rubbing is excellent, from plate, good heat resistance.

Claims (3)

1. polyacrylate modified Casein Leather finishing agent, is characterized in that:

Raw material weight proportioning

A, crylic acid ester mixture 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

Obtain through monomer emulsification, proteolysis, polyreaction;

Product chemical index; Outward appearance: faint yellow translucent emulsion

Ionic: cloudy

PH value: 8 ± 1

Solid content: 25 ± 1%;

Crylic acid ester mixture monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide, and wherein three kinds or more is used in combination;

Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds are used in combination.

2. polyacrylate modified Casein Leather finishing agent preparation method, is characterized in that:

Raw material is by weight ratio:

(1) monomer emulsification, prepared by pre-emulsion:

Be 10-20, sodium lauryl sulphate 5-10 by crylic acid ester mixture monomer 45-100, Emulsifier O N-50, 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, prepared by hydrolyzed casein liquid:

Deionized water 340-640 is added reactor, under stirring, adds casein 100-150, then intensification 75-80 DEG C, stir 0.5-1 hour, casein is fully dissolved, adds triethylamine 20-30, stirring reaction 1.5-2.5 hour, makes casein complete hydrolysis, obtains hydrolyzed casein liquid;

(3) polyreaction:

The initiator solution be mixed initiator 0.1-1 and deionized water 25-50 and step (1) pre-emulsion are added drop-wise in reactor at 75-80 DEG C of temperature simultaneously, within 2-3 hour, drip off, then be incubated at 70-80 DEG C of reaction 0.5-1 hour, 40 ± 5 DEG C of blowings of lowering the temperature obtain product;

Crylic acid ester mixture monomer is selected from butyl acrylate, ethyl propenoate, vinylbenzene, vinyl cyanide, and wherein three kinds or more is used in combination;

Initiator is that ammonium persulphate, Potassium Persulphate, Sodium Persulfate one of them or two kinds are used in combination.

3. the polyacrylate modified Casein Leather finishing agent that obtains of claim 2 method.