CN105735002A - Graphene in-situ modified polyurethane and method for manufacturing synthetic leather with high physical properties - Google Patents
Graphene in-situ modified polyurethane and method for manufacturing synthetic leather with high physical properties Download PDFInfo
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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
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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
- D06N3/0056—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
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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
- D06N3/0086—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
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- 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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Abstract
The invention discloses graphene in-situ modified polyurethane and a method for manufacturing synthetic leather with high physical properties. The graphene in-situ modified polyurethane is characterized in that graphene is firstly subjected to lipophilic modification, then the modified graphene is dispersed in a polyurethane solution in a certain proportion, and graphene in-situ modified polyurethane is prepared; the synthetic leather based on the in-situ modified graphene is prepared with traditional dry and wet processes. By means of the introduction of the graphene, the polyurethane can be strengthened and toughened, performances including abrasion resistance, scratch resistance, heat resistance, ageing resistance, static resistance, electromagnetic shielding, flame retardance and the like of a polyurethane coating are effectively improved, and the grade of the synthetic leather is improved; nevertheless, traditional processes and equipment are not changed; the polyurethane is applicable to manufacturing of various synthetic leather.
Description
Technical field
The invention belongs to synthetic leather and manufacture field, be specifically related to a kind of graphene in-situ modified polyurethane and high physical property synthetic leather manufacture method.
Background technology
China is world's artificial leather, synthetic leather production and consumption big country.At present, there are more than 1000 artificial leather, synthetic leather enterprise in China, 385 above enterprises of scale, 2000 Duo Jia back segment enterprise (Final finishing), more than 500 raw material, plant equipment enterprise, more than 10000 artificial leather, synthetic leather super fiber leather shelves mouth trader, annual production more than 70 hundred million square meter, account for the 73% of Gross World Product.According to State Statistics Bureau to the synthetic leather output statistics of scale above enterprise, China's synthetic leather overall productivity 218.9 ten thousand tons in 2010, close 3,900,000,000 square meters, exceed almost one times than China GDP growth rate, the strong growth of display China synthetic leather industry.
China is synthetic leather big producing country of the world, but not makes the country prosperous.The Kuraray of Japan, Supreme Being people, beautiful, the Zhong Fangdengji company in east represent the top level of whole world synthetic leather industry；Korea S knows production technology and the interior leather for automobiles market of superfine fiber chemical leather；TaiWan, China leads synthetic leather machine-building；The synthetic leather goods of " Italy manufacture " label make a name the world.The export volume of Italian synthetic leather goods in 2010 still maintains the strong growth impetus of 6.9%, has almost monopolized the high-end product market in the whole world.
Chinese people fabricate-leather, synthetic leather industry start from the end of the seventies, the a complete set of ground such as Introduced from Japan and Taiwan technology at that time, although through the development of nearly 30 years, a lot of technology such as DMF recovery technology, Recycle Technology of Waste Water, Machine Manufacturing Technology etc. have been reached advanced world standards, but the manufacturing process of artificial leather, synthetic leather and material still follow traditional technique and material, the most matter of synthetic leather produced time shelves are low, lack the market competitiveness.Such as the ecological synthetic leather of external exploitation is because of its good functional and eco-environmental prote, and price is increased to 7700.89 dollars per ton by common 3784.26 dollars per ton, and price exceeds twice.The microfiber synthetic leather average inlet unit price and for example with highly emulation property is 12000 beautiful yuan/ton, about 150 yuan/meter, and average outlet unit price is 3600 beautiful yuan/ton, and about 45 yuan/meter, price is not as good as 1/3rd of imported product price.Therefore, how to rebuild traditional industry by new and high technology, promote product hierarchy or the competitiveness in the international market of synthetic leather, be the key maintaining synthetic leather industry sustainable development.
The main coating material of synthetic leather manufacture is polyurethane, and the physical property of polyurethane decides the final physical property of synthetic leather.Synthetic leather is all closely related with the physical property of resin in hydrolytic resistance, tolerance to cold, antistick characteristic, antistatic behaviour, antibacterial and mouldproof, wear-resisting, scratch resistance, resistance to ag(e)ing (uv-resistant), accumulation of energy, electromagnetic wave shielding, flame-proof smoke-suppressing etc..In order to improve the physical property of polyurethane, forefathers have carried out substantial amounts of modified work, but often attend to one thing and lose sight of another, and improve a certain performance to sacrifice other performance for cost, and a kind of method of modifying cannot promote the multinomial performance of polyurethane and synthetic leather.
Summary of the invention
It is an object of the invention to provide a kind of graphene in-situ modified polyurethane and high physical property synthetic leather manufacture method for the deficiencies in the prior art.
Graphene (Graphene) is with sp by carbon atom2The monoatomic layer that hydridization connects is constituted, its basic structural unit is most stable of hexatomic ring New Two Dimensional atomic crystal (two-dimensional nano, single monolayer thick 0.35nm) in organic material.Graphene is the thinnest, a kind of novel nano-material that maximum intensity, electrical and thermal conductivity performance are the strongest that have now been found that, is referred to as " dark fund ", is " king of new material ".It is with a wide range of applications in fields such as solaode, sensor, nanoelectronics, high-performance nanometer electronic device, composite, field emmision material, gas sensor and energy storage materials.Graphene is used for the manufacture of synthetic leather, it is expected to be greatly improved synthetic leather coating wear-resisting scratch resistance (lubrication), antistatic behaviour, antibacterial and mouldproof, the ageing-resistant and combination property such as uv-resistant (electron excitation) property, wave absorbtion.
A kind of graphene in-situ modified polyurethane provided by the invention and high physical property synthetic leather manufacture method, it is characterised in that:
(1) Graphene first carries out oleophylic to modifiy, solve Graphene not easily scattered technical barrier in polyurethane；
(2) polyurethane is as dispersible carrier energy moistening, dispersing solid graphene powder very well, and Graphene has good containment role；
(3) introducing of Graphene, can effectively promote the combination properties such as the thermostability of synthetic leather coating, resistance to ag(e)ing, electric conductivity, electromagnetic wave shielding and anti-flammability, the General Promotion credit rating of synthetic leather；
(4) graphene in-situ modified polyurethane and high physical property synthetic leather manufacture method, neither change traditional technique and equipment, can be suitable for again the manufacture of multiple synthetic leather, have obvious novelty.
A kind of graphene in-situ modified polyurethane provided by the invention and high physical property synthetic leather manufacture method,It is characterized in that comprising the following steps:
(1) modified (weight portion) of Graphene
10 parts of Graphenes are added in 90 parts of wetting agent (organic solvent), add 5-10 part organo-silicon coupling agent, at 70 DEG C, react 24h, obtain the Graphene that oleophylic is modified；
(2) preparation (weight portion) of graphene in-situ modified polyurethane slurry；
1. the preparation of surface conditioning agent: add 0.5-1.0 part modified graphene in the surface treatment polyurethane of 100 parts of solid content 20-30%, auxiliary agent, the mill base mix homogeneously such as appropriate moistening flatting agent, defoamer, thickening agent, it is thus achieved that the surface conditioning agent of graphene in-situ modified；
2. the preparation of surface layer slurry: in the surface layer polyurethane solutions of 100 parts of solid content 30-35%, adds 0.3-0.5 part modified graphene, auxiliary agent, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the surface layer slurry of graphene in-situ modified；
3. the preparation of dry method slurry: in the dry method polyurethane solutions of 100 parts of solid content 30-35%, it is separately added into 0.3-0.5 part modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, mechanical foaming, it is thus achieved that the dry method foamed slurry of graphene in-situ modified；
4. the preparation of wet method slurry: in the wet method polyurethane solutions of 100 parts of solid content 30-35%, it is separately added into 0.3-0.5 part modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the wet method slurry of graphene in-situ modified；
(3) manufacture of synthetic leather:
The dry and wet technique manufacturing same routine of synthetic leather:
1. dry process: polyurethane cover slurry modified for Graphene is coated with and scrapes in release paper, coating layer thickness is 0.2-0.3mm, dry 90s in the baking oven of 110-130 DEG C, then it is coated with and scrapes the Polyurethane Interlayer dry method foamed slurry modifiied through Graphene, coating thickness controls at 0.8-1.2mm, dry 90s in 120-140 DEG C of baking oven, then it is coated with and scrapes conventional polyurethanes adhesive layer, it is dried to half-dried rear and base fabric hot pressing laminating, in 130-140 DEG C of dry 60s, cooling, paper leather separates, the surface conditioning agent modified then through Graphene processes, rub stricture of vagina, dry and obtain dry method foaming synthetic leather；
2. wet processing: the polyurethane wet slurry that the Graphene prepared is modified is evenly applied in the base fabric through being impregnated with in advance, then the base fabric scribbling slurry is put in the solidification liquid that pH is 5-7 and solidify, setting time 3-5min, then washes, dries, obtain wet-method synthetic leather bass；Wet method bass, then through the modified surface conditioning agent Final finishing of the modified surface layer resin dry method veneer of Graphene, Graphene, is rubbed stricture of vagina, dry is obtained wet-method synthetic leather.
Graphene is at least one in conductivity type Graphene, heat conductivity Graphene, accumulation energy type Graphene, reinforced graphite alkene and/or graphene oxide.
Wetting agent is at least one in dimethylformamide, dimethyl acetylamide and/or propylene glycol methyl ether acetate.
Silicone coupling agents is KH-550(3-aminopropyltriethoxywerene werene), KH-560(γ-glycidyl ether oxygen propyl trimethoxy silicane) and/or KH-602(N-β (aminoethyl)-γ-ammonia the third methyl dimethoxysilane at least one.
Gu the polyurethane solutions containing 30-35% includes surface treatment polyurethane, surface layer polyurethane, wet method polyurethane and dry method polyurethane etc..
High physical property synthetic leather includes multiple kinds such as clothing leather, sofa artificial leather, house ornamentation interior decoration leather, automobile, agricultural vehicle medicated cushion leather, luggage leather or upper leather.
Detailed description of the invention
By the examples below the present invention is specifically described; be necessary it is pointed out here that be that following example are only intended to the present invention is further detailed; it is not intended that limiting the scope of the invention; the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above, still falls within protection scope of the present invention.
Embodiment 1: the manufacture of dry method vamp synthetic leather
(1) modified (weight portion) of Graphene
10 parts of reinforced graphite alkene are added in 90 parts of propylene glycol methyl ether acetates, adds 10 parts of KH-550 organo-silicon coupling agents, at 70 DEG C, react 24h, obtain the Graphene that oleophylic is modified；
(2) preparation (weight portion) of graphene in-situ modified polyurethane slurry；
1. the preparation of surface conditioning agent: add auxiliary agent, the mill base mix homogeneously such as 1.0 parts of modified graphenes, appropriate moistening flatting agent, defoamer, thickening agent in the surface treatment polyurethane of 100 parts of solid contents 20%, it is thus achieved that the surface conditioning agent of graphene in-situ modified；
2. the preparation of surface layer slurry: in the surface layer polyurethane solutions of 100 parts of solid contents 30%, adds 0.5 part of modified graphene, auxiliary agent, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the surface layer slurry of graphene in-situ modified；
3. the preparation of dry method slurry: in the dry method polyurethane solutions of 100 parts of solid contents 35%, it is separately added into 0.5 part of modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, mechanical foaming, it is thus achieved that the dry method foamed slurry of graphene in-situ modified；
(3) manufacture of dry method vamp synthetic leather:
The dry process manufacturing same routine of synthetic leather:
Being coated with by polyurethane cover slurry modified for Graphene scrapes in release paper, coating layer thickness is 0.3mm, dry 90s in the baking oven of 110-130 DEG C, then it is coated with and scrapes the Polyurethane Interlayer dry method foamed slurry modifiied through Graphene, coating thickness controls at 1.0mm, dry 90s in 120-140 DEG C of baking oven, then it is coated with and scrapes conventional polyurethanes adhesive layer, it is dried to half-dried rear and base fabric hot pressing laminating, in 130-140 DEG C of dry 60s, cooling, paper leather separates, then through the surface conditioning agent Final finishing that Graphene is modified, rub stricture of vagina, dry obtain dry method foaming vamp synthetic leather.
It is simple that dry method manufactures upper leather technique, and good hand feeling after foaming, saturating vapour is good.Because wear-resisting, scratch resistance, anti-resistance to tearing and anti-deformation behavior are required all higher by upper leather, therefore Graphene content is all of a relatively high in surface layer, surface-treated layer, intermediate layer dry method resin, to improve the combination properties such as wear-resisting, the scratch resistance of upper leather, enhancing, toughness reinforcing, ageing-resistant, antibacterial and mouldproof.
Embodiment 2: the manufacture of wet method sofa synthetic leather
(1) modified (weight portion) of Graphene
5 parts are strengthened Graphene and 5 parts of thermal conductivity graphene add in 90 parts of dimethylformamides, add 5 parts of KH-560 organo-silicon coupling agents, at 70 DEG C, react 24h, obtain the Graphene that oleophylic is modified；
(2) preparation (weight portion) of graphene in-situ modified polyurethane slurry；
1. the preparation of surface conditioning agent: add auxiliary agent, the mill base mix homogeneously such as 0.8 part of modified graphene, appropriate moistening flatting agent, defoamer, thickening agent in the surface treatment polyurethane of 100 parts of solid contents 25%, it is thus achieved that the surface conditioning agent of graphene in-situ modified；
2. the preparation of surface layer slurry: in the surface layer polyurethane solutions of 100 parts of solid contents 30%, adds 0.4 part of modified graphene, auxiliary agent, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the surface layer slurry of graphene in-situ modified；
3. the preparation of wet method slurry: in the wet method polyurethane solutions of 100 parts of solid contents 30%, it is separately added into 0.5 part of modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate solvent, appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the wet method slurry of graphene in-situ modified；
(3) manufacture of wet method sofa synthetic leather:
The wet processing manufacturing same routine of synthetic leather:
Polyurethane wet slurry modified for the Graphene prepared is evenly applied in the base fabric through being impregnated with in advance, then the base fabric scribbling slurry is put in the solidification liquid that pH is 5-7 and solidify, setting time 3-5min, then aqueous, dry, obtain wet-method synthetic leather bass；Wet method bass, then through the modified surface conditioning agent Final finishing of the modified surface layer slurry dry method veneer of Graphene, Graphene, is rubbed stricture of vagina, dry is obtained wet-method synthetic leather.
The sofa artificial leather that this method manufactures is abundant, plentiful and steam permeability is good, because wear-resisting, scratch resistance, anti-resistance to tearing, heat conductivity are required all higher by sofa artificial leather, therefore enhancement mode and heat-conducting type Graphene content are all of a relatively high in surface layer, surface-treated layer, intermediate layer dry method resin, play the effects such as wear-resisting, scratch resistance, enhancing, toughness reinforcing, ageing-resistant, antibacterial and mouldproof.
Embodiment 3: the manufacture of dry method automobile cushion leather
(1) modified (weight portion) of Graphene
Strengthen Graphene by 10 parts to add in 45 part of third dimethylformamide and 45 parts of glycol methyl ether acetates, add 10 parts of KH-602 organo-silicon coupling agents, at 70 DEG C, react 24h, obtain the Graphene that oleophylic is modified；
(2) preparation (weight portion) of graphene in-situ modified polyurethane slurry；
1. the preparation of surface conditioning agent: add auxiliary agent, the mill base mix homogeneously such as 0.7 part of modified graphene, appropriate moistening flatting agent, defoamer, thickening agent in the surface treatment polyurethane of 100 parts of solid contents 20%, it is thus achieved that the surface conditioning agent of graphene in-situ modified；
2. the preparation of surface layer slurry: in the surface layer polyurethane solutions of 100 parts of solid contents 30%, adds 0.5 part of modified graphene, auxiliary agent, the mill base mix homogeneously such as appropriate flat agent, defoamer, thickening agent, it is thus achieved that the surface layer slurry of graphene in-situ modified；
3. the preparation of dry method foamed slurry: in the dry method polyurethane solutions of 100 parts of solid contents 35%, it is separately added into 0.3 part of modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, mechanical foaming, it is thus achieved that the dry method foamed slurry of graphene in-situ modified；
(3) manufacture of dry method automobile cushion leather:
The dry process manufacturing same routine of synthetic leather:
Being coated with by polyurethane cover slurry modified for Graphene scrapes in release paper, coating layer thickness is 0.3mm, dry 90s in the baking oven of 120-130 DEG C, then it is coated with and scrapes the Polyurethane Interlayer dry method slurry modifiied through Graphene, coating thickness controls at 1.2mm, dry 90s in 130-140 DEG C of baking oven, then it is coated with and scrapes conventional polyurethanes adhesive layer, it is dried to half-dried rear and base fabric hot pressing laminating, in 130-140 DEG C of dry 60s, cooling, paper leather separates, then through the surface conditioning agent Final finishing that Graphene is modified, rub stricture of vagina, dry obtain dry method automobile cushion leather.
The automobile leather that this method manufactures is abundant, plentiful, surface layer and surface treatment layer graphene content are higher, the wear-resisting scratch resistance of coating is excellent, and compared with the synthetic leather of traditional handicraft manufacture, the thermostability of its coating, resistance to ag(e)ing, electric conductivity, anti-flammability have to add and increase substantially.
Embodiment 4: the manufacture of wet method clothing leather
(1) modified (weight portion) of Graphene
10 parts of conductive graphenes are added in 90 parts of dimethyl acetylamide, adds 3.0 parts of KH-560 organo-silicon coupling agents, 4.0 parts of KH-602 organo-silicon coupling agents, at 70 DEG C, react 24h, obtain the Graphene that oleophylic is modified；
(2) preparation (weight portion) of graphene in-situ modified polyurethane slurry；
1. the preparation of surface conditioning agent: add auxiliary agent, the mill base mix homogeneously such as 0.5 part of modified graphene, appropriate moistening flatting agent, defoamer, thickening agent in the surface treatment polyurethane of 100 parts of solid contents 20%, it is thus achieved that the surface conditioning agent of graphene in-situ modified；
2. the preparation of surface layer slurry: in the surface layer polyurethane solutions of 100 parts of solid contents 30%, adds 0.3 part of modified graphene, auxiliary agent, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the surface layer slurry of graphene in-situ modified；
3. the preparation of wet method slurry: in the wet method polyurethane solutions of 100 parts of solid contents 35%, it is separately added into 0.3 part of modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate solvent, appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the wet method slurry of graphene in-situ modified；
(3) manufacture of wet method clothing leather:
The wet processing manufacturing same routine of synthetic leather: the polyurethane wet slurry that the Graphene prepared is modified is evenly applied in the base fabric through being impregnated with in advance, then the base fabric scribbling slurry is put in the solidification liquid that pH is 5-7 and solidify, setting time 3-5min, then aqueous, dry, obtains wet-method synthetic leather bass；Wet method bass, then through the modified surface conditioning agent Final finishing of the modified surface layer slurry dry method veneer of Graphene, Graphene, is rubbed stricture of vagina, dry is obtained wet method clothing leather.
The clothing leather that this method manufactures is slim and graceful, elegant, because wear-resisting, scratch resistance are required relatively low by clothing leather, and resistance to tearing, antistatic behaviour require higher, therefore the conductivity type Graphene content that surface layer and surface-treated layer are selected is relatively low, and Graphene content is of a relatively high in the wet method resin of intermediate layer, play certain enhancing, toughening effect.Compared with the clothing leather of traditional handicraft manufacture, tear resistance, wearability, antistatic behaviour significantly improve, and such as resistance to ag(e)ing, antibacterial and mouldproof are also improved to some extent other performances.
Claims (6)
1. a graphene in-situ modified polyurethane and high physical property synthetic leather manufacture method, it is characterised in that comprise the following steps:
(1) modified (weight portion) of Graphene
10 parts of Graphenes are added in 90 parts of wetting agent (organic solvent), add 5-10 part organo-silicon coupling agent, at 70 DEG C, react 24h, obtain the Graphene that oleophylic is modified；
(2) preparation (weight portion) of graphene in-situ modified polyurethane slurry；
1. the preparation of surface conditioning agent: add 0.5-1.0 part modified graphene in the surface treatment polyurethane of 100 parts of solid content 20-30%, auxiliary agent, the mill base mix homogeneously such as appropriate moistening flatting agent, defoamer, thickening agent, it is thus achieved that the surface conditioning agent of graphene in-situ modified；
2. the preparation of surface layer slurry: in the surface layer polyurethane solutions of 100 parts of solid content 30-35%, adds 0.3-0.5 part modified graphene, auxiliary agent, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the surface layer slurry of graphene in-situ modified；
3. the preparation of dry method slurry: in the dry method polyurethane solutions of 100 parts of solid content 30-35%, it is separately added into 0.3-0.5 part modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, mechanical foaming, it is thus achieved that the dry method foamed slurry of graphene in-situ modified；
4. the preparation of wet method slurry: in the wet method polyurethane solutions of 100 parts of solid content 30-35%, it is separately added into 0.3-0.5 part modified graphene, auxiliary agent, filler, the mill base mix homogeneously such as appropriate levelling agent, defoamer, thickening agent, it is thus achieved that the wet method slurry of graphene in-situ modified；
(3) manufacture of synthetic leather:
The dry and wet technique manufacturing same routine of synthetic leather:
1. dry process: polyurethane cover slurry modified for Graphene is coated with and scrapes in release paper, coating layer thickness is 0.2-0.3mm, dry 90s in the baking oven of 110-130 DEG C, then it is coated with and scrapes the Polyurethane Interlayer dry method foamed slurry modifiied through Graphene, coating thickness controls at 0.8-1.2mm, dry 90s in 120-140 DEG C of baking oven, then it is coated with and scrapes conventional polyurethanes adhesive layer, it is dried to half-dried rear and base fabric hot pressing laminating, in 130-140 DEG C of dry 60s, cooling, paper leather separates, then through the surface conditioning agent Final finishing that Graphene is modified, rub stricture of vagina, dry and obtain dry method foaming synthetic leather；
2. wet processing: the polyurethane wet slurry that the Graphene prepared is modified is evenly applied in the base fabric through being impregnated with in advance, then the base fabric scribbling slurry is put in the solidification liquid that pH is 5-7 and solidify, setting time 3-5min, then washes, dries, obtain wet-method synthetic leather bass；Wet method bass, then through the modified surface conditioning agent Final finishing of the modified surface layer slurry dry method veneer of Graphene, Graphene, is rubbed stricture of vagina, dry is obtained wet-method synthetic leather.
2. a kind of graphene in-situ modified polyurethane as claimed in claim 1 and high physical property synthetic leather manufacture method, it is characterised in that Graphene is at least one in conductivity type Graphene, heat conductivity Graphene, accumulation energy type Graphene, reinforced graphite alkene and/or graphene oxide.
3. a kind of graphene in-situ modified polyurethane as claimed in claim 1 and high physical property synthetic leather manufacture method, it is characterised in that wetting agent is at least one in dimethylformamide, dimethyl acetylamide and/or propylene glycol methyl ether acetate.
4. as claimed in claim 1 a kind of graphene in-situ modified polyurethane and high physical property synthetic leather manufacture method, it is characterised in that silicone coupling agents is KH-550(3-aminopropyltriethoxywerene werene), KH-560(γ-glycidyl ether oxygen propyl trimethoxy silicane) and/or KH-602(N-β (aminoethyl)-γ-ammonia the third methyl dimethoxysilane) at least one.
5. a kind of graphene in-situ modified polyurethane as claimed in claim 1 and high physical property synthetic leather manufacture method, it is characterised in that Gu the polyurethane solutions containing 30-35% includes surface treatment polyurethane, surface layer polyurethane, wet method polyurethane and dry method polyurethane etc..
6. a kind of graphene in-situ modified polyurethane as claimed in claim 1 and high physical property synthetic leather manufacture method, it is characterised in that described high physical property synthetic leather includes multiple kinds such as clothing leather, sofa artificial leather, house ornamentation interior decoration leather, interior leather for automobiles, luggage leather or upper leather.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610123815.8A CN105735002A (en) | 2016-03-07 | 2016-03-07 | Graphene in-situ modified polyurethane and method for manufacturing synthetic leather with high physical properties |
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| CN201610123815.8A CN105735002A (en) | 2016-03-07 | 2016-03-07 | Graphene in-situ modified polyurethane and method for manufacturing synthetic leather with high physical properties |
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| CN201610123815.8A Pending CN105735002A (en) | 2016-03-07 | 2016-03-07 | Graphene in-situ modified polyurethane and method for manufacturing synthetic leather with high physical properties |
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| CN106832880A (en) * | 2017-01-17 | 2017-06-13 | 南通强生安全防护科技股份有限公司 | Graphene oiliness PU composite mortars and its production and use |
| CN107761404A (en) * | 2017-12-06 | 2018-03-06 | 吴宗文 | A kind of preparation method of high abrasion-proof PU synthetic leather fabric |
| CN107904960A (en) * | 2017-10-28 | 2018-04-13 | 长沙秋点兵信息科技有限公司 | A kind of preparation method of smooth type artificial synthetic leather |
| CN108193506A (en) * | 2018-02-02 | 2018-06-22 | 天守(福建)超纤科技股份有限公司 | A kind of automotive trim graphene superfine fiber chemical leather |
| IT201700012184A1 (en) * | 2017-02-03 | 2018-08-03 | Fadel S R L | MANUFACTURED IN SHEET, PARTICULARLY INTENDED FOR THE REALIZATION OF FOOTWEAR, GARMENTS AND CLOTHING ACCESSORIES, UPHOLSTERY OR SIMILAR, AND ITS RELATED PROCEDURE |
| CN109112846A (en) * | 2018-07-23 | 2019-01-01 | 南通中奥车用新材料有限公司 | A kind of high-strength abrasion-proof plated film PVC artificial leather |
| CN109914115A (en) * | 2019-04-04 | 2019-06-21 | 天守(福建)超纤科技股份有限公司 | A kind of graphene superfine fibre, Synthetic Leather and preparation method |
| CN110804152A (en) * | 2019-10-14 | 2020-02-18 | 江苏华大新材料有限公司 | Wet graphene polyurethane resin for leather and preparation method and application thereof |
| IT201900002813A1 (en) * | 2019-02-27 | 2020-08-27 | Milmare Srl | LAMINATED COMPOSITE MATERIAL WITH GRAPHENE SURFACE TREATMENT |
| CN111923311A (en) * | 2020-07-29 | 2020-11-13 | 福建省德化鲁闽怡家陶瓷文创有限公司 | Production process of graphene PU insole |
| CN111979788A (en) * | 2020-07-08 | 2020-11-24 | 佛山市三水联美化工有限公司 | Waterborne polyurethane synthetic leather and application thereof |
| CN113981710A (en) * | 2021-11-19 | 2022-01-28 | 龙纤精密纺织有限公司 | Preparation method of artificial synthetic leather containing nitrogen-containing titanium dioxide |
| WO2022023137A1 (en) | 2020-07-29 | 2022-02-03 | Directa Plus S.P.A. | Method for making a conductive coating containing graphene on natural or synthetic leather, and natural or synthetic leather thus obtained. |
| CN114277582A (en) * | 2021-12-08 | 2022-04-05 | 福建省三源兴纺织科技有限公司 | High-cold-resistance wear-resistant synthetic leather and preparation method thereof |
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| CN106832880A (en) * | 2017-01-17 | 2017-06-13 | 南通强生安全防护科技股份有限公司 | Graphene oiliness PU composite mortars and its production and use |
| IT201700012184A1 (en) * | 2017-02-03 | 2018-08-03 | Fadel S R L | MANUFACTURED IN SHEET, PARTICULARLY INTENDED FOR THE REALIZATION OF FOOTWEAR, GARMENTS AND CLOTHING ACCESSORIES, UPHOLSTERY OR SIMILAR, AND ITS RELATED PROCEDURE |
| WO2018142335A1 (en) * | 2017-02-03 | 2018-08-09 | Fadel S.R.L. | Manufactured article in sheet form, particularly intended for use in the manufacture of footwear, clothing items and accessories, upholstery or the like, and related realization procedure |
| CN107904960A (en) * | 2017-10-28 | 2018-04-13 | 长沙秋点兵信息科技有限公司 | A kind of preparation method of smooth type artificial synthetic leather |
| CN107904960B (en) * | 2017-10-28 | 2020-09-15 | 安徽博朗凯德车用皮革科技有限公司 | Preparation method of smooth artificial synthetic leather |
| CN107761404A (en) * | 2017-12-06 | 2018-03-06 | 吴宗文 | A kind of preparation method of high abrasion-proof PU synthetic leather fabric |
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| CN108193506A (en) * | 2018-02-02 | 2018-06-22 | 天守(福建)超纤科技股份有限公司 | A kind of automotive trim graphene superfine fiber chemical leather |
| CN109112846A (en) * | 2018-07-23 | 2019-01-01 | 南通中奥车用新材料有限公司 | A kind of high-strength abrasion-proof plated film PVC artificial leather |
| CN109112846B (en) * | 2018-07-23 | 2021-03-02 | 南通中奥车用新材料有限公司 | High-strength wear-resistant coated PVC artificial leather |
| IT201900002813A1 (en) * | 2019-02-27 | 2020-08-27 | Milmare Srl | LAMINATED COMPOSITE MATERIAL WITH GRAPHENE SURFACE TREATMENT |
| CN109914115A (en) * | 2019-04-04 | 2019-06-21 | 天守(福建)超纤科技股份有限公司 | A kind of graphene superfine fibre, Synthetic Leather and preparation method |
| CN110804152A (en) * | 2019-10-14 | 2020-02-18 | 江苏华大新材料有限公司 | Wet graphene polyurethane resin for leather and preparation method and application thereof |
| CN111979788A (en) * | 2020-07-08 | 2020-11-24 | 佛山市三水联美化工有限公司 | Waterborne polyurethane synthetic leather and application thereof |
| CN111923311A (en) * | 2020-07-29 | 2020-11-13 | 福建省德化鲁闽怡家陶瓷文创有限公司 | Production process of graphene PU insole |
| WO2022023137A1 (en) | 2020-07-29 | 2022-02-03 | Directa Plus S.P.A. | Method for making a conductive coating containing graphene on natural or synthetic leather, and natural or synthetic leather thus obtained. |
| CN113981710A (en) * | 2021-11-19 | 2022-01-28 | 龙纤精密纺织有限公司 | Preparation method of artificial synthetic leather containing nitrogen-containing titanium dioxide |
| CN114277582A (en) * | 2021-12-08 | 2022-04-05 | 福建省三源兴纺织科技有限公司 | High-cold-resistance wear-resistant synthetic leather and preparation method thereof |
| CN115467174A (en) * | 2022-08-10 | 2022-12-13 | 苏州瑞高新材料有限公司 | Conductive PU synthetic leather and preparation method thereof |
| CN115467174B (en) * | 2022-08-10 | 2024-05-03 | 苏州瑞高新材料股份有限公司 | Conductive PU synthetic leather and preparation method thereof |
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