CN102408699B - Composite slurry, synthetic leather substrate and preparation method of synthetic leather substrate - Google Patents
Composite slurry, synthetic leather substrate and preparation method of synthetic leather substrate Download PDFInfo
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- CN102408699B CN102408699B CN201110262357.3A CN201110262357A CN102408699B CN 102408699 B CN102408699 B CN 102408699B CN 201110262357 A CN201110262357 A CN 201110262357A CN 102408699 B CN102408699 B CN 102408699B
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- waterborne polyurethane
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 65
- 239000002002 slurry Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000758 substrate Substances 0.000 title abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 81
- 239000004814 polyurethane Substances 0.000 claims abstract description 81
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 58
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004744 fabric Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000004088 foaming agent Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000007711 solidification Methods 0.000 claims abstract description 7
- 230000008023 solidification Effects 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 63
- 239000000463 material Substances 0.000 claims description 36
- -1 polysiloxane Polymers 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 230000001112 coagulating effect Effects 0.000 claims description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 125000000129 anionic group Chemical group 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000005187 foaming Methods 0.000 claims description 15
- 239000004902 Softening Agent Substances 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000003094 microcapsule Substances 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004156 Azodicarbonamide Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 6
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- 238000007603 infrared drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- 229920001610 polycaprolactone Polymers 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 31
- 239000010985 leather Substances 0.000 description 15
- 239000004677 Nylon Substances 0.000 description 12
- 229920001778 nylon Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 6
- 229920006052 Chinlon® Polymers 0.000 description 5
- 229920004933 Terylene® Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 229920005586 poly(adipic acid) Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 238000005485 electric heating Methods 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to waterborne polyurethane composite slurry, a waterborne polyurethane synthetic leather substrate, and a preparation method of the waterborne polyurethane synthetic leather substrate. The preparation method of the waterborne polyurethane synthetic leather substrate comprises the following steps: a. preparing waterborne polyurethane composite slurry; b. dipping a non-woven fabric with the composite slurry, strickling the surface of the non-woven fabric by a scraper; c. solidifying the treated non-woven fabric by waterborne solidification liquid; d. performing water washing by a water washing trough after the solidification of the waterborne polyurethane resin so as to form a substrate fabric; e. drying the substrate fabric in a drying box, increasing the temperature sectionally, allowing a foaming agent to foam during the drying process, performing hot setting to form the substrate fabric so as to obtain the synthetic leather substrate. The waterborne polyurethane synthetic leather substrate is prepared by the above preparation method. A foaming agent is adopted in the process of the invention, which foams during the drying process of the substrate so as to form a microporous structure, and thus the synthetic leather substrate is provided with excellent elasticity.
Description
Technical Field
The invention relates to a composite slurry, a synthetic leather base material and a preparation method of the synthetic leather base material, in particular to a waterborne polyurethane composite slurry, a waterborne polyurethane synthetic leather base material and a preparation method of the waterborne polyurethane synthetic leather base material, and belongs to the technical field of synthetic leather production.
Background
Polyurethane synthetic leather is currently used in various areas of people's lives, increasing at a rate of over 10% in recent years, and over 12 billion meters in 2009. The prior traditional polyurethane slurry for synthetic leather is a solvent-based slurry, has mature processing technology and various product varieties, is widely applied to wet synthetic leather for clothing leather, sofa leather, luggage leather and shoe leather, and is prepared by impregnating non-woven fabrics with the solvent-based polyurethane slurry, or coating the slurry on the non-woven fabrics impregnated with the slurry, then solidifying in Dimethylformamide (DMF) aqueous solution through a wet production process, and then washing and drying. DMF is required to be used for preparing the synthetic leather, and although most of the DMF is recovered, a small part of solvent which cannot be recovered is discharged in a gas and waste water mode; meanwhile, the sewage discharge of the national environmental protection department in the leather industry stipulates that the DMF content is respectively below 0.1mg/L and 0.2 mg/L. In addition, DMF remains in the product, and the DMF residue of many environment-friendly products is regulated to be 300ppm or even more and is required to be below 30 ppm.
The waterborne polyurethane resin takes water as a dispersion medium, has the advantages of no toxicity, environmental protection, safety, non-flammability and the like, and is the best substitute product of solvent type resin. The research and application of the waterborne polyurethane in various countries have great policy and fund support, the research and application of the waterborne polyurethane resin in China is also greatly invested, but the application of the waterborne polyurethane resin in the synthetic leather is relatively only a little progress in recent years, the main research is focused on the surface finishing of the synthetic leather, only the technologies such as a waterborne dry film transfer technology and printing are applied to the actual production, and the development of the overall technology of the waterborne polyurethane synthetic leather is still at the initial stage. With the development of the water-based polyurethane resin technology, the product performance is improved, and the application research investment of various related companies in China and China is increased in recent years. The waterborne polyurethane resin takes water as a dispersion medium, so the waterborne polyurethane resin has the characteristics of safety and environmental protection, but the hydrophilic characteristic ensures that the waterborne polyurethane resin has certain difference in water resistance and strength compared with the traditional solvent type polyurethane resin and has great difference in processing performance, and particularly, the waterborne polyurethane resin as an impregnating slurry and a synthetic leather base material cannot refer to the traditional technical process at all in technical process, so a new technical process must be developed. The company adopts the waterborne polyurethane resin to prepare the synthetic leather, and the research work for a long time makes great progress in nearly two years. We have a great breakthrough in this technology.
Disclosure of Invention
The invention aims to solve the technical problem of providing a synthetic leather base material which can be used as shoe lining leather after being printed and processed by waterborne polyurethane resin; secondly, preparing shoe leather and luggage leather by dry veneering of waterborne polyurethane resin, thirdly or performing dry mechanical foaming coating of waterborne polyurethane resin on the synthetic leather base material, and then preparing the shoe leather and the luggage leather by dry veneering or printing processing of waterborne polyurethane resin on the dry foaming coating.
The technical scheme for solving the technical problems is as follows: the waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 3-5 parts of foaming agent, 1-2 parts of softening agent, 0.5-2 parts of thickening agent and 100-210 parts of water.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the anionic waterborne polyurethane resin is composed of diisocyanate, macromolecular polyol, a micromolecular chain extender, a hydrophilic chain extender containing a carboxylic group, a neutralizer and water.
Further, the solid weight percentage content of the resin is 20-40%; the 100% tensile strength of the resin dry film is 2MPa to 10 MPa.
Further, the diisocyanate is toluene diisocyanate, diphenylmethane 4.4-diisocyanate, hydrogenated diphenylmethane 4.4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
Further, the macromolecular polyol is one or more of polyoxypropylene glycol ether, polyoxypropylene triol ether, polytetrahydrofuran glycol ether, poly-caprolactone glycol ester, poly-adipate glycol ester, polycarbonate polyol, poly-terephthalic acid glycol ester and poly-phthalic acid glycol ester.
Further, the micromolecular chain extender is ethylene glycol, butanediol, diethylene glycol and 1, 6-hexanediol.
Further, the carboxyl-containing hydrophilic chain extender is dimethylolpropionic acid and dimethylolbutyric acid.
Further, the neutralizing agent is triethylamine and triethanolamine.
Further, the water is deionized water.
Further, the molecular weight of the macromolecular polyol is 250-5000, preferably 500-4000.
Further, the solid weight percentage content of the resin is 20-40%; the 100% tensile strength of the resin dry film is 2MPa to 10 MPa.
Further, the foaming agent is azodicarbonamide (low-temperature leather foaming agent) or microcapsule foaming agent. The foaming temperature of the azodicarbonamide is 135-145 ℃; the foaming temperature of the microcapsule foaming agent is 110-145 ℃.
Further, the softening agent is a modified polysiloxane softening agent;
further, the thickening agent is an associated polyurethane thickening agent and an alkali swelling acrylic acid copolymer.
Another technical solution of the present invention for solving the above technical problems is as follows: a preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing a waterborne polyurethane composite slurry;
b. dipping the non-woven fabric by using the composite slurry, and scraping the surface of the non-woven fabric by using a scraper;
c. the non-woven fabric treated in the step b is solidified by the aqueous solidification liquid;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by a washing tank to form base cloth;
e. and (3) drying the base cloth in a drying oven at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, starting foaming by using a foaming agent in the drying process, and drying and shaping for 10-20 minutes to form the synthetic leather base cloth with micropores inside.
Further, in the step a, the preparation of the aqueous polyurethane composite slurry comprises the following specific steps: stirring the raw materials of the waterborne polyurethane composite slurry for 30-60 minutes at a speed of 600-1000 rpm to obtain the waterborne polyurethane composite slurry with the density of 700-900 g/L.
Further, the non-woven fabric is polyamide fiber, polyester fiber or a blended non-woven fabric of polyamide fiber and polyester fiber.
Further, the thickness of the non-woven fabric is 0.5-2 mm.
Further, in the step b, the impregnation amount of the aqueous polyurethane resin after the non-woven fabric is impregnated with the composite slurry is 200-600 g/m2。
Further, in the step c, the pH value of the aqueous solidification solution is 5.5-3.5, and the temperature of the aqueous solidification solution is 10-50 ℃.
Further, in step e, the drying oven is an infrared drying oven, a steam drying oven or an electric heating drying oven.
Another technical solution of the present invention for solving the above technical problems is as follows: the waterborne polyurethane synthetic leather base material is prepared by the preparation method.
The invention has the beneficial effects that:
firstly, the aqueous polyurethane resin is adopted to replace solvent type polyurethane resin, so that the environment is more protected; the waterborne polyurethane resin does not contain a solvent, and can be diluted by water in the using process; the traditional solvent type polyurethane resin contains more than 70% of DMF solvent, and the DMF solvent is also required to be used in the dilution process; after 95% of DMF is recovered, a small part of DMF can be recovered and still volatilizes, and the energy consumption is large;
secondly, in the traditional process, a microporous structure is formed in the wet solidification process, so that the synthetic leather base material has good elasticity; in the process, the foaming agent is adopted, foaming is carried out in the drying process of the base material, and a microporous structure can be formed, so that the synthetic leather base material has good elasticity, and the performance meets the index requirements of shoe leather and luggage leather;
thirdly, the synthetic leather does not contain a solvent, so that the harm of the solvent to a human body is discharged; the non-woven fabric used by the synthetic leather has wide source and low price; the preparation process of the waterborne polyurethane synthetic leather is simple, energy-saving and environment-friendly. Can replace part of the traditional synthetic leather products.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 3 parts of azodicarbonamide (low-temperature leather foaming agent), 1 part of modified polysiloxane softening agent, 0.5 part of associative polyurethane thickener and 100 parts of water.
The anionic waterborne polyurethane resin consists of toluene diisocyanate, polyoxypropylene glycol ether, polyoxypropylene triol ether, glycol, dimethylolpropionic acid, triethylamine and deionized water.
The solid weight percentage content of the resin is 20 percent; the 100% tensile strength of the resin dry film was 10 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 60 minutes at the speed of 1000 revolutions per minute to obtain the waterborne polyurethane composite slurry with the density of 700 g/L;
b. the composite slurry is used for impregnating nylon/terylene non-woven fabric with the thickness of 1.0mm, and the nylon/terylene non-woven fabric is impregnated and then extruded to ensure that the impregnation amount of resin is 200g/m2And the surface of the nylon/terylene non-woven fabric is scraped by a scraper;
c. the processed chinlon/terylene non-woven fabric enters a coagulating tank, the PH value of coagulating liquid is 5.5, and the temperature of the coagulating liquid is 25 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in an infrared drying oven at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, foaming the foaming agent in the drying process, and drying and shaping for 10 minutes to form the synthetic leather base cloth with micropores inside;
a waterborne polyurethane synthetic leather base material is prepared by the preparation method of the embodiment 1.
Example 2
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 4 parts of microcapsule foaming agent, 1.5 parts of modified polysiloxane softening agent, 1 part of associative polyurethane thickener and 160 parts of water.
The anionic waterborne polyurethane resin consists of diphenylmethane 4.4-diisocyanate, polytetrahydrofuran glycol ether, polyhexamethylene glycol ester, butanediol, dimethylol butyric acid, triethanolamine and deionized water.
The weight percentage of the solid content of the resin is 30 percent; the 100% tensile strength of the resin dry film was 5 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 40 minutes at the speed of 800 revolutions per minute to obtain waterborne polyurethane composite slurry with the density of 800 g/L;
b. the composite slurry is used for impregnating nylon non-woven fabric with the thickness of 1.5mm, and the nylon non-woven fabric is impregnated with the composite slurry and then extruded to ensure that the impregnation amount of resin is 450g/m2And the surface of the nylon non-woven fabric is scraped by a scraper;
c. the processed chinlon non-woven fabric enters a coagulating tank, the PH value of coagulating liquid is 4.5, and the temperature of the coagulating liquid is 40 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in a steam drying box at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, foaming a foaming agent in the drying process, and drying and shaping for 15 minutes to form the synthetic leather base cloth with micropores inside;
a waterborne polyurethane synthetic leather base material is prepared by the preparation method of the embodiment 2.
Example 3
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 5 parts of microcapsule foaming agent, 1.5 parts of modified polysiloxane softening agent, 1.5 parts of alkali-swelling acrylic copolymer associated polyurethane thickener and 180 parts of water.
The anionic waterborne polyurethane resin consists of hexamethylene diisocyanate, poly adipic acid series diol ester, poly terephthalic acid series diol ester, diethylene glycol, dimethylol propionic acid, triethanolamine and deionized water.
The weight percent solids content of the resin is 35%; the 100% tensile strength of the resin dry film was 2 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 50 minutes at the speed of 700 revolutions per minute to obtain the waterborne polyurethane composite slurry with the density of 800 g/L;
b. impregnating the polyester non-woven fabric with the composite slurry to a thickness of 1.2mm, and extruding after impregnating the polyester non-woven fabric to ensure that the impregnation amount of the resin is 400g/m2And the surface of the polyester non-woven fabric is scraped by a scraper;
c. the processed polyester non-woven fabric enters a coagulating tank, the PH value of coagulating liquid is 4.4, and the temperature of the coagulating liquid is 40 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in an infrared drying oven at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, foaming the foaming agent in the drying process, and drying and shaping for 16 minutes to form the synthetic leather base cloth with micropores inside;
a waterborne polyurethane synthetic leather base material prepared by the preparation method of embodiment 3.
Example 4
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 5 parts of azodicarbonamide (low-temperature leather foaming agent), 2 parts of modified polysiloxane softening agent, 2 parts of alkali-swelling acrylic copolymer and 190 parts of water.
The anionic waterborne polyurethane resin consists of isophorone diisocyanate, polycarbonate polyol, diol ester of a polyphthalate series, 1, 6-hexanediol, dimethylolbutyric acid, triethylamine and deionized water. The weight percent solids content of the resin is 35%; the 100% tensile strength of the resin dry film was 8 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 50 minutes at the speed of 600 revolutions per minute to obtain the waterborne polyurethane composite slurry with the density of 900 g/L;
b. the composite slurry is used for impregnating the chinlon/terylene blended non-woven fabric with the thickness of 1.4mm, and the resin is impregnated in the non-woven fabric and extruded to ensure that the impregnation amount of the resin is 600g/m2And the surface of the non-woven fabric is scraped by a scraper;
c. putting the treated non-woven fabric into a coagulating tank, wherein the pH value of a coagulating liquid is 4, and the temperature of the coagulating liquid is 50 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in a steam drying box at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, foaming a foaming agent in the drying process, and drying and shaping for 20 minutes to form the synthetic leather base cloth with micropores inside;
a waterborne polyurethane synthetic leather base material is prepared by the preparation method of the embodiment 4.
Example 5
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 4 parts of microcapsule foaming agent, 1.5 parts of modified polysiloxane softening agent, 1 part of associative polyurethane thickener and 210 parts of water.
The anionic waterborne polyurethane resin consists of diphenylmethane 4.4-diisocyanate, polytetrahydrofuran glycol ether, polyhexamethylene glycol ester, butanediol, dimethylol butyric acid, triethanolamine and deionized water.
The weight percentage of the solid content of the resin is 40 percent; the 100% tensile strength of the resin dry film was 4 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 40 minutes at the speed of 900 revolutions per minute to obtain waterborne polyurethane composite slurry with the density of 800 g/L;
b. the composite slurry is used for impregnating nylon non-woven fabric with the thickness of 1.5mm, and the nylon non-woven fabric is impregnated with the composite slurry and then extruded to ensure that the impregnation amount of resin is 450g/m2And the surface of the nylon non-woven fabric is scraped by a scraper;
c. the processed chinlon non-woven fabric enters a coagulating tank, the PH value of coagulating liquid is 3.5, and the temperature of the coagulating liquid is 10 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in a steam drying box at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, foaming a foaming agent in the drying process, and drying and shaping for 15 minutes to form the synthetic leather base cloth with micropores inside;
a waterborne polyurethane synthetic leather base material is prepared by the preparation method of embodiment 5.
The waterborne polyurethane synthetic leather base materials prepared in the embodiments 1 to 5 have good hand feeling.
Comparative example 1
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 1.5 parts of modified polysiloxane softening agent, 1.5 parts of alkali-swelling acrylic copolymer and 180 parts of water.
The anionic waterborne polyurethane resin consists of hexamethylene diisocyanate, poly adipic acid series diol ester, poly terephthalic acid series diol ester, diethylene glycol, dimethylol propionic acid, triethanolamine and deionized water. The weight percent solids content of the resin is 35%; the 100% tensile strength of the resin dry film was 2 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 50 minutes at the speed of 700 revolutions per minute to obtain the waterborne polyurethane composite slurry with the density of 800 g/L;
b. impregnating the polyester blended non-woven fabric with the composite slurry to a thickness of 1.2mm, and extruding after impregnating the non-woven fabric to ensure that the impregnation amount of the resin is 400g/m2And the surface of the non-woven fabric is scraped by a scraper;
c. the non-woven fabric subjected to the treatment enters a coagulating tank, the PH value of a coagulating liquid is 4.4, and the temperature of the coagulating liquid is 40 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in an infrared drying oven at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, and drying and shaping for 16 minutes to form the base cloth without micropores inside;
the waterborne polyurethane synthetic leather base material is prepared by the preparation method of the comparative example 1, and the prepared waterborne polyurethane synthetic leather base material is hard in hand feeling and poor in compression elasticity.
Comparative example 2
The waterborne polyurethane composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 2 parts of microcapsule foaming agent, 1 part of associative polyurethane thickener and 160 parts of water.
The anionic waterborne polyurethane resin consists of diphenylmethane 4.4-diisocyanate, polytetrahydrofuran glycol ether, polyhexamethylene glycol ester, butanediol, dimethylol butyric acid, triethanolamine and deionized water.
The weight percentage of the solid content of the resin is 30 percent; the 100% tensile strength of the resin dry film was 5 MPa.
A preparation method of a waterborne polyurethane synthetic leather base material comprises the following specific process steps:
a. preparing the aqueous polyurethane composite slurry: stirring the raw materials of the waterborne polyurethane composite slurry for 40 minutes at the speed of 800 revolutions per minute to obtain waterborne polyurethane composite slurry with the density of 800 g/L;
b. the composite slurry is used for impregnating nylon non-woven fabric with the thickness of 1.5mm, and the nylon non-woven fabric is impregnated with the composite slurry and then extruded to ensure that the impregnation amount of resin is 450g/m2And the surface of the nylon non-woven fabric is scraped by a scraper;
c. the processed chinlon non-woven fabric enters a coagulating tank, the PH value of coagulating liquid is 5.6, and the temperature of the coagulating liquid is 40 ℃;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by water at 50 ℃ in a washing tank to form base cloth;
e. drying the base cloth in a steam drying box at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in sections, foaming the foaming agent in the drying process, and drying and shaping for 15 minutes to form the synthetic leather base cloth with a small amount of micropores inside;
the waterborne polyurethane synthetic leather base material is prepared by the preparation method, and the prepared waterborne polyurethane synthetic leather base material is hard in hand feeling.
The physical properties of the synthetic leather substrates of the above examples are listed in table 1:
the synthetic leather base material can be prepared into the full-aqueous polyurethane synthetic leather by using the aqueous polyurethane resin through a printing process, a dry-method mechanical foaming coating process and a dry-method veneering process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (13)
1. A preparation method of a waterborne polyurethane synthetic leather base material is characterized by comprising the following specific process steps:
a. preparing a waterborne polyurethane composite slurry;
b. dipping the non-woven fabric by using the composite slurry, and scraping the surface of the non-woven fabric by using a scraper;
c. the non-woven fabric treated in the step b is solidified by the aqueous solidification liquid;
d. after the waterborne polyurethane resin is solidified, washing the solidified waterborne polyurethane resin by a washing tank to form base cloth;
e. drying the base cloth in a drying oven at the temperature of 110-130-145-155 ℃ from low to high, increasing the temperature in stages, starting foaming by a foaming agent in the drying process, drying and shaping for 10-20 minutes to form the base cloth with micropores inside, and obtaining the synthetic leather base material,
the composite slurry is prepared from the following raw materials in parts by weight: 100 parts of anionic waterborne polyurethane resin, 3-5 parts of foaming agent, 1-2 parts of softening agent, 0.5-2 parts of thickening agent and 100-210 parts of water; wherein,
the anionic waterborne polyurethane resin consists of diisocyanate, macromolecular polyol, micromolecular chain extender, hydrophilic chain extender containing carboxylic group, neutralizer and water;
the foaming agent is azodicarbonamide and a microcapsule foaming agent; the softening agent is a modified polysiloxane softening agent; the thickening agent is associated polyurethane thickening agent and alkali swelling acrylic acid copolymer.
2. The preparation method of claim 1, wherein in the step a, the concrete steps of preparing the aqueous polyurethane composite slurry are as follows: stirring the raw materials of the waterborne polyurethane composite slurry for 30-60 minutes at a speed of 600-1000 rpm to obtain the waterborne polyurethane composite slurry with the density of 700-900 g/L.
3. The production method according to claim 1, wherein the nonwoven fabric is a polyamide fiber, a polyester fiber, or a mixed nonwoven fabric of a polyamide fiber and a polyester fiber.
4. The method according to claim 3, wherein the thickness of the nonwoven fabric is 0.5 to 2 mm.
5. The preparation method according to claim 1, wherein in the step b, the impregnation amount of the aqueous polyurethane resin after the composite slurry is impregnated into the non-woven fabric is 200-600 g/m2。
6. The method as claimed in claim 1, wherein in the step c, the pH of the aqueous coagulating liquid is 5.5 to 3.5, and the temperature of the aqueous coagulating liquid is 10 to 50 ℃.
7. The method according to claim 1, wherein in step e, the drying oven is an infrared drying oven, a steam drying oven or an electrically heated drying oven.
8. The method according to any one of claims 1 to 7, wherein the resin has a solids content of 20 to 40% by weight; the 100% tensile strength of the resin dry film is 2 MPa-10 MPa.
9. The production method according to any one of claims 1 to 7, wherein the diisocyanate is toluene diisocyanate, diphenylmethane 4.4-diisocyanate, hydrogenated diphenylmethane 4.4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate; the macromolecular polyol is one or more of polyoxypropylene glycol ether, polyoxypropylene triol ether, polytetrahydrofuran glycol ether, polycaprolactone glycol ester, glycol ester of polycaproic acid, polycarbonate polyol, glycol ester of poly-terephthalic acid and glycol ester of poly-phthalic acid; the micromolecular chain extender is ethylene glycol, butanediol, diethylene glycol and 1, 6-hexanediol; the carboxyl-containing hydrophilic chain extender is dimethylolpropionic acid and dimethylolbutyric acid; the neutralizing agent is triethylamine and triethanolamine; the water is deionized water.
10. The method according to claim 9, wherein the molecular weight of the macromolecular polyol is 250 to 5000.
11. The method according to claim 10, wherein the molecular weight of the macromolecular polyol is 500 to 4000.
12. The process according to any one of claims 1 to 7, wherein the azodicarbonamide is foamed at a temperature of 135 ℃ to 145 ℃; the foaming temperature of the microcapsule foaming agent is 110-145 ℃.
13. An aqueous polyurethane synthetic leather base material, characterized in that the synthetic leather base material is prepared by the preparation method of any one of claims 7 to 12.
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