CN105350342B - A kind of preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather - Google Patents

A kind of preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather Download PDF

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CN105350342B
CN105350342B CN201510634193.0A CN201510634193A CN105350342B CN 105350342 B CN105350342 B CN 105350342B CN 201510634193 A CN201510634193 A CN 201510634193A CN 105350342 B CN105350342 B CN 105350342B
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polyether
type
solvent
aqueous
curing
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CN105350342A (en
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王锐林
姚和平
王海峰
孔为青
宋远周
李晓飞
吴文
黄万里
姚克俭
陈永志
王燕武
笪丽红
武春余
苏星
刘兵
罗运东
高兵
范培宏
王德松
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Anhui Anli Material Technology Co Ltd
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Anhui Anli Material Technology Co Ltd
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    • 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

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  • 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 invention discloses a kind of preparation methods of aqueous/solvent-free composite environment-friendly Synthetic Leather, the synthetic leather includes aqueous elastic dignity layer and non-solvent foamed middle layer, the aqueous elastomer surface layer resin is heat curing type polyether type aqueous polyurethane resin, the solvent-free middle layer is heat curing type two-component polyether-type non-solvent foamed polyurethane resin, and the two-component material is that polyether-type combines A material and polyether-type B expects performed polymer.The preparation process of the present invention does not use any organic solvent, realizes synthetic leather production and processing and the zero solvent use of finished product and health environment-friendly；Waterborne polyurethane resin is combined with the advantages of solvent-free polyurethane resin simultaneously, 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 are suitable with natural leather.

Description

A kind of preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather
One, technical field
The present invention relates to a kind of manufacturing methods of Synthetic Leather, specifically a kind of aqueous/solvent-free compound The preparation method of environment-friendly polyurethane synthetic leather belongs to synthetic leather manufacturing field.
Two, background technology
With the development and the improvement of people's living standards of national economy, consumer is not only for clothing, shoes and hats, sofa man Tool, automotive interior product quality have a high request, while the environmental-protecting performance of material is required also very high.Though corium product at present So have many advantages, such as that comfortable feel, elasticity is good, durability is preferable, but since natural leather resource is limited, is made with first layer lether High-performance, high quality, high value added product are even more that supply falls short of demand, and price persistently rises, and has become the code name of luxury consumer goods Word.And ideal alternative materials of the Synthetic Leather as corium, it is disadvantageous in that it must use highly polar organic solvent DMF is unfavorable for the health environment-friendly of production process and finished consumer process as solvent.Under these circumstances, the high physical property of environment-friendly type Synthetic Leather product provides a selection well for consumer.
Three, invention content
The present invention is intended to provide a kind of preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather, manufactured Journey and final products are environmentally friendly；The product third dimension of patterns developed is strong, soft, and the physical properties such as hydrolysis are superior, and And skin sense and skin sense are strong.
The preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather of the present invention, includes the following steps：
(1) aqueous covercoat slurry is coated in release paper, and aqueous covercoat is obtained after drying forming；
(2) water is cast in by PU low-pressure blowing machines after mixing polyether-type combination A material and polyether-type B material performed polymers Property face layer on, pass through and be sent into baking oven pre-reaction after scraper coating uniformly and obtain solvent-free middle layer；The solvent-free middle layer is Heat curing type two-component polyether-type non-solvent foamed polyurethane resin；
(3) the solvent-free middle layer of pre-reaction is bonded base fabric, is then fed into the sizing of baking oven crosslinking curing, winds and cure Stripping release paper can be obtained synthetic leather products afterwards.
The coating thickness of control aqueous covercoat slurry is 0-0.5mm, preferably 0.1-0.4mm in step (1)；Drying temperature is 50-150 DEG C, preferably 60-130 DEG C；Drying time is 0-4min, preferably 1-3min.
The mass ratio of polyether-type combination A material and polyether-type B material performed polymers is 2.5 in step (2):1-1:2.5；Pass through scraper The coating thickness of coating control mixed slurry is 0.05-1mm, preferably 0.15-0.8mm；The reaction temperature of the pre-reaction is 50-150 DEG C, preferably 80-130 DEG C, pre-reaction time 0-4min, preferably 1-3min.
In step (3) crosslinking curing shape temperature be 100-150 DEG C, preferably 110-140 DEG C, crosslinking curing sizing Time is 4-10min, preferably 5-8min.
In step (3) curing temperature be 40-100 DEG C, preferably 40-80 DEG C, curing time 6-72h, preferably 12- 72h。
The formula of the aqueous covercoat slurry is constituted as follows by mass fraction：
The aqueous polyurethane is anion heat curing type polyethers waterborne polyurethane resin, the anionic polyethers water Property polyurethane resin in anionic group be carboxylate group and/or sulfonate group.The aqueous polyurethane is preferably the moon Ion heat curing type polyether resin water-base resin 7377 (production of Yantai Wanhua chemical company).
The crosslinking agent be polyisocyanate crosslinker, epoxide, aziridine, polycarbodiimide, epoxy silane, One or more of N- methylol compounds and polyamine, preferably polyisocyanate crosslinker, polycarbodiimide, N- hydroxyls One or more of methyl compound；
The water-based thickener is inorganic thickening agent, cellulose thickener, polyacrylate-type thickeners, association type are poly- One or more of urethane thickener, association type polyether polyol thickener, preferably association type polyurethane thickener or/and Association type polyether polyol thickener；
The leveling auxiliary agent is silicone levelling agent containing hydrophilic radical, one kind in acroleic acid polymerization species levelling agent Or it is several；
The wetting aid be one kind during polysiloxanes, polysiloxane polyether copolymer, Organic fluoride are polymer-modified or It is several；
The antiwear assistant is super high molecular weight (number-average molecular weight >=1,000,000) polysiloxanes；
The nano material is aerosil.
The polyether-type combination A material are polyether-type combination material 72063/1 C-A of C (BASF AG's product).
The polyether-type B material performed polymer is 34670/1 C-B of polyether-type performed polymer C (BASF AG's product).
Synthetic leather of the present invention includes aqueous covercoat and solvent-free middle layer, and the aqueous covercoat resin is heat curing type polyether-type Waterborne polyurethane resin, the solvent-free middle layer is heat curing type two-component polyether-type non-solvent foamed polyurethane resin, described Two-component material is that polyether-type combines A material and polyether-type B expects performed polymer.
The preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather of the present invention, specifically comprises the following steps：
(1) preparation of aqueous covercoat：Aqueous covercoat slurry is coated in release paper, and aqueous covercoat is obtained after drying forming；
(2) preparation of solvent-free middle layer：It is low by PU after polyether-type combination A material are mixed with polyether-type B material performed polymers Foam machine is cast on the aqueous covercoat, and after scraping cutter painting and scraping, and passes through baking oven pre-reaction；
(3) it is bonded base fabric：The solvent-free middle layer of pre-reaction is bonded base fabric；
(4) crosslinking curing, winding：It is sent into the sizing of baking oven crosslinking curing after being bonded base fabric, is then wound；
(5) it cures：Resultant Leather after winding is sent with release paper to curing chamber and is cured；
(6) release paper is removed：Paper after curing, leather are subjected to release paper stripping, obtain synthetic leather products.
Aqueous/solvent-free composite environment-friendly Synthetic Leather of the method for the present invention processing and manufacturing, combines aqueous poly- ammonia The advantages of ester resin and solvent-free polyurethane resin, the product third dimension of patterns developed is strong, soft, the physics such as hydrolysis Superior performance, and skin sense and skin sense are strong, are suitable for sofa furniture leather, clothing leather, men and women's playshoes leather, packaging leather etc. no Same application field.
Manufacturing process of the present invention does not use any organic solvent, realizes zero solvent of synthetic leather production and processing and finished product and makes With and health environment-friendly；Waterborne polyurethane resin is combined with the advantages of solvent-free polyurethane resin simultaneously, the synthetic leather production of acquisition Not only third dimension of patterns is strong, soft for product, and the physical properties such as hydrolysis are superior, and skin sense and skin sense and natural leather phase When.Environment-protecting polyurethane synthetic leather made from the method for the present invention is suitable for sofa furniture leather, clothing leather, men and women's playshoes leather, packet The different applications fields such as dress leather.
Compared with the prior art, beneficial effects of the present invention are embodied in：
1, aqueous/solvent-free composite environment-friendly Synthetic Leather prepared by the present invention gathers aqueous polyurethane with solvent-free The advantages of urethane combination material, is combined, and has third dimension of patterns strong, soft, the physical properties such as hydrolysis are superior, and flesh The features such as skin sense and skin sense suitable with natural leather；
2, aqueous/solvent-free composite environment-friendly Synthetic Leather preparation process that prepared by the present invention is advanced, moderate cost The advantages that, and prepare whole environment protection health, final finished environment protection health；
3, aqueous/solvent-free composite environment-friendly Synthetic Leather prepared by the present invention, passes through nano material gas phase dioxy The reasonable employment of SiClx has well solved the binding force problem of aqueous covercoat and solvent-free middle layer in process.
Four, specific implementation mode
Below by several specific embodiments, the present invention is further illustrated, but it is to be noted that the present invention Specific material proportion, process conditions and result described in embodiment etc. are merely to illustrate the present invention, can not be limited with this Protection scope of the present invention processed, equivalent change or modification made by every Spirit Essence according to the present invention, should all cover In protection scope of the present invention.
The source of each raw material is in following embodiments：
Aqueous covercoat resin is that Yantai Wanhua chemistry is public using anion heat curing type polyether resin water-base resin 7377 Take charge of product；
Waterborne curing agent is produced using Carbodiimides crosslinking agent UN-557 for Shanghai You En Chemical Co., Ltd.s Product；
Water-based thickener is Borchers companies of Germany using association type polyurethane thickener Borchi Gel W44 Product；
Aqueous color paste is Suzhou Shi Ming scientific ＆ technical corporation product using aqueous black paste TSE LR01；
Aqueous leveling auxiliary agent is Germany's Bi Ke Products using organic silicon surfactant BYK-346；
Aqueous wetting aid is Yantai Wanhua chemical company product using polysiloxane polyether copolymer TEGU245；
Aqueous wear-resistant auxiliary agent is Dow Corning Corporation's product using super high molecular weight polysiloxane emulsion DC-51；
Nano material is aerosil HL-150, is Guangzhou Science and Technology Ji Sheng Industrial Co's product；
It is polyether-type combination material 72063/1 C-A of C that polyether-type, which combines A material, is BASF AG's product；
Polyether-type B material performed polymers are 34670/1 C-B of polyether-type performed polymer C, are BASF AG's product；
Embodiment 1：
The present embodiment synthetic leather includes aqueous covercoat and solvent-free middle layer, and the aqueous covercoat resin is heat curing type polyethers Type waterborne polyurethane resin, the solvent-free middle layer are heat curing type two-component polyether-type non-solvent foamed polyurethane resin, institute It is that polyether-type combines A material and polyether-type B expects performed polymer to state two-component material.
The preparation method of composite environment-friendly Synthetic Leather aqueous in the present embodiment/solvent-free, specifically includes following step Suddenly：
(1) preparation of aqueous covercoat：Aqueous covercoat slurry is coated in release paper, the coating for controlling aqueous covercoat slurry is thick Degree is 0.2mm, and 120 DEG C dry curing molding after 3min, obtain aqueous covercoat；
The aqueous covercoat is heat curing type polyethers waterborne polyurethane resin；
Each raw material is by the proportioning of mass parts in the aqueous covercoat slurry：
(2) preparation of solvent-free middle layer：Polyether-type combination A material and polyether-type B are expected into performed polymer in mass ratio 2:1 is mixed Close, be cast on aqueous covercoat by PU low-pressure blowing machines, and scrape by scraping cutter painting, it is 0.4mm to scrape cutter painting and scrape gap, then in 130 DEG C of pre-reaction 2min, obtain solvent-free middle layer；The solvent-free middle layer is the solvent-free hair of heat curing type two-component polyether-type Steep polyurethane resin；Wherein polyether-type combination A material are polyether-type combination material 72063/1 C-A of C, and polyether-type B material performed polymers are poly- 34670/1 C-B of ether type performed polymer C；
(3) it is bonded base fabric：Solvent-free middle layer is bonded base fabric；
(4) crosslinking curing, winding：Baking oven is sent into 140 DEG C through the sizing of 8min crosslinking curings, then by it after being bonded base fabric Winding；
(5) it cures：Resultant Leather after winding is sent with release paper to curing chamber and cures 48h in 60 DEG C；
(6) release paper is removed：Paper after curing, leather are subjected to release paper stripping, obtain synthetic leather products.
Embodiment 2：
The present embodiment synthetic leather includes aqueous covercoat and solvent-free middle layer, and the aqueous covercoat resin is heat curing type polyethers Type waterborne polyurethane resin, the solvent-free middle layer are heat curing type two-component polyether-type non-solvent foamed polyurethane resin, institute It is that polyether-type combines A material and polyether-type B expects performed polymer to state two-component material.
The preparation method of composite environment-friendly Synthetic Leather aqueous in the present embodiment/solvent-free, specifically includes following step Suddenly：
(1) preparation of aqueous covercoat：Aqueous covercoat slurry is coated in release paper, the coating for controlling aqueous covercoat slurry is thick Degree is 0.4mm, and 130 DEG C dry curing molding after 3min, obtain aqueous covercoat；
The aqueous covercoat is heat curing type polyethers waterborne polyurethane resin；
Each raw material is by the proportioning of mass parts in the aqueous covercoat slurry：
(2) preparation of solvent-free middle layer：Polyether-type combination A material and polyether-type B are expected into performed polymer in mass ratio 1.25:1 Mixing, is cast in by PU low-pressure blowing machines on aqueous covercoat, and is scraped by scraping cutter painting, and it is 0.6mm to scrape cutter painting and scrape gap, then In 130 DEG C of pre-reaction 3min, solvent-free middle layer is obtained；The solvent-free middle layer is that heat curing type two-component polyether-type is solvent-free Foaming polyurethane resin；Wherein polyether-type combination A material are polyether-type combination material 72063/1 C-A of C, and polyether-type B material performed polymers are 34670/1 C-B of polyether-type performed polymer C；
(3) it is bonded base fabric：Solvent-free middle layer is bonded base fabric；
(4) crosslinking curing, winding：Baking oven is sent into 120 DEG C through the sizing of 8min crosslinking curings, then by it after being bonded base fabric Winding；
(5) it cures：Resultant Leather after winding is sent with release paper to curing chamber and cures 36h in 80 DEG C；
(6) release paper is removed：Paper after curing, leather are subjected to release paper stripping, obtain synthetic leather products.
The correlated characteristic of above-mentioned two embodiment is as follows：
Feel Decorative pattern Skin sense Anti-hydrolytic performance
Embodiment 1 It is soft It is full By force 5-10 weeks
Embodiment 2 It is soft It is full By force 5-10 weeks
The present invention provides a kind of convenient feasible methods of the full environment-protecting polyurethane synthetic leather of manufacture, and by aqueous polyurethane It is effectively combined with the advantages of two kinds of materials of no-solvent polyurethane, aqueous/solvent-free compound Synthetic Leather prepared Not only have third dimension of patterns strong, soft, the features such as anti-hydrolytic performance is superior, and skin sense and skin sense and natural leather Quite, it is suitable for the application of the different fields such as sofa furniture leather, clothing leather, men and women's playshoes leather, packaging leather.

Claims (6)

1. a kind of preparation method of aqueous/solvent-free composite environment-friendly Synthetic Leather, it is characterised in that include the following steps：
(1) aqueous covercoat slurry is coated in release paper, and aqueous covercoat is obtained after drying forming；
(2) the aqueous face is cast in by PU low-pressure blowing machines after mixing polyether-type combination A material and polyether-type B material performed polymers On layer, solvent-free middle layer is obtained by being sent into baking oven pre-reaction after scraper coating uniformly；The solvent-free middle layer is thermosetting Type two-component polyether-type non-solvent foamed polyurethane resin；
(3) the solvent-free middle layer of pre-reaction is bonded base fabric, is then fed into the sizing of baking oven crosslinking curing, winds and shelled after curing Synthetic leather products are can be obtained from release paper；The temperature of crosslinking curing sizing is 100-150 DEG C, crosslinking curing sizing when Between be 4-10min；Curing temperature is 40-100 DEG C, curing time 6-72h；
The formula of the aqueous covercoat slurry is constituted as follows by mass fraction：
The aqueous polyurethane is anion heat curing type polyether resin water-base resin 7377；
The crosslinking agent is polyisocyanate crosslinker, epoxide, aziridine, polycarbodiimide, epoxy silane, N- hydroxyls One or more of methyl compound and polyamine；
The water-based thickener is association type polyurethane thickener or/and association type polyether polyol thickener；
The leveling auxiliary agent is silicone levelling agent containing hydrophilic radical, one kind or several in acroleic acid polymerization species levelling agent Kind；
The wetting aid is that polysiloxanes, polysiloxane polyether copolymer, Organic fluoride are one or more of polymer-modified；
The antiwear assistant is super high molecular weight polysiloxanes；
The nano material is aerosil；
The polyether-type combination A material are polyether-type combination material C 72063/1C-A；
The polyether-type B material performed polymer is polyether-type performed polymer C 34670/1C-B.
2. preparation method according to claim 1, it is characterised in that：
The coating thickness of control aqueous covercoat slurry is 0-0.5mm in step (1), and drying temperature is 50-150 DEG C, drying time For 0-4min.
3. preparation method according to claim 1 or 2, it is characterised in that：
The coating thickness of control aqueous covercoat slurry is 0.1-0.4mm in step (1), and drying temperature is 60-130 DEG C, when drying Between be 1-3min.
4. preparation method according to claim 1, it is characterised in that：
The mass ratio of polyether-type combination A material and polyether-type B material performed polymers is 2.5 in step (2):1-1:2.5；It is coated by scraper The coating thickness for controlling mixed slurry is 0.05-1mm；The reaction temperature of the pre-reaction is 50-150 DEG C, and pre-reaction time is 0-4min。
5. preparation method according to claim 1 or 4, it is characterised in that：
The mass ratio of polyether-type combination A material and polyether-type B material performed polymers is 2.5 in step (2):1-1:2.5；It is coated by scraper The coating thickness for controlling mixed slurry is 0.15-0.8mm；The reaction temperature of the pre-reaction is 80-130 DEG C, pre-reaction time For 1-3min.
6. preparation method according to claim 1, it is characterised in that：
The temperature that crosslinking curing is shaped in step (3) is 110-140 DEG C, and the time of crosslinking curing sizing is 5-8min；Curing temperature Degree is 40-80 DEG C, curing time 12-72h.
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