CN115478441B - Elastic soft synthetic leather - Google Patents
Elastic soft synthetic leather Download PDFInfo
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- CN115478441B CN115478441B CN202211163460.7A CN202211163460A CN115478441B CN 115478441 B CN115478441 B CN 115478441B CN 202211163460 A CN202211163460 A CN 202211163460A CN 115478441 B CN115478441 B CN 115478441B
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- powder
- wet
- synthetic leather
- polyurethane resin
- leather
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 69
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 78
- 239000010985 leather Substances 0.000 claims abstract description 65
- 239000000835 fiber Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000004744 fabric Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims description 104
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 77
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 68
- 229920000570 polyether Polymers 0.000 claims description 68
- 229920002545 silicone oil Polymers 0.000 claims description 64
- 239000002904 solvent Substances 0.000 claims description 58
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 57
- 241001465754 Metazoa Species 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 33
- 229920002522 Wood fibre Polymers 0.000 claims description 19
- 239000002025 wood fiber Substances 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 229920013822 aminosilicone Polymers 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 150000001768 cations Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 2
- 150000002500 ions Chemical class 0.000 claims 1
- 239000010703 silicon Substances 0.000 abstract description 50
- 229910052710 silicon Inorganic materials 0.000 abstract description 50
- 239000000463 material Substances 0.000 abstract description 21
- 238000001035 drying Methods 0.000 abstract description 13
- 235000013372 meat Nutrition 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 20
- 239000004902 Softening Agent Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 239000004671 silicon softener Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000011268 mixed slurry Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 241001494479 Pecora Species 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007665 sagging Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007790 scraping Methods 0.000 description 5
- 210000003491 skin Anatomy 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003161 proteinsynthetic effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000007730 finishing process Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 241000321398 Dermatolepis dermatolepis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 210000004207 dermis Anatomy 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002344 surface layer 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
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
-
- 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
- D06N3/0047—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 obtained by incorporating air, i.e. froth
-
- 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
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic 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
- D06N3/12—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
-
- 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
- D06N2209/1642—Hardnes
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to elastic soft synthetic leather, which comprises a base cloth layer, a wet-process bass and a dry-process veneering layer, wherein the wet-process bass consists of polyurethane resin, organic silicon and a filler, and the organic silicon is adhered to the fiber micropores of the filler, the micropores and gaps in the polyurethane resin. The elastic soft synthetic leather has soft and comfortable hand feeling, strong meat quality and good strength, is a cheap and good synthetic leather material, and can be applied to the fields of decorative materials such as clothing leather, luggage leather and the like.
Description
Technical Field
The invention relates to the technical field of synthetic leather manufacturing, relates to elastic soft synthetic leather, and relates to a softener.
Background
The natural resources of the soft dermis are limited, so that the price is high, and the ever-increasing market demands cannot be met. In order to improve the soft hand feeling of synthetic leather, a leather-making factory generally adopts a graining process, an organic silicon softening agent is added into a water trough, finished leather is quickly soaked in the water trough and rolled, and then baked, kneaded and dried, because polyurethane resin is water-repellent, and micropore gaps and fiber gaps of wood fiber powder or paper pulp fiber powder are filled and blocked by the polyurethane resin, the softening agent cannot permeate into the internal tissues of the fiber powder, and cannot permeate into micropores of leather bass, under the limitation of the process, only a very small amount of the softening agent is adsorbed into the pores formed by shrinkage of Bessen filler fibers, the concentration of the softening agent cannot be high, and if the softening agent is too high, excessive silicone oil is adhered to the surface of the bass, so that the dry-method surface layer and the bass are easily attached to be unstable.
In recent years, soft protein synthetic leather appears on the market, the bass obtains rich and compact cells due to the action of the polyvinyl alcohol in production ingredients, so that the soft feel is realized, and meanwhile, the polyvinyl alcohol is easy to block in a solvent recovery system, so that the production stopping and dredging are needed, a large amount of manpower and financial resources are consumed, and safety problems such as solvent leakage and pollution are easily caused. The existing manufacturing process of the soft protein synthetic leather is not suitable for mass production and difficult to popularize, so that the production efficiency is low, the manufacturing cost is high, and the price is high. The soft hand feeling of the soft protein synthetic leather at present depends on the compactness of the base cells unilaterally, and if the base cells are more compact, the softness is better, but the peeling strength is poorer. Meanwhile, the existing synthetic leather only pursues the softness of leather, and the texture of a finished product of contract leather is not considered, so that the existing synthetic leather has heavier plastic feel and has no resilience of meat texture. Under the condition that the living demands of people are increasingly increased, the industries of clothing, shoes, caps, bags, sofas and the like especially need to design a synthetic leather material with low price, soft hand feeling and good strength, and simultaneously ensure the surface texture of the synthetic leather.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the elastic soft synthetic leather which is low in cost, soft in handfeel and good in strength.
The elastic soft synthetic leather comprises base cloth, wet bass and dry veneering, wherein the wet bass comprises polyurethane resin, organic silicon and filler, and the organic silicon is adhered to the fiber micropores of the filler, the micropores and gaps in the polyurethane resin.
Further, the filler comprises animal leather powder.
Further, the filling material is formed by mixing animal leather powder and fiber powder, wherein the fiber powder comprises one or more of wood fiber powder, paper pulp fiber powder and light calcium powder.
Further, the weight ratio of the polyurethane resin to the animal leather powder is 30:5-30.
Further, the weight ratio of the polyurethane resin to the animal leather powder to the fiber powder is 30:5-30:10-35.
Further, the weight ratio of the polyurethane resin to the organic silicon in the wet-process bass is 30:0.5-3.8.
Further, the organic silicon is 1 or 2 of amino silicone oil and amino polyether block silicone oil.
Further, the wet bass is prepared from a wet mixture coated on a base cloth, wherein the wet mixture comprises polyurethane resin solvent liquid, a softener, N-dimethylformamide and a filler, and the softener comprises organic silicon or an organic silicon softener containing organic silicon.
Further, the ionic type of the softener is cation, and the pH value of the organosilicon softener is less than 5.
Further, the molecular weight of the amino polyether block silicone oil is 5000-30000, and the amino polyether block silicone oil is formed by compounding 2 or more amino polyether block silicone oils with different molecular weights.
Further, the weight ratio of the polyurethane resin solvent liquid to the organic silicon softening agent is 100:2-15.
Further, the wood fiber powder or the paper pulp fiber powder is high-expansion fiber powder, the expansion rate is 17-25, and the mesh number is 350-700.
Further, the animal leather powder consists of one or more of cowhide leather powder, sheep hide leather powder and pig hide leather powder, and the mesh number of the animal leather powder is 200-1000.
The invention has the beneficial effects that:
1. The wet bass contains animal leather powder, and the animal leather powder has certain softness and fullness and has the resilience effect of meat texture, so that the prepared wet bass is softer, plump and has meat texture. The wet hair bays are used to enable the prepared synthetic leather to have the elasticity of human skin, and the grade of the synthetic leather finished product is improved.
2. The wet bass mixed with the animal leather powder has extremely high water absorption performance, and the synthetic leather after moisture regaining and water absorption has very good sagging feel, thereby increasing the weight and improving the softness. Meanwhile, the hydrophilic organic silicon further promotes the water absorption capacity of the animal leather powder, and the produced synthetic leather has a sagging feel.
3. The animal leather powder has fluffy fiber structure and good combination property with resin, and the produced synthetic leather has good strength.
4. The inside of the wet bass contains organic silicon, and the organic silicon is adhered to the inner wall of a bubble formed by shrinkage of fibers of animal leather powder and fiber powder in the filling material, the fiber micropores of the filling material and the micropores and gaps in the polyurethane resin, so that the organic silicon has the effects of lubricating and reducing friction coefficient, and the touch feeling is soft and comfortable. The organic silicon is matched with the animal leather powder, and the produced synthetic leather is soft and plump in meat feel. The softness, fullness and firmness of the synthetic leather are higher than those of the sheep skin, so that the high-end of the synthetic leather is realized, and the high added value of the synthetic leather production is realized.
5. The bass relies on the softening action of soft organosilicon, and the foam does not need to be excessively dense, so the bass has good firmness and good peel strength and tearing strength.
6. Soft organic silicon is adsorbed in pores and gaps of the bass, and is rarely carried away by water in a water washing process of a solidification tank. Meanwhile, soft organic silicon is liquid, and a solvent recovery system is not easy to block.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the intended purpose of the present invention, the following detailed description will refer to the specific implementation, structure, characteristics and effects according to the present invention in conjunction with the preferred embodiments.
The invention provides elastic soft synthetic leather, which comprises a base cloth layer, a wet-process bass and a dry-process veneer layer, wherein the wet-process bass comprises polyurethane resin, organic silicon and a filler, and the filler can be selected from fillers containing animal leather powder. And organosilicon is adhered to the inner walls of the cells formed by shrinkage of the fibers of the filling material, the micropores of the fibers of the filling material, and the micropores and gaps in the polyurethane resin. The weight ratio of the polyurethane resin to the organic silicon in the wet-process bass is 30:0.5-3.8, and the optimal ratio is 30:1.5.
Wherein the organosilicon is preferably one or two of amino silicone oil and amino polyether block silicone oil, and the amino polyether block silicone oil is preferably hydrophilic amino polyether block silicone oil. The hydrophilic amino polyether block silicone oil is prepared by adding a penetrating agent material on the basis of amino polyether block silicone oil. The organic silicon is adhered to the positions of the cells, the micropores and the gaps in the wet-process bass to lubricate and reduce friction coefficient, and the touch feeling is soft and comfortable.
Wet bass is made of wet mixture coated on base cloth. The wet mixture is prepared from polyurethane resin solvent liquid, a softening agent, N-dimethylformamide and a filler. Or the other proportion of the wet mixture is made of polyurethane resin solvent liquid, softening agent, polyvinyl alcohol, N-dimethylformamide and filling material. The softener is organic silicon or organic silicon softener containing organic silicon, and the polyurethane resin solvent liquid contains polyurethane resin. The weight ratio of water in the wet mixture is less than 3.5%. If the moisture in the wet-process mixture with the dye is more, the pigment easily permeates into water in the process of washing the wet-process mixture with the coagulating tank after the coating of the wet-process mixture, and the base cloth is polluted. Therefore, the weight ratio of water in the wet mixture is less than 3.5%, and the pollution to the base cloth is reduced.
The filling material comprises animal leather powder or is formed by mixing animal leather powder and fiber powder. When the filler is animal leather powder, the weight ratio of the polyurethane resin to the animal leather powder is 30:5-30, and the optimal ratio is 30:10-15. The animal leather powder is composed of one or more of cowhide leather powder, sheep hide leather powder and pig hide leather powder, and the mesh number of the animal leather powder is 200-1000, and the optimal mesh number is 300-350. When the filler is formed by mixing animal leather powder and fiber powder, the weight ratio of the polyurethane resin to the animal leather powder to the fiber powder is 30:5-30:10-35, and the optimal ratio is 30:10-15:25-30. The fiber powder comprises one or more of wood fiber powder and pulp fiber powder. The filler also comprises one or more of light calcium powder or heavy calcium powder. The fiber powder is high-expansion fiber powder with expansion ratio of 17-25 and mesh number of 350-700, wherein the optimal expansion ratio is about 20 and the optimal mesh number is about 600. The expansion coefficients of the wood fiber powder and the paper pulp fiber powder are large, the cells of the wood fiber powder and the paper pulp fiber powder after shrinkage are relatively large, and the bass is relatively softer. Meanwhile, the finer the wood fiber powder or the paper pulp fiber powder is, the denser the cells of the wood fiber powder or the paper pulp fiber powder after shrinkage are, and the softer the bass is.
The filler adopts animal leather powder or the mixture of the animal leather powder and fiber powder for the following functions:
1. the wet bass contains animal leather powder, and the animal leather powder has certain softness and fullness and has the resilience effect of meat texture, so that the prepared wet bass is softer, plump and has meat texture. The wet hair bayesian is used for enabling the prepared synthetic leather to have the elasticity of human skin, so that the hand feeling of the synthetic leather can exceed that of leather, and the grade of a synthetic leather finished product is improved.
2. The wet bass mixed with the animal leather powder has extremely high water absorption performance, and the synthetic leather after moisture regaining and water absorption has very good sagging feel, thereby increasing the weight and improving the softness. Meanwhile, the hydrophilic organic silicon further promotes the water absorption capacity of the animal leather powder, and the produced synthetic leather has a sagging feel.
3. The animal leather powder has fluffy fiber structure and good combination property with resin, and the produced synthetic leather has good strength.
4. The inside of the wet-process bass contains organic silicon, and the organic silicon plays roles in lubricating and reducing friction coefficient, and has soft and comfortable touch feeling. The organic silicon is matched with the animal leather powder, and the produced synthetic leather is soft and plump in meat feel. The softness, fullness and firmness of the synthetic leather are higher than those of the sheep skin, so that the high-end of the synthetic leather is realized, and the high added value of the synthetic leather production is realized.
The ionic type of the organosilicon softener is cation, and the softness of the cation organosilicon softener is obviously higher than that of the anion organosilicon softener and the nonionic organosilicon softener. Meanwhile, the surface of polysiloxane of the cationic organosilicon softener has positive charges, and the surface of fiber of the base cloth has negative charges, so that the polysiloxane can be well adsorbed on the surface of the fiber and is not easy to fall off.
The organosilicon softener comprises raw materials of amino silicone emulsion or amino polyether block silicone oil solvent liquid or hydrophilic amino polyether block silicone oil emulsion or hydrophilic amino polyether block silicone oil. Wherein the amino silicone oil emulsion comprises amino silicone oil, an emulsifier and water. The amino polyether block silicone oil emulsion consists of amino polyether block silicone oil and water. The amino polyether block silicone oil solvent liquid consists of amino polyether block silicone oil and a solvent, or the amino polyether block silicone oil solvent liquid consists of amino polyether block silicone oil, acetic acid and a solvent, wherein the weight ratio of the amino polyether block silicone oil to the acetic acid is 60:9-18, and the optimal ratio is 60:12. Wherein the solvent is one or more of butyl ether, isopropanol, N-dimethylformamide and water. The solvent is one or more of butyl ether, isopropanol and N, N-dimethylformamide.
The amino polyether block silicone oil refers to a polyorganosiloxane polyether block copolymer which is blocked by polysiloxane, amino and polyether. Or the amino polyether block silicone oil is prepared by mixing epoxy-terminated polyether silicone oil, polyether amine and a solvent. The amino polyether block silicon has excellent heat resistance stability and shearing resistance, keeps softer and silky feel of amino silicone oil, is not sticky and greasy, resists yellowing, and can provide ideal moisture absorption and antistatic performance, and the leather after moisture absorption has sagging feel.
The molecular weight of the amino polyether block silicone oil is 5000-30000, and the amino polyether block silicone oil is formed by compounding a plurality of amino polyether block silicone oils with different molecular weights. Specifically, the amino polyether block silicone oil can be selected from two or three combinations of three kinds of molecular weight, wherein the three kinds of molecular weight of the amino polyether block silicone oil respectively comprise a. The low molecular weight is 7000-9000, b. The medium molecular weight is 10000-12000, c. The high molecular weight is 13000-15000. Wherein the optimal weight part and the molecular weight ratio of the optimal amino polyether block silicone oil are that 70 parts of amino polyether block silicone oil with molecular weight of 8000 and 30 parts of amino polyether block silicone oil with molecular weight of 12000 are compounded. The softness and the fluffiness of the amino polyether block silicone oil with low molecular weight are relatively good, the smoothness of the amino polyether block silicone oil with high molecular weight is relatively good, and the soft organic silicon emulsion formed by compounding amino polyether block silicone oils with different molecular weights has better softening effect.
The solid content of the organic silicon softener is 15-70%, the solid content of the wet polyurethane resin solvent liquid is 28-32%, and the weight ratio of the wet polyurethane resin solvent liquid to the organic silicon softener is 100:2-15. The optimal scheme is that the wet polyurethane resin solvent liquid with the solid content of 30% and the organic silicon softener with the solid content of 25% are combined, and the optimal weight ratio of the wet polyurethane resin solvent liquid to the organic silicon softener is 100:6.
The organic silicon softener has the following functions:
1. The wet-process mixed material has the function of uniform dispersion, so that the filler is uniformly dispersed, the wet-process mixed material is washed and dried by a solidification tank after being coated, the wood fiber powder of the filler is contracted to form a uniformly distributed cell structure, the organosilicon plays a role of lubricating, reducing friction coefficient and having strong touch foam feeling.
2. The organic silicon softener is wrapped by polyurethane resin solvent liquid, and after the wet mixture is coated, the wet mixture is washed by a coagulation tank and dried, very compact micropores containing soft organic silicon are formed in the resin, so that the Bedset is soft. The pores and the fibers of the filler adsorb soft organic silicon, so that the filler is soft.
3. Soft organic silicon is basically adsorbed in the pores and gaps of the bass, the soft organic silicon is rarely carried away by water in the water washing process of the solidification tank, and meanwhile, the solvent recovery system is not easy to be blocked because the soft organic silicon is liquid.
4. The bass relies on the softening action of soft organosilicon, so that excessive densification of cells is not needed, and the bass has good firmness and good peel strength and tearing strength.
The pH value of the organic silicon softening agent is less than 5, and the optimal pH value is 2.2. Because the filling material is alkaline, the alkalinity can be heavier and heavier in the process of washing the wet mixed material with water in a coagulation tank, the organosilicon softening agent with the pH value more than 7 can demulsifie, and the organosilicon floating on the water surface can pollute the base cloth to cause oil spots, so that the pH value of the organosilicon softening agent is designed to be less than 5, thereby being beneficial to alkali acid neutralization. Acetic acid is added into the organic silicon softener to adjust the pH value of the softener, so that the pH value of the organic silicon softener is ensured to be slightly acidic.
The polyurethane resin solvent liquid has a solid content of 28-32%, and the optimal solid content is 30%. The polyurethane resin solvent liquid is a mixed liquid of wet polyurethane resin and solvent, or the polyurethane resin solvent liquid is wet soft polyurethane resin solvent liquid, and the modulus of the wet soft polyurethane resin is 5-10kgf/cm < 2 >.
Dry veneering the dry veneering in the elastic soft synthetic leather is prepared from dry mixed liquid coated on release paper. The dry mixed liquid is prepared from dry polyurethane resin, N-dimethylformamide and toner, the dry veneering is divided into an inner layer and an outer layer, the inner layer is adhered to a wet bass, the hardness of the dry polyurethane resin in the inner layer is smaller than that of the dry polyurethane resin in the outer layer, the modulus of the dry polyurethane resin in the inner layer is smaller than 30kgf/cm < 2 >, and the optimal modulus is 10kgf/cm < 2 >. The modulus of the dry polyurethane resin of the outer layer is greater than 45kgf/cm2, wherein the optimal modulus is 80kgf/cm2. The outer layer of the dry-method veneer layer is composed of dry-method organic silicon polyurethane or is composed of dry-method organic silicon polyurethane and dry-method polyurethane resin in a mixing mode. The resin has the characteristics of soft hand feeling, soft and smooth feeling, strong skin feeling and deep and bright color, and is suitable for stripping release paper with strong fog feeling. Because the price of the resin is higher, the dry silicone resin and the dry polyurethane resin are matched, so that the dry veneer layer has the advantages of the resin, the cost is reduced, and the dry veneer layer is formed by mixing the dry organic silicone polyurethane and the dry polyurethane resin.
The manufacturing process of the elastic soft synthetic leather comprises the following steps:
1. The preparation of the mixed liquor comprises the preparation of wet mixed liquor and dry mixed liquor.
1) The wet mixed liquid is prepared by mixing and stirring soft organosilicon emulsion, N-dimethylformamide, filler, color paste and other raw materials uniformly, adding polyurethane resin solvent liquid, mixing and stirring uniformly, and defoaming.
2) The preparation method of the dry mixed solution comprises the following steps:
The dry-process outer layer mixed solution A is prepared by mixing and stirring high-modulus dry-process polyurethane resin, N-dimethylformamide, butanone, polyether modified organosilicon and toner uniformly, and defoaming;
and b, preparing a dry-process inner layer mixed solution, namely mixing and stirring the low-modulus dry-process polyurethane resin, N-dimethylformamide, butanone, polyether modified organosilicon and toner uniformly, and defoaming.
2. Preparation of wet bass:
1) The base cloth is pretreated, the base cloth is immersed into an N, N-dimethylformamide water solution with the concentration of 15-25%, the excessive water solution is pressed by a squeezing roller, and the base cloth is ironed by an ironing wheel, wherein the humidity is 40%.
2) Coating and solidifying, namely uniformly coating the wet mixed solution on the pretreated base cloth, and immersing the base cloth in an N, N-dimethylformamide aqueous solution with the concentration of 20% in a solidification tank for solidification.
3) And (3) washing, namely drying, namely extruding excessive coagulating liquid through the squeeze rollers after the coagulating liquid is completely coagulated, washing with clean water through a washing tank, extruding through five groups of squeeze rollers in the first section of washing, extruding through six groups of squeeze rollers in the second section of washing, and finally drying, expanding and shaping to obtain the wet bass.
3. The dry-method veneering comprises the following steps:
1) The preparation of the release paper coating comprises the steps of carrying out zero-clearance coating on a release paper film, namely, carrying out zero-clearance coating on the release paper film, carrying out baking to be semi-dry by using a baking oven, then coating the release paper film with the dry mixed solution of 2) b, and carrying out baking to be semi-dry by using the baking oven to obtain the release paper coating.
2) And 3) dry veneering, namely directly laminating the wet bass on the release paper coating prepared in the step three 1) by using pressure, drying in an oven, cooling by a cooling roller, and respectively rolling the release paper and the wet bass on the surface to obtain finished leather.
4. And (3) finishing the surface of the finished leather, namely printing finishing agent on the front surface of the finished leather by using three-plate printing, and drying by using an oven to obtain the finished leather with a finishing effect.
5. The finished leather graining treatment comprises the following steps:
1) Adding a softening agent into a water trough, and uniformly mixing;
2) Immersing finished leather into the water solution passing through the water tank, dehydrating, rolling to dryness, and then rubbing and drying by a rubbing machine;
3) Finally, the synthetic leather material with soft hand feeling, strong meat quality, good strength, low price and good quality is obtained after inspection, rolling and packing.
The following provides a specific example of the wet mixture ratio of the elastic soft synthetic leather:
The wet-process mixture in the soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
1300 Parts of N, N-dimethylformamide,
80 Parts of hydrophilic amino polyether block silicone oil emulsion,
250 Parts of bovine leather powder.
The wet-process mixture in the soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
1300 Parts of N, N-dimethylformamide,
80 Parts of hydrophilic amino polyether block silicone oil emulsion,
250 Parts of wood fiber powder,
50 Parts of bovine leather powder.
The wet-process mixture of the soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
1200 Parts of N, N-dimethylformamide,
80 Parts of amino polyether block silicone oil emulsion,
250 Parts of wood fiber powder,
45 Parts of sheep leather powder.
The wet-process mixture of the soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
1200 Parts of N, N-dimethylformamide,
80 Parts of amino silicone oil emulsion,
250 Parts of paper pulp fiber powder,
100 Parts of heavy calcium powder
45 Parts of pig leather powder.
The fifth embodiment is another proportion of the wet mixture of the soft synthetic leather, which comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
1200 Parts of N, N-dimethylformamide,
250 Parts of wood fiber powder,
45 Parts of sheep leather powder
80 Parts of soft organosilicon emulsion.
In the sixth embodiment, the wet mixture of the soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
1200 Parts of N, N-dimethylformamide,
250 Parts of wood fiber powder,
48 Parts of animal leather powder mixture
80 Parts of soft organosilicon emulsion.
The wet-process mixture in the elastic soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
80 Parts of soft organic silicon emulsion,
1200 Parts of N, N-dimethylformamide,
300 Parts of wood fiber powder.
Soft organic silicon is not introduced into the traditional mixed slurry of the wet-process bass of the synthetic leather, a polyether silicone oil leveling agent is used for reducing tension in the preparation of the mixed slurry of the wet-process bass, a dimethyl silicone oil defoaming agent is used for defoaming, a diorganopolysiloxane flexibilizer is used for improving the flexibility of the cured resin, and the use amount is very small. The organic silicon softening agent used in the post-finishing process generally has the organic silicon content of 8 percent, is added into a water-kneading trough according to the use amount of 3 percent, and calculates according to the liquid carrying rate of 30 percent, so that the specific gravity of the attached organic silicon accounting for the bass is 0.72 per mill, the specific gravity of the attached organic silicon accounting for the bass in the bass is about 4 percent, and is obviously far higher than the specific gravity of the organic silicon accounting for the bass in the post-finishing process, so that the softening effect of the organic silicon softening agent used in the wet mixture is far higher than the effect of the organic silicon softening agent used in the post-finishing process.
The wet-process mixture of the elastic soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
80 Parts of soft organic silicon emulsion,
1200 Parts of N, N-dimethylformamide,
300 Parts of wood fiber powder,
125 Parts of light calcium powder.
The wet-process mixture in the elastic soft synthetic leather comprises the following components in parts by weight:
700 parts of wet polyurethane resin solvent solution with the modulus of 5kgf/cm2,
300 Parts of wet polyurethane resin solvent solution with the modulus of 10kgf/cm2,
60 Parts of soft organic silicon emulsion,
100 Parts of polyvinyl alcohol powder
1200 Parts of N, N-dimethylformamide,
250 Parts of wood fiber powder.
The polyvinyl alcohol in the proportion can provide compact micro-cells, the inner walls of the micro-cells are adsorbed with the organic silicon softener, the produced Berster is soft, and compared with the prior soft protein synthetic leather Bebster mixture, the dosage of the polyvinyl alcohol is greatly reduced, so that the blocking period of the polyvinyl alcohol in a solvent recovery system is greatly prolonged.
The following specific examples of two proportions of the organosilicon softener in the wet mixture of the elastic soft synthetic leather are provided:
Embodiment ten the organic silicon softener in the wet mixture in the elastic soft synthetic leather comprises the following components in parts by weight:
60 parts of amino polyether block silicone oil;
9-18 parts of acetic acid, wherein the most preferable part is 12 parts;
35-50 parts of ethylene glycol monobutyl ether and isopropanol, wherein the optimal weight is 40 parts;
Water, 35-185 parts of N, N-dimethylformamide, and the most preferred part is 150 parts.
The amino polyether block silicon has excellent heat resistance stability and shearing resistance, keeps softer and silky feel of amino silicone oil, is not sticky and greasy, resists yellowing, and can provide ideal moisture absorption and antistatic performance, and the leather after moisture absorption has sagging feel.
An eleventh embodiment of the present invention is an elastic soft synthetic leather, wherein the weight portion of the other formulation of the organic silicon softener in the wet mixture is as follows:
60 parts of amino polyether block silicone oil;
9-18 parts of acetic acid, and optimally 12 parts;
35-50 parts of ethylene glycol monobutyl ether and isopropanol, and optimally 40 parts;
35-185 parts of N, N-dimethylformamide, and most preferably 150 parts.
Wherein butyl ether, isopropanol and N, N-dimethylformamide are used as solvents. The compatibility of pigment paste in the wet mixed slurry and water is poor, excessive water doping in the wet mixed slurry can influence the peeling strength, so that after water in the proportion is replaced by N, N-dimethylformamide, pigment in the first wet mixed slurry is not easy to run into water in the water washing process of a coagulation tank, the base cloth is not easy to pollute the color, the second wet mixed slurry improves the peeling strength, the third softness is better, and the fourth wet mixed slurry is favorable for the dispersion of the mixed slurry.
Example twelve the steps of the softener manufacturing process are as follows:
1) The amino polyether block silicone oil with 60 percent of organosilicon content is prepared,
The first step, the addition reaction, the reaction temperature is about 70 ℃, the heat preservation is about 5 hours, and the catalyst is prepared from the following raw materials by weight:
800 kg of 8000 molecular weight epoxy-terminated polyether silicone oil,
96 Kg of polyether,
12 G of chloroplatinic acid was used,
370 Kg of isopropanol.
And the second step, amination reaction, wherein the reaction temperature is about 80 ℃, and the heat preservation is about 8 hours. The material is prepared from the following raw materials in parts by weight:
1266 kg of amino polyether block silicone oil with 60% of organosilicon content is prepared in the first step,
20 Kg of polyether amine,
240 Kg of ethylene glycol monobutyl ether.
2) Preparation of an aminopolyether block silicone oil emulsion with 25% of organic silicon content. The bass softener can be obtained by emulsifying a stirred tank with a high shearing machine by scraping the wall, and the emulsified composition materials are as follows:
1526 kg of amino polyether block silicone oil with 60% of organosilicon content,
180 Kg of acetic acid,
1956 Kg of water.
The thirteenth example is essentially the same as the twelfth example except that an aminopolyether block silicone oil emulsion having a silicone content of 25% is prepared. The bass softener can be obtained by emulsifying a stirred tank with a high shearing machine by scraping the wall, and the emulsified composition materials are as follows:
1526 kg of amino polyether block silicone oil with 60 organosilicon content,
180 Kg of acetic acid,
956 Kg of water was used to prepare a gel,
1000 Kg of N, N-dimethylformamide.
Example fourteen essentially the same as in example eleven except that a 25% silicone content aminopolyether block silicone oil solution was prepared. The bass softener can be obtained by mixing, stirring and dispersing a stirring kettle with a high shearing machine by scraping the wall, and the mixed constituent materials are as follows:
1526 kg of amino polyether block silicone oil with 60 organosilicon content,
180 Kg of acetic acid,
1956 Kg of N, N-dimethylformamide.
Further, an aminopolyether block silicone oil solution with 25 percent of organic silicon content is prepared.
The bass softener can be obtained by mixing, stirring and dispersing a stirring kettle with a high shearing machine by scraping the wall, and the mixed constituent materials are as follows:
1526 kg of amino polyether block silicone oil with 60 organosilicon content,
180 Kg of acetic acid,
156 Kg of polyvinyl alcohol is used for preparing the adhesive,
1800 Kg of water.
Fifteen embodiments provide another proportion of the dry-mixed material of the elastic soft synthetic leather, wherein the dry-mixed material comprises a dry-mixed outer layer mixed liquid and a dry-mixed inner layer mixed liquid, and the dry-mixed outer layer mixed liquid comprises the following components in parts by weight:
The dry-process outer layer mixed solution is prepared from the following raw materials in percentage by weight:
40 parts of dry polyurethane resin having a modulus of 80kgf/cm2,
30 Parts of N, N-dimethylformamide,
21.8 Parts of butanone,
0.2 Part of leveling agent, and the balance of the water-soluble polymer,
8 Parts of toner.
The dry-process inner layer mixed solution is prepared from the following raw materials in percentage by weight:
30 parts of dry polyurethane resin with the modulus of 10kgf/cm2,
10 Parts of dry polyurethane resin with the modulus of 15kgf/cm2,
30 Parts of N, N-dimethylformamide,
21.5 Parts of butanone,
0.2 Part of leveling agent, and the balance of the water-soluble polymer,
0.3 Part of emulsifier AEO-3,
8 Parts of toner.
Sixthly, the wet-process base medium softening agent and the wet-process polyurethane resin solvent liquid are proportioned into the wet-process polyurethane resin solvent liquid with the softening agent. The wet polyurethane resin solvent liquid with the softener comprises nonionic wet polyurethane resin, amino polyether block silicone oil, acetic acid and a solvent. Wherein the solvent is composed of several of butyl ether, isopropanol and N, N-dimethylformamide.
The wet polyurethane resin solvent liquid preparation process with the softening agent and 30% of solid content comprises the following steps of mixing, stirring and dispersing by a stirring kettle with a high-speed wall scraping dispersing machine:
30 percent of solid content of 1000 kg of non-ionic wet polyurethane resin solvent,
100 Kg of amino polyether block silicone oil with 60% of organosilicon content,
10 Kg of acetic acid,
90 Kg of N, N-dimethylformamide.
Because the siloxane in the amino polyether block silicone oil is connected with a large amount of polyether, the nonionic wet polyurethane resin solvent liquid, the N, N-dimethylformamide and the cationic amino polyether block silicone oil are mixed together stably, and the amino polyether block silicone oil can be stored for a long time.
The present invention is not limited in any way by the above-described preferred embodiments, but is not limited to the above-described preferred embodiments, and any person skilled in the art will appreciate that the present invention can be embodied in the form of a program for carrying out the method of the present invention, while the above disclosure is directed to equivalent embodiments capable of being modified or altered in some ways, it is apparent that any modifications, equivalent variations and alterations made to the above embodiments according to the technical principles of the present invention fall within the scope of the present invention.
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| CN116815417B (en) * | 2023-07-05 | 2025-08-15 | 重庆双象超纤材料有限公司 | Preparation method of high-hygroscopicity breathable inner leather |
| CN119102125B (en) * | 2024-11-08 | 2025-02-18 | 温州同赢科技有限公司 | A wet foaming material for resistant leather and resistant leather prepared by the same |
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| CN106436342A (en) * | 2016-11-15 | 2017-02-22 | 福建华夏合成革有限公司 | Ultra-soft protein synthetic leather and preparing method thereof |
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| CN102080332B (en) * | 2010-12-27 | 2012-05-09 | 陕西科技大学 | A kind of manufacture method of waterborne polyurethane synthetic leather bass |
| CN102408699B (en) * | 2011-09-06 | 2014-10-22 | 华大化学集团有限公司 | Composite slurry, synthetic leather substrate and preparation method of synthetic leather substrate |
| CN105064064A (en) * | 2015-08-07 | 2015-11-18 | 无锡双象超纤材料股份有限公司 | Preparation method of microfiber soft leather sofa leather |
| CN107513867A (en) * | 2017-08-19 | 2017-12-26 | 安徽安利材料科技股份有限公司 | Durable durable type sofa furniture Synthetic Leather of a kind of low VOC height of wet method and preparation method thereof |
| CN111264972A (en) * | 2020-03-16 | 2020-06-12 | 兴业皮革科技股份有限公司 | Leather shoe upper surface made of natural leather and preparation method thereof |
| CN111534650B (en) * | 2020-05-20 | 2022-04-29 | 杭州天龙手袋股份有限公司 | Durable antibacterial soft leather for leather bags and preparation method thereof |
| CN111493473B (en) * | 2020-06-15 | 2022-07-12 | 杭州天龙手袋股份有限公司 | Waterproof antibacterial soft material handbag |
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| CN105568709A (en) * | 2016-01-30 | 2016-05-11 | 山东同大海岛新材料股份有限公司 | Preparation method for ultrafine fiber clothing leather |
| CN106436342A (en) * | 2016-11-15 | 2017-02-22 | 福建华夏合成革有限公司 | Ultra-soft protein synthetic leather and preparing method thereof |
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