CN103882726A - Method for preparing dry-process PU/PVDF (polyurethane/polyvinylidene fluoride) hydrophobic polyurethane coating for synthetic leather - Google Patents
Method for preparing dry-process PU/PVDF (polyurethane/polyvinylidene fluoride) hydrophobic polyurethane coating for synthetic leather Download PDFInfo
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- CN103882726A CN103882726A CN201410116982.0A CN201410116982A CN103882726A CN 103882726 A CN103882726 A CN 103882726A CN 201410116982 A CN201410116982 A CN 201410116982A CN 103882726 A CN103882726 A CN 103882726A
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Abstract
The invention discloses a method for preparing a dry-process PU/PVDF (polyurethane/polyvinylidene fluoride) hydrophobic polyurethane coating for synthetic leather. The method comprises the following steps: (1) mixing PU with PVDF; (2) adding an organic solvent with N,N-dimethylformamide (DMF) and methyl ethyl ketone (MEK) in a mass ratio of (0-50): (0-20), adding a color paste aid to prepare a surface layer, preparing a bonding layer in a ratio of PU to DMF to MEK to color paste of (0-100): (0-50): (0-20): (0-15), and fully stirring slurry of the surface layer and a surface material of the bonding layer by a vacuum mixer at room temperature respectively to form viscous solution slurry; and (3) applying a dry-process surface layer coating to release paper, solidifying for forming to obtain a dry-process PU/PVDF surface layer, applying the bonding layer to the surface layer, bonding a wet-process base material of the synthetic leather with the dry-process surface layer by a semi-dry bonding method, and drying and curing to obtain the dry-process PU/PVDF hydrophobic polyurethane coating. After PU/PVDF blending modification, the coating is high in hydrophobicity, pollution resistance, flame retardance coefficient and mechanical tensile strength; the method is simple, low in requirement and low in cost and facilitates industrialization production application of the synthetic leather.
Description
Technical field
The hydrophobically modified technical field that the invention belongs to use for synthetic leather polyurethane coating, is specifically related to the method that one is prepared the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF.
Background technology
Hydrophobic polyurethane coating is a kind of polyurethane material that has property, because its special performance is widely used in coatings art.Hydrophobic polyurethane coating always is as a kind of special material and using in synthetic leather Application Areas, its within the specific limits effectively hydrophobic function can make use for synthetic leather material become the more comfortable more suitable mankind to use.In the situation that not changing existing sanitation performance, it is particularly important that hydrophobic performance becomes, and it is widely used in the fields such as high-performance apparel leather, footwear leather, building materials outsourcing coating.What application study polyurethane hydrophobically modified mainly used at present is that nano silicon is inorganic material-modified, by adopting vinyl-based siloxanes coupling agent to modify silica, thereby obtains having the material of hydrophobic function.The method complicated process of preparation is unfavorable for commercial Application fast.Along with the development of polyurethane material, hydrophobic polyurethane coating will will be widely used in building coats, special material, substrate coating and paint field with its special performance.
PVDF has good corrosion resisting property, except the not polar solvent of resistance to only a few (DMF, acetone, butanone etc.), fuming sulphuric acid, fuming nitric aicd, chlorosulfonic acid, the dense alkali of high temperature, the corrosion of the most of inorganic acids of ability, alkali salt, organic acid, organic solvent, halogen compounds, aromatic hydrocarbons medium.Hydrophobic antipollution and the weatherability of PVDF are fabulous, its film article drenches and shines 3000h in outdoor sunlight wind and rain, tensile strength is without large variation, in chemical atmosphere, use 1 year, its mechanical performance also has no decline, for large-scale tall buildings, application PVDF skin, can stand ultraviolet ray in 30 years and irradiate and erosion by wind and rain, still not pollute, not embrittlement, not aging, this is the hydrophobic and weatherability of the not available antipollution of any other fluoroplastics.
Current synthetic leather for city shoe, synthetic leather, automobile cushion synthetic leather for sofa, the surface layer polyurethane major part of use is all common resin, although they have certain hydrophobic function, hydrophobic performance and antifouling property are poor.On market, main silica filler and the hydrophobic auxiliary agent of relying on processed at present, and to reaching hydrophobic resistant to pollution object, but this kind of method industrialization cost is high, is unfavorable for the lifting of suitability for industrialized production and economic benefit.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide the method that one is prepared the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, the method has easy to operation, is easy to industrial applications, the feature that raw material is cheap and easy to get.
To achieve these goals, the technical solution used in the present invention is the method that one is prepared the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, includes following steps:
1) first polyurethane PU and Kynoar PVDF are mixed than the ratio for 100:5,100:10 or 100:15 according to mass fraction;
2) add nitrogen dimethylformamide DMF: the solvent of acetone MEK=0～50:0～20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the mill base auxiliary addition agent material of 0～15 part, be configured to surface layer slurry; Equally according to polyurethane PU: nitrogen dimethylformamide DMF: acetone MEK: the proportional arrangement of mill base=0～100:0～50:0～20:0～15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, and formation by surface layer slurry viscosity is
, gluing layer fabric viscosity is
solution slurry; Solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) adopt spraying or the method for blade coating, coated after solidifying in release liners and obtain a kind of hydrophobic and polyurethane coating anti-flaming function that has, the dry method that this polyurethane coating is mainly used in synthetic leather production process is moved membrane process.
the invention has the beneficial effects as follows:
The dry method that this polyurethane coating is mainly used in synthetic leather production process is moved membrane process.After PU/PVDF blending and modifying, the hydrophobicity of coating, resistance tocrocking, fire-retardant coefficient increase, and the mechanical tensile strength of this dry coating is also improved, and in the time of PU:PVDF=100:15, this dry coating TENSILE STRENGTH is brought up to 0.150MPa by 0.142MPa.This preparation method is simple, requirement condition is low, cost is low, be easy to the application of synthetic leather suitability for industrialized production.In addition, Kynoar PVDF has both the characteristic of resins for universal use and fluororesin, except having good heat-resisting quantity, chemical resistance, oxidative resistance, resistance to x radiation x, weather resistance, also there is the properties such as good piezoelectricity, dielectricity, pyroelectricity.The hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF of the present invention has very large economic worth.
Adding of Kynoar PVDF filler auxiliary agent is very convenient, directly proportionally mixes with polyurethane PU early stage in batching, makes surface layer slurry.And industrial PVDF low price, on market, hydrophobic polyurethane synthetic leather has very large application prospect.Therefore the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, has very large through being worth.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.We take city shoe by the manufacture craft of synthetic leather as case study on implementation.
(1) resin raw material
(2) process program
Surface layer: HDS-50HF, tack coat: HDA-20; Surface layer slurry coating thickness 0.10mm, gluing layer slurry coating thickness 0.10mm; Release liners AW-67; The common wet method footwear leather of base material 0.8mm semi-finished product; Laminating type: half dry doubling; Nip 0.5mm; Peel off
(3) technical recipe
embodiment mono-
One is prepared the method for the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, includes following steps:
1) first HDS-50HF polyurethane PU is mixed than the ratio that is 100:5 according to mass fraction with Kynoar PVDF;
2) add nitrogen dimethylformamide DMF: the solvent of acetone MEK=40:20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the mill base auxiliary addition agent material of 15 parts, be configured to surface layer; Equally according to HDA-20 polyurethane PU: nitrogen dimethylformamide DMF: the proportional arrangement of acetone MEK: mill base=100:20:20:15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, its viscosity is existed respectively
, the solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) by surface layer solution spraying in release liners, coating thickness is 0.1mm dry 10min at 120 ℃ in baking oven; Take out release liners, the gluing layer slurry of blade coating 0.1mm thickness; Put it into again oven drying 4min; Take out common 0.8mm wet method leather semi-finished product and its laminating; Put into oven drying 10min; Take out to leave standstill and be down to room temperature and peel off, obtain having the synthetic leather of hydrophobic polyurethane coating, comparatively 67 ° of this hydrophobicity synthetic leather surface layer contacts.
embodiment bis-
One is prepared the method for the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, includes following steps:
1) first HDS-50HF polyurethane PU resin is mixed than the ratio that is 100:10 according to mass fraction with Kynoar PVDF;
2) add into nitrogen dimethylformamide DMF: the solvent of acetone MEK=40:20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the auxiliary addition agent materials such as the mill base of 15 parts, be configured to surface layer; Equally according to polyurethane PU: nitrogen dimethylformamide DMF: the proportional arrangement of acetone MEK: mill base=100:20:20:15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, its viscosity is existed respectively
, the solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) by surface layer solution spraying or blade coating in release liners, coating thickness is 0.1mm dry 10min at 120 ℃ in baking oven; Take out release liners, the gluing layer slurry of blade coating 0.1mm thickness; Put it into again oven drying 4min; Take out common 0.8mm wet method leather semi-finished product and its laminating; Put into oven drying 10min; Take out to leave standstill and be down to room temperature and peel off, obtain having the synthetic leather of hydrophobic polyurethane coating.This hydrophobicity synthetic leather surface layer contact angle is 72 °.
embodiment tri-
One is prepared the method for the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, includes following steps:
1) first HDS-50HF polyurethane PU and Kynoar PVDF are mixed than the ratio for 100:15 according to mass fraction, after the ratio of PU and PVDF exceedes 100:15, film can become fragile in hardening, is unfavorable for use for synthetic leather;
2) add nitrogen dimethylformamide DMF: the solvent of acetone MEK=40:20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the auxiliary addition agent materials such as the mill base of 15 parts, be configured to surface layer; Equally according to HDA-20 polyurethane PU: nitrogen dimethylformamide DMF: the proportional arrangement of acetone MEK: mill base=100:20:20:15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, its viscosity is respectively
, the solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) by surface layer solution blade coating in release liners, coating thickness is 0.1mm dry 10min at 120 ℃ in baking oven; Take out release liners, the gluing layer slurry of blade coating 0.1mm thickness; Put it into again oven drying 4min; Take out common 0.8mm wet method leather semi-finished product and its laminating; Put into oven drying 10min; Take out to leave standstill and be down to room temperature and peel off, obtain having the synthetic leather of hydrophobic polyurethane coating.This synthetic leather surface layer contact angle is 81 °.
With the use for synthetic leather polyurethane coating after PVDF modification, its hydrophobicity has larger raising, by the measurement to its contact angle, we can find, in the time not adding PVDF modification, the contact angle of its dry method surface layer is 42 °, add respectively after the PVDF modification of 5/10/15 umber, the contact angle of dry method surface layer is brought up to respectively 67 °, 72 °, 81 °.Illustrated fully and had hydrophobicity to a certain extent with the use for synthetic leather polyurethane dry method surface layer after PVDF modification, contamination resistance has obtained improving significantly.By the test of the polyurethane coating flame-retarding characteristic to after modification, we find that its flame-retarding characteristic also has raising to a certain extent.By the test of the polyurethane dry method surface layer TENSILE STRENGTH to after modification, its TENSILE STRENGTH is also greatly improved.This absolutely proved with the dry method film-forming polyurethanes coating after PVDF modification not only hydrophobicity have significant improvement, and its flame-retarding characteristic, TENSILE STRENGTH all increase, and can not affect other performances of this polyurethane surface layer.These characteristics will make this method of modifying have application more widely in following polyurethane coating, coating, clad material field.
Claims (4)
1. a method of preparing the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, is characterized in that, includes following steps:
1) first polyurethane PU and Kynoar PVDF are mixed than the ratio for 100:5,100:10 or 100:15 according to mass fraction;
2) add nitrogen dimethylformamide DMF: the solvent of acetone MEK=0～50:0～20 mass fraction, solvent comprises nitrogen dimethylformamide DMF and acetone MEK, the two is scattered in organic solvent, adding mass fraction is the mill base auxiliary addition agent material of 0～15 part again, is configured to surface layer slurry; Equally according to polyurethane PU: nitrogen dimethylformamide DMF: acetone MEK: the proportional arrangement of mill base=0～100:0～50:0～20:0～15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, and formation by surface layer slurry viscosity is
, gluing layer fabric viscosity is
solution slurry; Solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) adopt spraying or the method for blade coating, coated after solidifying in release liners and obtain a kind of hydrophobic and polyurethane coating anti-flaming function that has.
2. one according to claim 1 is prepared the method for the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, it is characterized in that, includes following steps:
1) first polyurethane PU is mixed than the ratio that is 100:5 according to mass fraction with Kynoar PVDF;
2) and then add nitrogen dimethylformamide DMF: the solvent of acetone MEK=40:20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the mill base auxiliary addition agent material of 15 parts, be configured to surface layer; According to polyurethane PU: nitrogen dimethylformamide DMF: the proportional arrangement of acetone MEK: mill base=100:20:20:15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, its viscosity is existed respectively
, the solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) surface layer polyurethane slurry is sprayed in release liners, coating thickness is that 0.1mm is dried 10min in baking oven at 120 ℃; Take out release liners, the gluing layer slurry of blade coating 0.1mm thickness; Put it into again oven drying 4min; Take out common 0.8mm wet method leather semi-finished product and its laminating; Put into oven drying 10min; Take out to leave standstill and be down to room temperature and peel off, obtain the synthetic leather of modification PU-PVDF hydrophobic polyurethane coating.
3. one according to claim 1 is prepared the method for the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, it is characterized in that, includes following steps:
1) first polyurethane PU resin is mixed than the ratio that is 100:10 according to mass fraction with Kynoar PVDF;
2) and then add nitrogen dimethylformamide DMF: the solvent of acetone MEK=40:20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the mill base auxiliary addition agent material of 15 parts, be configured to surface layer; According to polyurethane PU: nitrogen dimethylformamide DMF: the proportional arrangement of acetone MEK: mill base=100:20:20:15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, its viscosity is existed respectively
, the solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) surface layer polyurethane slurry is sprayed in release liners, coating thickness is that 0.1mm is dried 10min in baking oven at 120 ℃; Take out release liners, the gluing layer slurry of blade coating 0.1mm thickness; Put it into again oven drying 4min; Take out common 0.8mm wet method leather semi-finished product and its laminating; Put into oven drying 10min; Take out to leave standstill and be down to room temperature and peel off, obtain the synthetic leather of modification PU/PVDF hydrophobic polyurethane coating.
4. one according to claim 1 is prepared the method for the hydrophobic polyurethane coating of synthetic leather dry process PU/PVDF, it is characterized in that, includes following steps:
1) first polyurethane PU and Kynoar PVDF are mixed than the ratio for 100:15 according to mass fraction;
2) and then add nitrogen dimethylformamide DMF: the solvent of acetone MEK=40:20 mass fraction, solvent comprises dimethyl formamide DMF and acetone MEK, the two is scattered in organic solvent, then to add mass fraction be the mill base auxiliary addition agent material of 15 parts, be configured to surface layer; According to polyurethane PU: nitrogen dimethylformamide DMF: the proportional arrangement of acetone MEK: mill base=100:20:20:15 becomes gluing layer, surface layer slurry, gluing layer fabric are fully at room temperature stirred to 2h with de-airing mixer respectively, its viscosity is respectively
, the solution vacuumizing and defoaming 2h after utilizing evacuator to this modification, then standing and defoaming 12h;
3) surface layer polyurethane slurry is sprayed in release liners, coating thickness is that 0.1mm is dried 10min in baking oven at 120 ℃; Take out release liners, the gluing layer slurry of blade coating 0.1mm thickness; Put it into again oven drying 4min; Take out common 0.8mm wet method leather semi-finished product and its laminating; Put into oven drying 10min; Take out to leave standstill and be down to room temperature and peel off, obtain the synthetic leather of modification PU/PVDF hydrophobic polyurethane coating.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479616A (en) * | 2014-12-17 | 2015-04-01 | 广东菲安妮皮具股份有限公司 | Adhesive with strong adhesion performance and preparation method thereof |
| CN108049241A (en) * | 2017-11-30 | 2018-05-18 | 湖北大学 | A kind of preparation method of the shape memory Janus materials with energy conversion effet |
| CN108587113A (en) * | 2018-03-20 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of self-cleaning polyurethane elastomer film |
| CN113136136A (en) * | 2021-05-13 | 2021-07-20 | 苏州贝斯特装饰新材料有限公司 | Surface finishing agent for PVC synthetic leather, preparation method thereof and PVC synthetic leather |
| CN113638263A (en) * | 2021-09-10 | 2021-11-12 | 苏州大学 | High-adhesion quasi-super-hydrophobic material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479616A (en) * | 2014-12-17 | 2015-04-01 | 广东菲安妮皮具股份有限公司 | Adhesive with strong adhesion performance and preparation method thereof |
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| CN108587113A (en) * | 2018-03-20 | 2018-09-28 | 浙江工业大学 | A kind of preparation method of self-cleaning polyurethane elastomer film |
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| CN113136136A (en) * | 2021-05-13 | 2021-07-20 | 苏州贝斯特装饰新材料有限公司 | Surface finishing agent for PVC synthetic leather, preparation method thereof and PVC synthetic leather |
| CN113638263A (en) * | 2021-09-10 | 2021-11-12 | 苏州大学 | High-adhesion quasi-super-hydrophobic material and preparation method thereof |
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