CN105350342A - Preparation method of aqueous / solvent-free composite environmentally friendly polyurethane synthetic leather - Google Patents
Preparation method of aqueous / solvent-free composite environmentally friendly polyurethane synthetic leather Download PDFInfo
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- CN105350342A CN105350342A CN201510634193.0A CN201510634193A CN105350342A CN 105350342 A CN105350342 A CN 105350342A CN 201510634193 A CN201510634193 A CN 201510634193A CN 105350342 A CN105350342 A CN 105350342A
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- polyether
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- aqueous
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004814 polyurethane Substances 0.000 title claims abstract description 22
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 24
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000002562 thickening agent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 11
- 238000010030 laminating Methods 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- 238000004513 sizing Methods 0.000 claims description 11
- -1 polycarbodiimide Substances 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 150000001450 anions Chemical group 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920001577 copolymer Chemical class 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 6
- 230000036541 health Effects 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000005187 foaming Methods 0.000 abstract 3
- 229920001971 elastomer Polymers 0.000 abstract 2
- 239000000806 elastomer Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 abstract 2
- 239000002344 surface layer Substances 0.000 abstract 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract 2
- 210000004207 dermis Anatomy 0.000 abstract 1
- 210000003491 skin Anatomy 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0065—Organic pigments, e.g. dyes, brighteners
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
- D06N2211/106—Footwear
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/20—Packaging
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention discloses a preparation method of aqueous / solvent-free composite environmentally friendly polyurethane synthetic leather, the synthetic leather comprises an aqueous elastomer surface layer and a solvent-free foaming intermediate layer, the aqueous elastomer surface layer resin is thermosetting polyether aqueous polyurethane resin, the solvent-free foaming intermediate layer is thermosetting two-component polyether solvent-free foaming polyurethane resin, and the two-component material is polyether combination A material and polyether B material prepolymer. The preparation process does not use any organic solvent, achieves the synthetic leather production and processing, finished product zero solvent use and health and environmental friendliness; at the same time, the advantages of the aqueous polyurethane resin and the solvent-free polyurethane resin are combined, and the obtained synthetic leather products has strong pattern stereoscopic impression, soft hand feeling, superior hydrolysis resistance and other physical properties, and skin and leather feeling equivalent to natural dermis.
Description
One, technical field
The present invention relates to a kind of manufacture method of Synthetic Leather, the preparation method of specifically a kind of water-based/solvent-free composite environment-friendly Synthetic Leather, belong to synthetic leather and manufacture field.
Two, background technology
Along with the development of national economy and the raising of people's living standard, consumer not only has high request for the quality of clothing, shoes and hats, sofa furniture, automotive trim product, requires also very high to the environmental-protecting performance of material simultaneously.Although current corium product has the advantages such as comfortable feel, good springiness, durability be better, but due to natural leather resource-constrained, with high-performance, the high-quality of first layer lether making, supply falls short of demand especially for high value added product, and price continues soaring, has become the synonym of luxury consumer goods.And Synthetic Leather is as the desirable alternative materials of corium, weak point is that it must use strong polar organic solvent DMF as solvent, is unfavorable for the health environment-friendly of production process and finished consumer process.Under these circumstances, environment-friendly type high physical property Synthetic Leather product is well selected for consumer provides one.
Three, summary of the invention
The present invention aims to provide the preparation method of a kind of water-based/solvent-free composite environment-friendly Synthetic Leather, manufacture process and the equal environmental protection of final products; The product third dimension of patterns developed is strong, soft, and the physical properties such as hydrolysis are superior, and skin sense and skin sense strong.
The preparation method of water-based of the present invention/solvent-free composite environment-friendly Synthetic Leather, comprises the steps:
(1) in release liners, apply aqueous covercoat slurry, after drying forming, obtain aqueous covercoat;
(2) be cast on described aqueous covercoat by PU low-pressure blowing machine after polyether-type being combined A material and the mixing of polyether-type B material performed polymer, obtain solvent-free intermediate layer by feeding baking oven pre-reaction after scraper coating evenly; Described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type;
(3) by the solvent-free intermediate layer of pre-reaction laminating base cloth, then send into the sizing of baking oven crosslinking curing, rolling is also peeled off release liners and can be obtained synthetic leather finished product after slaking.
The coating thickness controlling aqueous covercoat slurry in step (1) is 0-0.5mm, preferred 0.1-0.4mm; Bake out temperature is 50-150 DEG C, is preferably 60-130 DEG C; Drying time is 0-4min, is preferably 1-3min.
In step (2), polyether-type combination A material and polyether-type B expect that the mass ratio of performed polymer is 2.5:1-1:2.5; The coating thickness being controlled mixed slurry by scraper coating is 0.05-1mm, is preferably 0.15-0.8mm; The reaction temperature of described pre-reaction is 50-150 DEG C, and be preferably 80-130 DEG C, pre-reaction time is 0-4min, is preferably 1-3min.
In step (3), the temperature of crosslinking curing sizing is 100-150 DEG C, is preferably 110-140 DEG C, and the time of crosslinking curing sizing is 4-10min, is preferably 5-8min.
In step (3), curing temperature is 40-100 DEG C, and be preferably 40-80 DEG C, the curing time is 6-72h, is preferably 12-72h.
The formula of described aqueous covercoat slurry is constructed as follows by mass fraction:
Described aqueous polyurethane is anion heat curing-type polyethers waterborne polyurethane resin, and the anionic group in described anionic polyethers waterborne polyurethane resin is carboxylate group and/or sulfonate group.Described aqueous polyurethane is preferably anion heat curing-type polyether resin water-base resin 7377 (production of Yantai Wan Hua chemical company).
Described crosslinking agent is one or more in polyisocyanate crosslinker, epoxide, aziridine, polycarbodiimide, epoxy silane, N-methylol compound and polyamine, is preferably one or more in polyisocyanate crosslinker, polycarbodiimide, N-methylol compound;
Described water-based thickener is one or more in inorganic thickening agent, cellulose thickener, polyacrylate-type thickeners, association type polyurethane thickener, association type polyether polyol thickener, is preferably association type polyurethane thickener or/and association type polyether polyol thickener;
Described leveling auxiliary agent is containing one or more in the silicone based levelling agent of hydrophilic radical, acrylate copolymer class levelling agent;
Described wetting aid be polysiloxanes, polysiloxane polyether copolymer, Organic fluoride polymer-modified in one or more;
Described antiwear assistant is super high molecular weight (number-average molecular weight >=1,000,000) polysiloxanes;
Described nano material is aerosil.
Described polyether-type combination A material is polyether-type premixed systems C72063/1C-A (BASF AG's product).
Described polyether-type B expects that performed polymer is polyether-type performed polymer C34670/1C-B (BASF AG's product).
Synthetic leather of the present invention comprises aqueous covercoat and solvent-free intermediate layer, described aqueous covercoat resin is the polyether type aqueous polyurethane resin of heat curing-type, described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type, and described pair of component material is that polyether-type combination A material and polyether-type B expect performed polymer.
The preparation method of water-based of the present invention/solvent-free composite environment-friendly Synthetic Leather, specifically comprises the steps:
(1) preparation of aqueous covercoat: apply aqueous covercoat slurry in release liners, obtain aqueous covercoat after drying forming;
(2) preparation in solvent-free intermediate layer: be cast on described aqueous covercoat by PU low-pressure blowing machine after polyether-type being combined A material and the mixing of polyether-type B material performed polymer, and after scraper painting is scraped, by baking oven pre-reaction;
(3) laminating base cloth: by the solvent-free intermediate layer laminating base cloth of pre-reaction;
(4) crosslinking curing, rolling: send into the sizing of baking oven crosslinking curing, then by its rolling after laminating base cloth;
(5) slaking: the resultant Leather after rolling and release liners are delivered to curing chamber slaking;
(6) release liners is peeled off: the paper after slaking, leather are carried out release liners stripping, obtains synthetic leather finished product.
Water-based/solvent-free composite environment-friendly the Synthetic Leather of the inventive method processing and manufacturing, combine the advantage of waterborne polyurethane resin and solvent-free polyurethane resin, the product third dimension of patterns developed is strong, soft, the physical properties such as hydrolysis are superior, and skin sense and skin sense are strong, be applicable to the different application fields such as sofa furniture leather, clothing leather, men and women's playshoes leather, packaging leather.
Manufacture process of the present invention does not use any organic solvent, and zero solvent achieving synthetic leather production and processing and finished product uses and health environment-friendly; Simultaneously by the advantages of waterborne polyurethane resin and solvent-free polyurethane resin, not only third dimension of patterns is strong, soft for the synthetic leather product of acquisition, and the physical properties such as hydrolysis are superior, and skin sense and skin sense suitable with natural leather.The environment-protecting polyurethane synthetic leather that the inventive method obtains is applicable to the different application fields such as sofa furniture leather, clothing leather, men and women's playshoes leather, packaging leather.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The advantage of aqueous polyurethane with no-solvent polyurethane premixed systems combines by water-based/solvent-free composite environment-friendly Synthetic Leather that 1, prepared by the present invention, there is third dimension of patterns strong, soft, the physical properties such as hydrolysis are superior, and skin sense and the feature such as skin sense is suitable with natural leather;
2, the water-based/solvent-free composite environment-friendly Synthetic Leather preparation technology for preparing of the present invention is advanced, the advantages such as moderate cost, and prepares omnidistance environment protection health, final finished environment protection health;
3, water-based/solvent-free composite environment-friendly Synthetic Leather of preparing of the present invention, by the reasonable employment of nano material aerosil, solves the adhesion problem in aqueous covercoat and solvent-free intermediate layer in process well.
Four, detailed description of the invention
Below by several specific embodiment, the present invention is further illustrated; but it is to be noted that concrete material proportion, process conditions and result etc. described in embodiments of the invention are only for illustration of the present invention; can not limit the scope of the invention with this; the equivalence change that every Spirit Essence according to the present invention is done or modification, all should be encompassed in protection scope of the present invention.
In following embodiment, the source of each raw material is:
What aqueous covercoat resin adopted is anion heat curing-type polyether resin water-base resin 7377, is Yantai Wan Hua chemical company product;
That waterborne curing agent adopts is Carbodiimides crosslinking agent UN-557, is Shanghai You En Chemical Co., Ltd. product;
That water-based thickener adopts is association type polyurethane thickener BorchiGelW44, is German Borchers Products;
That aqueous color paste adopts is aqueous black paste TSELR01, is Suzhou Shi Ming scientific & technical corporation product;
That water-based leveling auxiliary agent adopts is organic silicon surfactant BYK-346, is German Bi Ke Products;
That water-based wetting aid adopts is polysiloxane polyether copolymer TEGU245, is Yantai Wan Hua chemical company product;
That aqueous wear-resistant auxiliary agent adopts is super high molecular weight polysiloxane emulsion DC-51, is Dow Corning Corporation's product;
Nano material is aerosil HL-150, is Guangzhou Science and Technology Ji Sheng Industrial Co's product;
Polyether-type combination A material is polyether-type premixed systems C72063/1C-A, is BASF AG's product;
Polyether-type B expects that performed polymer is polyether-type performed polymer C34670/1C-B, is BASF AG's product;
Embodiment 1:
The present embodiment synthetic leather comprises aqueous covercoat and solvent-free intermediate layer, described aqueous covercoat resin is the polyether type aqueous polyurethane resin of heat curing-type, described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type, and described pair of component material is that polyether-type combination A material and polyether-type B expect performed polymer.
The preparation method of water-based in the present embodiment/solvent-free composite environment-friendly Synthetic Leather, specifically comprises the steps:
(1) preparation of aqueous covercoat: apply aqueous covercoat slurry in release liners, the coating thickness controlling aqueous covercoat slurry is 0.2mm, and 120 DEG C of oven dry 3min Post RDBMS are shaping, obtain aqueous covercoat;
Described aqueous covercoat is heat curing-type polyethers waterborne polyurethane resin;
In described aqueous covercoat slurry, each raw material by the proportioning of parts by mass is:
(2) preparation in solvent-free intermediate layer: polyether-type is combined A material and the 2:1 mixing in mass ratio of polyether-type B material performed polymer, be cast on aqueous covercoat by PU low-pressure blowing machine, and scrape through scraper painting, scraper is coated with and scrapes gap is 0.4mm, then in 130 DEG C of pre-reaction 2min, solvent-free intermediate layer is obtained; Described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type; Wherein polyether-type combination A material is that polyether-type premixed systems C72063/1C-A, polyether-type B expect that performed polymer is polyether-type performed polymer C34670/1C-B;
(3) laminating base cloth: by solvent-free intermediate layer laminating base cloth;
(4) crosslinking curing, rolling: send into baking oven after laminating base cloth in 140 DEG C through the sizing of 8min crosslinking curing, then by its rolling;
(5) slaking: the resultant Leather after rolling and release liners are delivered to curing chamber in 60 DEG C of slaking 48h;
(6) release liners is peeled off: the paper after slaking, leather are carried out release liners stripping, obtains synthetic leather finished product.
Embodiment 2:
The present embodiment synthetic leather comprises aqueous covercoat and solvent-free intermediate layer, described aqueous covercoat resin is the polyether type aqueous polyurethane resin of heat curing-type, described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type, and described pair of component material is that polyether-type combination A material and polyether-type B expect performed polymer.
The preparation method of water-based in the present embodiment/solvent-free composite environment-friendly Synthetic Leather, specifically comprises the steps:
(1) preparation of aqueous covercoat: apply aqueous covercoat slurry in release liners, the coating thickness controlling aqueous covercoat slurry is 0.4mm, and 130 DEG C of oven dry 3min Post RDBMS are shaping, obtain aqueous covercoat;
Described aqueous covercoat is heat curing-type polyethers waterborne polyurethane resin;
In described aqueous covercoat slurry, each raw material by the proportioning of parts by mass is:
(2) preparation in solvent-free intermediate layer: polyether-type is combined A material and the 1.25:1 mixing in mass ratio of polyether-type B material performed polymer, be cast on aqueous covercoat by PU low-pressure blowing machine, and scrape through scraper painting, scraper is coated with and scrapes gap is 0.6mm, then in 130 DEG C of pre-reaction 3min, solvent-free intermediate layer is obtained; Described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type; Wherein polyether-type combination A material is that polyether-type premixed systems C72063/1C-A, polyether-type B expect that performed polymer is polyether-type performed polymer C34670/1C-B;
(3) laminating base cloth: by solvent-free intermediate layer laminating base cloth;
(4) crosslinking curing, rolling: send into baking oven after laminating base cloth in 120 DEG C through the sizing of 8min crosslinking curing, then by its rolling;
(5) slaking: the resultant Leather after rolling and release liners are delivered to curing chamber in 80 DEG C of slaking 36h;
(6) release liners is peeled off: the paper after slaking, leather are carried out release liners stripping, obtains synthetic leather finished product.
The correlated characteristic of above-mentioned two embodiments is as follows:
| Feel | Decorative pattern | Skin sense | Anti-hydrolytic performance | |
| Embodiment 1 | Soft | Full | By force | 5-10 week |
| Embodiment 2 | Soft | Full | By force | 5-10 week |
The invention provides a kind of convenient feasible method manufacturing full environment-protecting polyurethane synthetic leather, and the advantage of aqueous polyurethane with no-solvent polyurethane bi-material is combined effectively, it is strong, soft that the water-based prepared/solvent-free compound Synthetic Leather not only has third dimension of patterns, the features such as anti-hydrolytic performance is superior, and skin sense and skin sense are suitable with natural leather, be applicable to the application of the different field such as sofa furniture leather, clothing leather, men and women's playshoes leather, packaging leather.
Claims (10)
1. a preparation method for water-based/solvent-free composite environment-friendly Synthetic Leather, is characterized in that comprising the steps:
(1) in release liners, apply aqueous covercoat slurry, after drying forming, obtain aqueous covercoat;
(2) be cast on described aqueous covercoat by PU low-pressure blowing machine after polyether-type being combined A material and the mixing of polyether-type B material performed polymer, obtain solvent-free intermediate layer by feeding baking oven pre-reaction after scraper coating evenly; Described solvent-free intermediate layer is the two component polyether-type non-solvent foamed polyurethane resin of heat curing-type;
(3) by the solvent-free intermediate layer of pre-reaction laminating base cloth, then send into the sizing of baking oven crosslinking curing, rolling is also peeled off release liners and can be obtained synthetic leather finished product after slaking.
2. preparation method according to claim 1, is characterized in that:
The formula of described aqueous covercoat slurry is constructed as follows by mass fraction:
3. preparation method according to claim 2, is characterized in that:
Described aqueous polyurethane is anion heat curing-type polyethers waterborne polyurethane resin, and the anionic group in described anionic polyethers waterborne polyurethane resin is carboxylate group and/or sulfonate group;
Described crosslinking agent is one or more in polyisocyanate crosslinker, epoxide, aziridine, polycarbodiimide, epoxy silane, N-methylol compound and polyamine;
Described water-based thickener is one or more in inorganic thickening agent, cellulose thickener, polyacrylate-type thickeners, association type polyurethane thickener, association type polyether polyol thickener;
Described leveling auxiliary agent is containing one or more in the silicone based levelling agent of hydrophilic radical, acrylate copolymer class levelling agent;
Described wetting aid be polysiloxanes, polysiloxane polyether copolymer, Organic fluoride polymer-modified in one or more;
Described antiwear assistant is super high molecular weight polysiloxanes;
Described nano material is aerosil.
4. preparation method according to claim 3, is characterized in that:
Described aqueous polyurethane is anion heat curing-type polyether resin water-base resin 7377;
Described crosslinking agent is that association type polyurethane thickener is or/and association type polyether polyol thickener;
Described polyether-type combination A material is polyether-type premixed systems C72063/1C-A;
Described polyether-type B expects that performed polymer is polyether-type performed polymer C34670/1C-B.
5. preparation method according to claim 2, is characterized in that:
The coating thickness controlling aqueous covercoat slurry in step (1) is 0-0.5mm, and bake out temperature is 50-150 DEG C, and drying time is 0-4min.
6. the preparation method according to claim 2 or 5, is characterized in that:
The coating thickness controlling aqueous covercoat slurry in step (1) is 0.1-0.4mm, and bake out temperature is 60-130 DEG C, and drying time is 1-3min.
7. preparation method according to claim 2, is characterized in that:
In step (2), polyether-type combination A material and polyether-type B expect that the mass ratio of performed polymer is 2.5:1-1:2.5; The coating thickness being controlled mixed slurry by scraper coating is 0.05-1mm; The reaction temperature of described pre-reaction is 50-150 DEG C, and pre-reaction time is 0-4min.
8. the preparation method according to claim 2 or 7, is characterized in that:
In step (2), polyether-type combination A material and polyether-type B expect that the mass ratio of performed polymer is 2.5:1-1:2.5; The coating thickness being controlled mixed slurry by scraper coating is 0.15-0.8mm; The reaction temperature of described pre-reaction is 80-130 DEG C, and pre-reaction time is 1-3min.
9. preparation method according to claim 2, is characterized in that:
In step (3), the temperature of crosslinking curing sizing is 100-150 DEG C, and the time of crosslinking curing sizing is 4-10min; Curing temperature is 40-100 DEG C, and the curing time is 6-72h.
10. preparation method according to claim 2, is characterized in that:
In step (3), the temperature of crosslinking curing sizing is 110-140 DEG C, and the time of crosslinking curing sizing is 5-8min; Curing temperature is 40-80 DEG C, and the curing time is 12-72h.
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