CN104005237A - Water-dilutable resin-based impregnation method for ultrafine fiber synthetic leather base fabrics - Google Patents
Water-dilutable resin-based impregnation method for ultrafine fiber synthetic leather base fabrics Download PDFInfo
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Abstract
The invention discloses a water-dilutable resin-based impregnation method for ultrafine fiber synthetic leather base fabrics. The method comprises the following steps: firstly, 100 parts of water-dilutable alkali proof hydrolysis type polyurethane emulsion with the solid content of 20-50%, 40-100 parts of emulsion of alkali soluble acrylic acid and ester copolymer thereof with the solid content of 30-40%, 0-250 parts of water, and 0.6-3 parts of thickening agents are mixed evenly to prepare a water-dilutable impregnation sizing agent; then, ultrafine fiber non-woven fabrics are infused into the water-dilutable impregnation sizing agents, and then the ultrafine fiber non-woven fabrics are dried for 5-20 min; sodium hydroxide aqueous solutions with 5-15% of sodium hydroxide are used for alkali weight reduction treatment, the weight reduction temperature is 80-95 DEG C, the weight reduction time is 30-120 min, and the acrylic acid and the ester copolymer thereof are hydrolyzed and dissolved, so that cellular structures are formed in ultrafine fiber synthetic leather; the base fabrics are rinsed and baked after alkali weight reduction, and finally, the ultrafine fiber synthetic leather is obtained through after finishing. The technology of the method provided by the invention is ecological and environmental friendly; the production method is simple and easy to implement; the structures and the sizes of cells can be regulated through the amount of the acrylic acid and the ester copolymer thereof, so that the requirements of different products are satisfied.
Description
Technical field
The invention belongs to synthetic leather and manufacture field, specifically refer to a kind of impregnation method of the superfine fiber synthetic leather base cloth based on water-base resin.
Background technology
Synthetic leather, with characteristics such as its good physical property, feel and outward appearances, is widely used in the industries such as clothes, shoemaking, case and bag, furniture, occupies very consequence in people's productive life.Superfine fiber chemical leather is as the synthetic leather product of latest generation, there is splendid resilience, flexibility, emulation, gas permeability, replace significantly corium and common synthetic leather, to meet the demand of domestic and international market to expensive goods, embodying the main direction of synthetic leather technical development.Superfine fibre can be divided into determines island fiber and indefinite island fiber, and correspondingly the manufacturing technique of superfine fiber chemical leather is divided into technique He Ding island, indefinite island technique, and its technological process is as follows respectively:
(i) indefinite island technique: the not nonwoven fabric → polyurethane impregnation → toluene decrement → dyeing and finishing of island fiber with figured sea-island → needle point method or top finishing;
(ii) determine island technique: the island fiber with figured sea-island → impregnation → sodium hydroxide alkali decrement → dyeing and finishing of highly dense needle point method nonwoven fabric → polyurethane or top finishing.
In the technique of technique He Ding island, indefinite island, nonwoven fabric all must first form island phase structure and microcellular structure through decrement with polyurethane impregnation again.Indefinite island process using toluene decrement wherein, environmental pollution is large.And environment facies to close friend island ultrafine fiber synthetic leather still adopt solvent borne polyurethane impregnation superfine fibre nonwoven cloth in producing, then containing N, in the aqueous solution of dinethylformamide (DMF), solidify, again through washing, alkali decrement, dry, after the operation that arranges, finally make superfine fiber chemical leather.The advantage of this method is that finished leather is plentiful, bubble sense is sufficient, soft, and shortcoming is in solvent borne polyurethane, to contain a large amount of toxic solvents such as DMF, has not only caused serious environmental pollution, and solvent recovery has consumed a large amount of energy and needed very large equipment investment.
Aqueous polyurethane be take water as decentralized medium, free from environmental pollution, and water price is honest and clean, use safety, and the application in synthetic leather has become development trend and industry common recognition.But the application of aqueous polyurethane in synthetic leather, mainly concentrates on top finishing aspect.When replacing solvent borne polyurethane for the impregnation of superfine fiber synthetic leather base cloth with it, cannot adopt wet processing and obtain polyurethane/superfine fibre complex with loose structure, can not meet superfine fiber chemical leather in the requirement of the aspects such as feel, elasticity and richness; Also someone directly dries the superfine fiber synthetic leather base cloth making after attempting adopting aqueous polyurethane impregnation, but hard, shrivelled, the still sense of finished leather plate does not reach desired sense of touch and richness far away.Therefore the superfine fiber chemical leather that, how to adopt water-base resin preparation to there is microcellular structure become restriction industry development key technology.
For addressing this problem, each enterprise and R&D institution have carried out relevant work in succession both at home and abroad, have proposed the method for some foaming, as mechanical foaming method, chemical blowing process etc.But mechanical foaming method exists technological requirement high (need after the steady bubble of long period, steady bubble the life-span of foam shorter), foam structure is difficult to control and the shortcoming such as cost high (aqueous polyurethane solid content need be greater than 50%, need to add the auxiliary agents such as foam stabilizer, foam stabilizer).And chemical blowing process is owing to there is no at present the blowing agent that is suitable for aqueous polyurethane system, be difficult to realize.Summary of the invention
The object of the invention is the shortcoming and defect existing in order to overcome prior art, and a kind of impregnation method of the superfine fiber synthetic leather base cloth based on water-base resin is provided.
For achieving the above object, technical scheme of the present invention is to comprise the following steps:
(1) preparation of water-based impregnation slurry (weight fraction meter):
100 parts of water-based hydrolysis resistant polyurethane emulsions
40 ~ 100 parts of acrylic acid series co-ploymer emulsions
0 ~ 250 part, water
0.6 ~ 3 part of thickener
Said components is mixed, obtain water-based impregnation slurry, viscosity is controlled at 4000 ~ 8000mPas;
(2) impregnation: superfine fibre nonwoven cloth be impregnated in described water-based impregnation slurry, and impregnation amount is 200 ~ 1200g/m
2;
(3) dry: by the dry 5 ~ 20min in the baking oven of 100 ~ 130 ℃ of the superfine fibre nonwoven cloth after impregnation, to make impregnation base cloth;
(4) decrement: impregnation base cloth is carried out in 5 ~ 15% sodium hydrate aqueous solution to alkali decrement treatment, decrement temperature is 80 ~ 95 ℃, the decrement time is 30 ~ 120min, and in this operation, acrylic acid series co-ploymer is dissolved in sodium hydrate aqueous solution, and forms abscess in base cloth;
(5) washing, dry: the base cloth after alkali decrement is washed to neutrality is dried at 100 ~ 130 ℃, obtains superfine fiber synthetic leather base cloth;
(6) after, arrange: comprise dyeing, flour milling, dry method veneer, change colour, embossing, table place, rub all same common process such as line.
Wherein said acrylic acid series co-ploymer is the copolymer of alkali-soluble acrylicacidandesters, solid content 30-40%.
Wherein said water-based hydrolysis resistant polyurethane emulsion is alkaline-resisting hydrolysis-type, solid content 20-50%, modulus aliphatic or the aromatic waterborne polyurethane between 30-50MPa.
Wherein said superfine fibre nonwoven cloth is a kind of in the figured type superfine fibre nonwoven cloth that makes of polyamide and/or terylene and alkali soluble polyester blend.
Inventive principle of the present invention is to using the mixed emulsion of the alkaline-resisting hydrolysis-type polyurethane of water-based and alkali solubility acrylic acid series co-ploymer as containing immersion liquid, dry after the copolymer of acrylicacidandesters be wrapped in polyurethane matrix.In alkali decrement process, alkali solubility acrylic acid series co-ploymer dissolves and separates out under the effect of NaOH, thereby forms foam structure in superfine fiber synthetic leather base cloth.Foam structure and large I are regulated by the consumption of acrylic acid series co-ploymer, thereby give plentiful, the soft feel of finished leather and meet the demand of different product.
The present invention compared with prior art, has advantages of following several respects:
(1) utilize the copolymer of acrylicacidandesters to be hydrolyzed and the characteristic of stripping under alkali condition, thereby in superfine fiber chemical leather, form microcellular structure.This step has been synchronizeed with the alkali decrement operation of superfine fiber chemical leather, without changing existing equipment, does not also increase technological process, and production method is simple.
(2) by changing polyurethane and the ratio of acrylic acid series co-ploymer in impregnation slurry, can realize easily the adjustment to microcellular structure, richness and pliability in superfine fiber chemical leather, to meet the needs of different product.
(3) adopt aqueous polyurethane replace solvents type polyurethane, from source, eliminated the environmental pollution of organic solvent, also without solvent recovery unit, reduced equipment investment and energy resource consumption.The superfine fiber chemical leather of simultaneously producing, containing organic solvent, does not meet the requirement of American-European ecological synthetic leather, has improved the international competitiveness of product.
(4) the aqueous ultrafine fiber synthetic leather good hand feeling, the high resilience that make, be similar to corium.
Below in conjunction with the specific embodiment, the present invention is described further.
The specific embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
embodiment 1
First by solid content, be 20%, modulus is 100 parts of the water-based hydrolysis resistant polyurethane emulsions of 30MPa, solid content is 60 parts of 40% acrylic acid series co-ploymer emulsions, 20 parts, water, 0.6 part of water-based nonionic polyurethane thickener mixes, and being made into viscosity is the water-based impregnation slurry of 4000mPas left and right; Then PA/COPET figured type superfine fibre nonwoven cloth be impregnated in water-based impregnation slurry, impregnation amount is 200-300 g/m
2; Again by the dry 5min in the baking oven of 120 ℃ of the superfine fibre nonwoven cloth after impregnation; Then in 10% sodium hydrate aqueous solution, carry out alkali decrement treatment, decrement temperature is 90 ℃, and the decrement time is 60min; Base cloth after alkali decrement is washed to neutrality, at 100 ~ 130 ℃, dries, and obtains superfine fiber synthetic leather base cloth.Superfine fiber synthetic leather base cloth, again through flour milling, dyeing, napping, makes matte superfine fiber chemical leather, can be used as clothing leather or glove leather.
Finished leather performance: the superfine fiber chemical leather obtaining is soft, bubble sense and richness are moderate, and the elasticity of compression is good, and VOC content is removed from office lower than 5mg/kg, ecological, environmental protective.
embodiment 2
First by solid content, be 35%, modulus is 100 parts of the water-based hydrolysis resistant polyurethane emulsions of 36MPa, solid content is 80 parts of 35% acrylic acid series co-ploymer emulsions, and 1.5 parts of water-based nonionic polyurethane thickeners mix, and being made into viscosity is the water-based impregnation slurry of 7000mPas left and right; Then PA/COPET figured type superfine fibre nonwoven cloth be impregnated in water-based impregnation slurry, impregnation amount is 350 ~ 450/m
2; Again by the dry 10min in the baking oven of 130 ℃ of the superfine fibre nonwoven cloth after impregnation; Then in 10% sodium hydrate aqueous solution, carry out alkali decrement treatment, decrement temperature is 80 ℃, and the decrement time is 120min; Base cloth after alkali decrement is washed to neutrality, at 100 ~ 130 ℃, dries, and obtains superfine fiber synthetic leather base cloth.Superfine fiber synthetic leather base cloth through dry method veneer, makes superfine fiber chemical leather again, can be used as furniture leather.
Finished leather performance: soft in the superfine fiber chemical leather feel obtaining, richness is medium, and the elasticity of compression is good, and VOC content is removed from office lower than 5mg/kg, ecological, environmental protective.
embodiment 3
First by solid content, be 30%, modulus is 100 parts of the water-based hydrolysis resistant polyurethane emulsions of 42MPa, solid content is 40 parts of 30% acrylic acid series co-ploymer emulsions, 40 parts, water, 1.7 parts of water-based nonionic polyurethane thickeners mix, and being made into viscosity is the water-based impregnation slurry of 7500mPas left and right; Then PET/COPET figured type superfine fibre nonwoven cloth be impregnated in water-based impregnation slurry, impregnation amount is 600 ~ 700g/m
2; Again by the dry 10min in the baking oven of 130 ℃ of the superfine fibre nonwoven cloth after impregnation; Then in 5% sodium hydrate aqueous solution, carry out alkali decrement treatment, decrement temperature is 90 ℃, and the decrement time is 60min; Base cloth after alkali decrement is washed to neutrality, at 100 ~ 130 ℃, dries, and obtains superfine fiber synthetic leather base cloth.Superfine fiber synthetic leather base cloth again through changing colour, embossing, make superfine fiber chemical leather, can be used as luggage leather.
Finished leather performance: hard in the superfine fiber chemical leather feel obtaining, the elasticity of compression is good, and VOC content is removed from office lower than 1mg/kg, ecological, environmental protective.
embodiment 4
First by solid content, be 45%, modulus is 100 parts of the water-based hydrolysis resistant polyurethane emulsions of 50MPa, 40 parts of the acrylic acid series co-ploymer emulsions that solid content is 30%, 125 parts, water, 2 parts of water-based nonionic polyurethane thickeners mix, and being made into viscosity is the water-based impregnation slurry of 8000mPas left and right; Then PA/COPET figured type superfine fibre nonwoven cloth be impregnated in water-based impregnation slurry, impregnation amount is 1000 ~ 1200g/m
2; Again by the dry 10min in the baking oven of 130 ℃ of the superfine fibre nonwoven cloth after impregnation; Then in 15% sodium hydrate aqueous solution, carry out alkali decrement treatment, decrement temperature is 90 ℃, and the decrement time is 30min; Base cloth after alkali decrement is washed to neutrality, at 100 ~ 130 ℃, dries, and obtains superfine fiber synthetic leather base cloth.Superfine fiber synthetic leather base cloth through dry method veneer, makes superfine fiber chemical leather again.
Finished leather performance: hard in the superfine fiber chemical leather feel obtaining, abundant, the elasticity of compression is good, and VOC content is removed from office lower than 5mg/kg, ecological, environmental protective, can be used as footwear leather and luggage leather.
embodiment 5
First by solid content, be 50%, modulus is 100 parts of the water-based hydrolysis resistant polyurethane emulsions of 30MPa, solid content is 100 parts of 30% acrylic acid series co-ploymer emulsions, 250 parts, water, 3 parts of water-based nonionic polyurethane thickeners mix, and being made into viscosity is the water-based impregnation slurry of 5000mPas left and right; Then PA/COPET figured type superfine fibre nonwoven cloth be impregnated in water-based impregnation slurry, impregnation amount is 400-500 g/m
2; Again by the dry 20min in the baking oven of 100 ℃ of the superfine fibre nonwoven cloth after impregnation; Then in 15% sodium hydrate aqueous solution, carry out alkali decrement treatment, decrement temperature is 95 ℃, and the decrement time is 30min; Base cloth after alkali decrement is washed to neutrality, at 100 ~ 130 ℃, dries, and obtains superfine fiber synthetic leather base cloth.Superfine fiber synthetic leather base cloth, again through flour milling, dyeing, napping, makes matte superfine fiber chemical leather, can be used as clothing leather or glove leather.
Finished leather performance: the superfine fiber chemical leather obtaining is soft, bubble sense and richness are moderate, and the elasticity of compression is good, and VOC content is removed from office lower than 5mg/kg, ecological, environmental protective.
comparative example 1
In embodiment 1, water-based impregnation slurry does not add acrylic acid series co-ploymer emulsion, for guaranteeing that in water-based impregnation slurry, solid content and viscosity are constant, add 80 parts of water and 1 part of water-based nonionic PU thickener, all the other raw materials and technique are constant, make superfine fiber chemical leather.
Finished leather performance: the shrivelled still sense of superfine fiber chemical leather obtaining, the elasticity of compression is poor, and VOC content is removed from office lower than 5mg/kg.
Claims (4)
1. an impregnation method for the superfine fiber synthetic leather base cloth based on water-base resin, is characterized in that comprising the following steps:
(1) preparation of water-based impregnation slurry, in parts by weight:
100 parts of aqueous polyurethane emulsions
40 ~ 100 parts of acrylic acid series co-ploymer emulsions
0 ~ 250 part, water
0.6 ~ 3 part of thickener
Said components is mixed, obtain water-based impregnation slurry, viscosity is controlled at 4000 ~ 8000mPas;
(2) impregnation: superfine fibre nonwoven cloth be impregnated in described water-based impregnation slurry, and impregnation amount is 200 ~ 1200g/m
2;
(3) dry: by the dry 5 ~ 20min in the baking oven of 100 ~ 130 ℃ of the superfine fibre nonwoven cloth after impregnation, to make impregnation base cloth;
(4) decrement: impregnation base cloth is carried out in 5 ~ 15% sodium hydrate aqueous solution to alkali decrement treatment, decrement temperature is 80 ~ 95 ℃, the decrement time is 30 ~ 120min, and in this operation, acrylic acid series co-ploymer is dissolved in sodium hydrate aqueous solution, and forms abscess in base cloth;
(5) washing, dry: the base cloth after alkali decrement is washed to neutrality is dried at 100 ~ 130 ℃, obtains superfine fiber synthetic leather base cloth;
(6) arrange.
2. the impregnation method of a kind of superfine fiber synthetic leather base cloth based on water-base resin according to claim 1, it is characterized in that: the copolymer that in described water-based impregnation slurry, acrylic acid series co-ploymer emulsion is alkali-soluble acrylicacidandesters, solid content 30-40%.
3. the impregnation method of a kind of superfine fiber synthetic leather base cloth based on water-base resin according to claim 1, is characterized in that: described aqueous polyurethane emulsion is alkaline-resisting hydrolysis-type, solid content 20 ~ 50%, modulus aliphatic or the aromatic waterborne polyurethane between 30-50MPa.
4. the impregnation method of a kind of superfine fiber synthetic leather base cloth based on water-base resin according to claim 1, is characterized in that: described superfine fibre nonwoven cloth is a kind of in the figured type superfine fibre nonwoven cloth that makes of polyamide and/or terylene and alkali soluble polyester blend.
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