CN104005237B - A kind of impregnation method of the superfine fiber synthetic leather base cloth based on water-base resin - Google Patents
A kind of impregnation method of the superfine fiber synthetic leather base cloth based on water-base resin Download PDFInfo
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Abstract
The invention discloses a kind of impregnation method of the superfine fiber synthetic leather base cloth based on water-base resin.First be the alkaline-resisting hydrolysis-type polyaminoester emulsion of water-based 100 parts of 20 ~ 50% by solid content, the Alkali-soluble acrylic of solid content 30 ~ 40% and ester copolymer emulsion 40-100 part thereof, 0 ~ 250 part, water, thickener 0.6 ~ 3 part mixes, obtained water-based impregnation slurry; Then fine for superfine fibre nonwoven fabric be impregnated in water-based impregnation slurry, then dry 5 ~ 20min; Then use in the sodium hydrate aqueous solution of 5 ~ 15% and carry out alkali decrement treatment, decrement temperature is 80 ~ 95 DEG C, and the decrement time is 30 ~ 120min, acrylic acid series co-ploymer hydrolysis stripping, thus forms foam structure in superfine fiber chemical leather; Ji Bu after Alkali reduction carries out washing, drying, and obtains superfine fiber chemical leather finally by Final finishing.Present invention process ecological, environmental protective; Production method is simple; Foam structure and size are regulated by the consumption of acrylic acid series co-ploymer, thus meet the demand of different product.
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 the productive life of people.Superfine fiber chemical leather is as the synthetic leather product of latest generation, there is splendid resilience, flexibility, emulation, gas permeability, replace corium and common synthetic leather significantly, to meet the demand of domestic and international market to expensive goods, embody the Main way 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 indefinite island technique and determines island technique, and its technological process is as follows respectively:
(i) indefinite island technique: not island fiber with figured sea-island → needlepunched nonwoven cloth → polyurethane impregnation → toluene decrement → dyeing and finishing or top finishing;
(ii) island technique is determined: island fiber with figured sea-island → highly dense needlepunched nonwoven cloth → polyurethane impregnation → NaOH Alkali reduction → dyeing and finishing or top finishing.
In indefinite island technique and determine in the technique of island, nonwoven fabric all must first with polyurethane impregnation again through decrement formation island phase structure and microcellular structure.Wherein indefinite island technique adopts toluene decrement, and environmental pollution is large.And environment facies to close friend island ultrafine fiber synthetic leather produce in still adopt solvent borne polyurethane impregnation superfine fibre nonwoven cloth, then N is being contained, solidify in the aqueous solution of dinethylformamide (DMF), again through the operation of washing, Alkali reduction, drying, Final finishing, finally obtained superfine fiber chemical leather.The advantage of this method is that finished leather is plentiful, bubble sense is sufficient, soft, and shortcoming contains the toxic solvents such as a large amount of DMF in solvent borne polyurethane, not only causes serious environmental pollution, and solvent recovery consumes a large amount of energy and needs very large equipment investment.
Aqueous polyurethane 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 the impregnation replacing solvent borne polyurethane for superfine fiber synthetic leather base cloth with it, cannot wet processing be adopted and obtain the polyurethane/superfine fibre complex with loose structure, the requirement of superfine fiber chemical leather in feel, elasticity and richness etc. can not be met; Also someone directly dries obtained superfine fiber synthetic leather base cloth after attempting adopting aqueous polyurethane impregnation, but hard, shrivelled, the still sense of finished leather plate, do not reach required sense of touch and richness far away.Therefore, how to adopt water-base resin prepare the superfine fiber chemical leather with microcellular structure become restriction industry development key technology.
For addressing this problem, domestic and international each enterprise and R&D institution have carried out relevant work in succession, propose the method for some foaming, as mechanical foaming method, chemical blowing process etc.But mechanical foaming method also exists technological requirement high (after needing the steady bubble of long period, steady bubble, the life-span of foam is shorter), foam structure is difficult to the shortcomings such as control and cost high (aqueous polyurethane solid content need be greater than 50%, need add the auxiliary agent such as foam stabilizer, foam stabilizer).And chemical blowing process is owing to there is no the blowing agent being suitable for aqueous polyurethane system at present, be difficult to realize.Summary of the invention
The object of the invention is the shortcoming and defect existed 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 comprises the following steps:
(1) preparation (weight fraction meter) of water-based impregnation slurry:
Water-based hydrolysis resistant polyurethane emulsion 100 parts
Acrylic acid series co-ploymer emulsion 40 ~ 100 parts
0 ~ 250 part, water
Thickener 0.6 ~ 3 part
Said components mixed, obtain water-based impregnation slurry, viscosity controls at 4000 ~ 8000mPas;
(2) impregnation: be impregnated in by superfine fibre nonwoven cloth in described water-based impregnation slurry, impregnation amount is 200 ~ 1200g/m
2;
(3) dry: by the dry 5 ~ 20min in the baking oven of 100 ~ 130 DEG C of the superfine fibre nonwoven cloth after impregnation, obtained impregnation base cloth;
(4) decrement: impregnation base is distributed in the sodium hydrate aqueous solution of 5 ~ 15% and carries out alkali decrement treatment, decrement temperature is 80 ~ 95 DEG C, 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, drying: the Ji Bu after Alkali reduction is washed to neutrality, dry, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C;
(6) Final finishing: 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 aliphatic between 30-50MPa of alkaline-resisting hydrolysis-type, solid content 20-50%, modulus or aromatic waterborne polyurethane.
Wherein said superfine fibre nonwoven cloth is the one in polyamide and/or terylene and the blended obtained figured type superfine fibre nonwoven cloth of alkali soluble polyester.
Inventive principle of the present invention is that after dry, the copolymer of acrylicacidandesters is wrapped in polyurethane matrix using the mixed emulsion of the alkaline-resisting hydrolysis-type polyurethane of water-based and Alkali-soluble acrylic and ester copolymer thereof as containing immersion liquid.In Alkali reduction process, Alkali-soluble acrylic and ester copolymer thereof solution modeling under the effect of NaOH, thus foam structure is formed in superfine fiber synthetic leather base cloth.Foam structure and size are regulated by the consumption of acrylic acid series co-ploymer, thus give plentiful, the soft feel of finished leather and meet the demand of different product.
The present invention compared with prior art, has the advantage of following several respects:
(1) utilize the copolymer of acrylicacidandesters to be hydrolyzed in the basic conditions and the characteristic of stripping, thus form microcellular structure in superfine fiber chemical leather.The Alkali reduction operation of this step and superfine fiber chemical leather synchronously completes, and without the need to changing existing equipment, also do not increase technological process, production method is simple.
(2) by changing polyurethane and the ratio of acrylic acid series co-ploymer in impregnation slurry, the adjustment to microcellular structure, richness and pliability in superfine fiber chemical leather can be realized easily, to meet the needs of different product.
(3) adopt aqueous polyurethane replace solvents type polyurethane, eliminate the environmental pollution of organic solvent from source, also without the need to solvent recovery unit, reduce equipment investment and energy resource consumption.The superfine fiber chemical leather simultaneously produced containing organic solvent, does not meet the requirement of American-European ecological synthetic leather, improves the international competitiveness of product.
(4) obtained aqueous ultrafine fiber synthetic leather good hand feeling, high resilience, be similar to corium.
Below in conjunction with detailed description of the invention, the present invention is described further.
Detailed description of the invention
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 according to the content of foregoing invention to the present invention.
embodiment 1
First be 20% by solid content, modulus is the water-based hydrolysis resistant polyurethane emulsion 100 parts of 30MPa, solid content is the acrylic acid series co-ploymer emulsion 60 parts of 40%, 20 parts, water, water-based nonionic polyurethane thickener 0.6 part mixes, and is made into the water-based impregnation slurry that viscosity is about 4000mPas; Then impregnated in water-based impregnation slurry by PA/COPET figured type superfine fibre nonwoven cloth, impregnation amount is 200-300g/m
2; Again by the dry 5min in the baking oven of 120 DEG C of the superfine fibre nonwoven cloth after impregnation; Then in the sodium hydrate aqueous solution of 10%, carry out alkali decrement treatment, decrement temperature is 90 DEG C, and the decrement time is 60min; Ji Bu after Alkali reduction is washed to neutrality, dries, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C.Superfine fiber synthetic leather base cloth is again through flour milling, dyeing, napping, and obtained suede superfine fiber synthetic leather, can be used as clothing leather or glove leather.
Finished leather performance: the superfine fiber chemical leather obtained is soft, bubble sense and richness moderate, the elasticity of compression is good, and VOC content is removed from office lower than 5mg/kg, ecological, environmental protective.
embodiment 2
First be 35% by solid content, modulus is the water-based hydrolysis resistant polyurethane emulsion 100 parts of 36MPa, solid content is the acrylic acid series co-ploymer emulsion 80 parts of 35%, and water-based nonionic polyurethane thickener 1.5 parts mixes, and is made into the water-based impregnation slurry that viscosity is about 7000mPas; Then impregnated in water-based impregnation slurry by PA/COPET figured type superfine fibre nonwoven cloth, impregnation amount is 350 ~ 450/m
2; Again by the dry 10min in the baking oven of 130 DEG C of the superfine fibre nonwoven cloth after impregnation; Then in the sodium hydrate aqueous solution of 10%, carry out alkali decrement treatment, decrement temperature is 80 DEG C, and the decrement time is 120min; Ji Bu after Alkali reduction is washed to neutrality, dries, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C.Superfine fiber synthetic leather base cloth is again through dry method veneer, and obtained superfine fiber chemical leather, can be used as furniture leather.
Finished leather performance: soft in the superfine fiber chemical leather feel obtained, 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 be 30% by solid content, modulus is the water-based hydrolysis resistant polyurethane emulsion 100 parts of 42MPa, solid content is the acrylic acid series co-ploymer emulsion 40 parts of 30%, 40 parts, water, water-based nonionic polyurethane thickener 1.7 parts mixes, and is made into the water-based impregnation slurry that viscosity is about 7500mPas; Then impregnated in water-based impregnation slurry by PET/COPET figured type superfine fibre nonwoven cloth, impregnation amount is 600 ~ 700g/m
2; Again by the dry 10min in the baking oven of 130 DEG C of the superfine fibre nonwoven cloth after impregnation; Then in the sodium hydrate aqueous solution of 5%, carry out alkali decrement treatment, decrement temperature is 90 DEG C, and the decrement time is 60min; Ji Bu after Alkali reduction is washed to neutrality, dries, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C.Superfine fiber synthetic leather base cloth again through changing colour, embossing, obtained superfine fiber chemical leather, can be used as luggage leather.
Finished leather performance: hard in the superfine fiber chemical leather feel obtained, the elasticity of compression is good, and VOC content is removed from office lower than 1mg/kg, ecological, environmental protective.
embodiment 4
First be 45% by solid content, modulus is the water-based hydrolysis resistant polyurethane emulsion 100 parts of 50MPa, and solid content is the acrylic acid series co-ploymer emulsion 40 parts of 30%, 125 parts, water, water-based nonionic polyurethane thickener 2 parts mixes, and is made into the water-based impregnation slurry that viscosity is about 8000mPas; Then impregnated in water-based impregnation slurry by PA/COPET figured type superfine fibre nonwoven cloth, impregnation amount is 1000 ~ 1200g/m
2; Again by the dry 10min in the baking oven of 130 DEG C of the superfine fibre nonwoven cloth after impregnation; Then in the sodium hydrate aqueous solution of 15%, carry out alkali decrement treatment, decrement temperature is 90 DEG C, and the decrement time is 30min; Ji Bu after Alkali reduction is washed to neutrality, dries, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C.Superfine fiber synthetic leather base cloth, again through dry method veneer, obtains superfine fiber chemical leather.
Finished leather performance: hard in the superfine fiber chemical leather feel obtained, 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 be 50% by solid content, modulus is the water-based hydrolysis resistant polyurethane emulsion 100 parts of 30MPa, solid content is the acrylic acid series co-ploymer emulsion 100 parts of 30%, 250 parts, water, water-based nonionic polyurethane thickener 3 parts mixes, and is made into the water-based impregnation slurry that viscosity is about 5000mPas; Then impregnated in water-based impregnation slurry by PA/COPET figured type superfine fibre nonwoven cloth, impregnation amount is 400-500g/m
2; Again by the dry 20min in the baking oven of 100 DEG C of the superfine fibre nonwoven cloth after impregnation; Then in the sodium hydrate aqueous solution of 15%, carry out alkali decrement treatment, decrement temperature is 95 DEG C, and the decrement time is 30min; Ji Bu after Alkali reduction is washed to neutrality, dries, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C.Superfine fiber synthetic leather base cloth is again through flour milling, dyeing, napping, and obtained suede superfine fiber synthetic leather, can be used as clothing leather or glove leather.
Finished leather performance: the superfine fiber chemical leather obtained is soft, bubble sense and richness moderate, 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 ensureing 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 constant, obtained superfine fiber chemical leather.
Finished leather performance: the shrivelled still sense of the superfine fiber chemical leather obtained, the elasticity of compression is poor, and VOC content is removed from office lower than 5mg/kg.
Claims (1)
1., based on an impregnation method for the superfine fiber synthetic leather base cloth of water-base resin, it is characterized in that comprising the following steps:
(1) preparation of water-based impregnation slurry, with weight parts:
Aqueous polyurethane emulsion 100 parts
Acrylic acid series co-ploymer emulsion 40 ~ 100 parts
0 ~ 250 part, water
Thickener 0.6 ~ 3 part
Said components mixed, obtain water-based impregnation slurry, viscosity controls at 4000 ~ 8000mPas;
(2) impregnation: be impregnated in by superfine fibre nonwoven cloth in described water-based impregnation slurry, impregnation amount is 200 ~ 1200g/m
2;
(3) dry: by the dry 5 ~ 20min in the baking oven of 100 ~ 130 DEG C of the superfine fibre nonwoven cloth after impregnation, obtained impregnation base cloth;
(4) decrement: impregnation base is distributed in the sodium hydrate aqueous solution of 5 ~ 15% and carries out alkali decrement treatment, decrement temperature is 80 ~ 95 DEG C, 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, drying: the Ji Bu after Alkali reduction is washed to neutrality, dry, obtain superfine fiber synthetic leather base cloth at 100 ~ 130 DEG C;
(6) arrange
;
In described water-based impregnation slurry, acrylic acid series co-ploymer emulsion is the copolymer of alkali-soluble acrylicacidandesters, solid content 30-40%
,described aqueous polyurethane emulsion is aliphatic between 30-50MPa of alkaline-resisting hydrolysis-type, solid content 20 ~ 50%, modulus or aromatic waterborne polyurethane
,described superfine fibre nonwoven cloth is the one in polyamide and/or terylene and the blended obtained figured type superfine fibre nonwoven cloth of alkali soluble polyester.
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