CN113152114A - Preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes - Google Patents
Preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes Download PDFInfo
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- CN113152114A CN113152114A CN202110212056.3A CN202110212056A CN113152114A CN 113152114 A CN113152114 A CN 113152114A CN 202110212056 A CN202110212056 A CN 202110212056A CN 113152114 A CN113152114 A CN 113152114A
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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
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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
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
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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
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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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
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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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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- 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
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
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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
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1685—Wear resistance
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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
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1692—Weather resistance
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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
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
- D06N2211/106—Footwear
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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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention provides a preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes, belonging to the field of manufacturing of waterborne polyurethane artificial leather. A preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes comprises the following steps: firstly, preparing the waterborne polyurethane base by an acid/salt solidification process, then preparing a waterborne polyurethane dry-process semi-finished product by a release paper transfer film method, and finally obtaining the high-physical-property waterborne polyurethane synthetic leather by the processes of printing, embossing and the like. The waterborne polyurethane synthetic leather manufactured by the invention solves the problems of unstable sizing, easy wrinkle and low yield in the manufacturing process of waterborne polyurethane synthetic leather sizing shoes, fills the blank of high-physical-property products of waterborne polyurethane synthetic leather, and adds a new solution for replacing environment-friendly and poor high-physical-property oily synthetic leather.
Description
Technical Field
The invention belongs to the field of manufacturing of waterborne polyurethane artificial leather, and particularly relates to a preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes.
Background
The shaping shoe is mainly characterized in that: the sole is high in the front and low in the back, namely the sole is worn on a foot, and the height of the tiptoe is higher than that of the heel, so the sole is also called as a negative heel shoe. The related disciplines involved are as follows: foot surgery, non-surgical orthotics, gait analysis, rehabilitation medicine, (dance) physical training, motion biology, footprints are one of the hot research directions of human mechanics, orthopedics and gait analytics, and products are common abroad.
The material for manufacturing the shaped shoes must ensure proper hardness. The soft material has insufficient hardness, is easy to deform under compression, has hardness closely related to correction strength, and has no correction function even if the soft material has no hardness. Materials with excessive hardness, such as wood, plastic and metal, cannot bend the sole, are difficult to walk normally, have abnormal gait, and have no correction function. The high-quality rubber and leather have proper hardness, are not easy to deform and are wear-resistant.
In the prior art, the waterborne polyurethane synthetic leather is often used as a manufacturing material of a sizing shoe, but sizing is unstable in the manufacturing process, wrinkles are easy to appear, the yield is low, the weather resistance is poor, and particularly the low-temperature bending resistance is high, so that the application field of the waterborne polyurethane synthetic leather is limited.
Disclosure of Invention
The invention provides a preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes, aiming at the problems that in the prior art, shaping is unstable, wrinkles are easy to appear, weather resistance is poor and the rate of finished products is low in the manufacturing process of waterborne polyurethane synthetic leather shaped shoes. Compared with the prior art, the waterborne polyurethane synthetic leather prepared by the invention has high physical property, good flexing resistance and low-temperature flexing resistance, good wear resistance and capability of realizing mass production of winter shaping shoes.
The invention provides a preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes, which comprises the following steps:
1) preparing the waterborne polyurethane base by an acid/salt solidification process:
firstly, taking aqueous polyurethane resin with solid content of 45-55%, adding 0.1-0.5% of calcium powder dispersant, 30-60% of filler calcium powder, 0.5-2.0% of anti-cracking agent, 1-10% of foaming agent, 1-10% of foam stabilizer, 0.2-1.0% of isocyanate cross-linking agent and 0.2-1.0% of thickening agent according to the weight percentage of the aqueous polyurethane resin, and uniformly mixing and defoaming to obtain foaming slurry for later use;
secondly, the fabric is dried after being treated by 0.5 to 2.0 percent of oxalic acid/tartaric acid water solution, the wet-process slurry obtained in the first step is coated on the surface of the fabric for foaming by utilizing a water-based polyurethane foaming machine, the foaming density is controlled to be 0.65 to 0.80, and then the fabric is solidified and washed by 0.5 to 3.0 percent of acid/salt water solution, and the water-based polyurethane base is obtained by drying and rolling in different temperature areas for standby;
2) preparing a dry-process semi-finished product of the waterborne polyurethane:
thirdly, the surface layer resin is water-based polyurethane resin copolymerized or mixed by polyether and polycarbonate, 0.2 to 1.0 percent of flatting agent, 2 to 10 percent of pigment, 0.2 to 1.0 percent of isocyanate cross-linking agent and 0.2 to 1.0 percent of thickening agent are added according to the weight percentage of the resin, and water-based surface layer slurry is obtained after even mixing;
fourthly, the middle layer and the bonding layer are polyether type waterborne polyurethane resin, 0.2 to 1.0 percent of leveling agent, 2 to 10 percent of pigment and 0.2 to 1.0 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is uniformly mixed to obtain waterborne middle layer slurry and waterborne bonding layer slurry;
3) preparing a finished product by a release paper transfer film method:
fifthly, unreeling release paper; then coating the water-based surface layer slurry, the water-based middle layer slurry and the water-based bonding layer slurry on release paper in sequence; finally, the waterborne polyurethane base is attached to the bonding layer coated by the release paper, and the bonding layer is dried and cooled;
and sixthly, stripping the release paper, and then printing and embossing to obtain the high-physical-property waterborne polyurethane synthetic leather.
Further, the viscosity of the wet slurry in the step (i) is 10000-30000 cps.
Further, the fabric is woven fabric, knitted fabric or non-woven fabric, the elongation at break of the 45-degree angle cutting strip is 50% -90%, and the hair effect of the back side is in a hairless or micro-hair state.
Further, the coating amount of the wet slurry coating operation is 400-800g/m2。
Further, the acid/salt water solution is a mixed solution of oxalic acid or tartaric acid and sodium chloride or potassium chloride, and the preparation method comprises the following steps: dissolving 0.5-3 parts by weight of oxalic acid or tartaric acid and 0.5-3 parts by weight of sodium chloride or potassium chloride in 100 parts by weight of water, and uniformly stirring to obtain a mixed solution.
Further, the temperature range of the different temperature zones is 80-170 ℃, and the temperature interval is 5-10 ℃.
Furthermore, the physical properties of the waterborne polyurethane base prepared in the step 1) can reach 1.5 kg/cm in dry stripping, 1.0 kg/cm in wet stripping, 10 ten thousand in dry bending, 10 ten thousand in wet bending and 2 ten thousand in bending at minus 15 degrees.
And step three, the solid content of the waterborne polyurethane resin copolymerized or mixed with the polyether and the polycarbonate is 28-35%, and the 100% modulus is 4-6 MPa.
Further, the viscosity of the aqueous surface layer slurry is 2000-5000 cps.
Further, the solid content of the polyether type waterborne polyurethane resin in the step (IV) is 40-50%, and the 100% modulus is 2-4 MPa.
Further, the viscosity of the aqueous middle layer slurry and the viscosity of the aqueous bonding layer slurry are respectively 2000-5000cps and 4000-8000 cps.
Further, the coating amounts of the water-based surface layer sizing agent, the water-based middle layer sizing agent and the water-based bonding layer sizing agent are all 60-150g/m2。
And further, after the aqueous surface layer slurry and the aqueous middle layer slurry are coated, drying for one time, and after the aqueous bonding layer slurry is coated, wet bonding or semi-dry bonding with the aqueous polyurethane base can be carried out.
Further, the physical properties of the waterborne polyurethane semi-finished product prepared in the step 2) can reach 1.5 kg/cm in dry stripping, 1.0 kg/cm in wet stripping, 10 ten thousand in dry bending, 10 ten thousand in wet bending, 2 ten thousand in bending at minus 15 ℃, 6 ten thousand in dry martindale wear resistance, 8000 times in wet martindale wear resistance and 50% -90% in breaking elongation of 45-degree cutting strips.
The aqueous polyurethane resin can adopt conventional raw materials in the field, for example, the aqueous polyurethane resin which is produced by using acetone or water as a solvent is carboxylic acid type or sulfonic acid type aqueous polyurethane selected in the embodiment of the invention.
The foaming agent can be prepared from raw materials conventional in the art, for example, the foaming agent selected in the embodiment of the invention is an organic silicon modified foaming agent, a stearate foaming agent or a sodium dodecyl sulfate composite foaming agent.
The foam stabilizer can be prepared from raw materials conventional in the art, for example, the foam stabilizer selected in the embodiment of the invention is a silicone polyether emulsion foam stabilizer.
The thickening agent can adopt the conventional raw materials in the field, for example, the thickening agent selected by the embodiment of the invention is an associative polyurethane thickening agent or an alkali swelling acrylic acid thickening agent.
The leveling agent can be prepared from conventional raw materials in the field, for example, the leveling agent selected in the embodiment of the invention is leveling agent H produced by Langshan chemical company, Inc.
Further, the physical properties of the high-physical-property waterborne polyurethane finished product prepared in the step 3) can reach dry stripping 1.2 kg/cm, wet stripping 1.0 kg/cm, dry bending 5 ten thousand times, wet bending 5 ten thousand times, bending 2 ten thousand times at minus 15 degrees, dry martindale wear resistance 6 ten thousand times, wet martindale wear resistance 6400 times, and the elongation at break of a 45-degree cutting strip is 50% -90%, so that the requirements of products such as shaping shoes and the like are met.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the wet-process bass with high physical property is selected as the base material, so that the physical property of the final synthetic leather is improved; the dry method veneering adopts the high-physical-property polycarbonate or polyether resin, so that the flexing resistance and the wear resistance of the finished product, particularly the low-temperature flexing resistance, are further improved, the mass production of the winter-shaped shoes is realized, and the application field of the waterborne polyurethane is widened.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples. The process is conventional unless otherwise specified, and the starting materials are commercially available from the public unless otherwise specified.
Example 1
A preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes comprises the following steps:
1) preparing the waterborne polyurethane base by an acid/salt solidification process:
firstly, taking aqueous polyurethane resin with 50 percent of solid content, adding 0.3 percent of calcium powder dispersant, 40 percent of filler calcium powder, 1.2 percent of anti-cracking agent, 6 percent of foaming agent, 6 percent of foam stabilizer, 0.6 percent of isocyanate cross-linking agent and 0.5 percent of thickening agent according to the weight percent of the aqueous polyurethane resin, and uniformly mixing and defoaming to obtain wet-process slurry with the viscosity of 20000cps for later use;
secondly, the woven fabric is dried after being treated by 1.5 percent oxalic acid aqueous solution, the wet slurry obtained in the first step is coated on the surface of the woven fabric for foaming by utilizing a waterborne polyurethane foaming machine, and the coating amount is 600g/m2Controlling the foaming density to be 0.75, then solidifying and washing in a 2.0% oxalic acid/sodium chloride aqueous solution (in parts by weight, 2 parts of oxalic acid and 2 parts of sodium chloride are dissolved in 100 parts of water and uniformly stirred), drying and rolling in different temperature zones with the temperature range of 80-170 ℃ and the temperature interval of 5-10 ℃ to obtain waterborne polyurethane base for later use;
2) preparing a dry-process semi-finished product of the waterborne polyurethane:
③ the surface layer resin is 100 percent of waterborne polyurethane resin copolymerized by polyether and polycarbonate with the solid content of 32 percent and the modulus of 5MPa, 0.6 percent of flatting agent, 8 percent of pigment, 0.7 percent of isocyanate cross-linking agent and 0.7 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is uniformly mixed to obtain waterborne surface layer slurry with the viscosity of 3500 cps;
fourthly, the middle layer and the bonding layer are polyether type waterborne polyurethane resin with the solid content of 46 percent and the modulus of 100 percent being 3MPa, 0.6 percent of flatting agent, 8 percent of pigment and 0.7 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is uniformly mixed to obtain waterborne middle layer and waterborne bonding layer sizing agent with the viscosities of 4000cps and 6000cps respectively;
3) preparing a finished product by a release paper transfer film method:
fifthly, unreeling release paper; then the step (c) and the step (c) are carried out to obtain the water-based noodlesThe layer slurry, the aqueous middle layer slurry and the aqueous bonding layer slurry are all coated according to the coating weight of 110g/m2Sequentially coating on release paper; the surface layer slurry and the middle layer slurry are dried for the first time after being coated, and the water-based bonding layer slurry can be wet-bonded or semi-dry-bonded with the water-based polyurethane base after being coated;
and sixthly, stripping the release paper, and then printing and embossing to obtain the finished product of the high-physical-property waterborne polyurethane synthetic leather.
Example 2
A preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes comprises the following steps:
1) preparing the waterborne polyurethane base by an acid/salt solidification process:
firstly, taking aqueous polyurethane resin with solid content of 45%, adding 0.4% of calcium powder dispersant, 50% of filler calcium powder, 1.4% of anti-cracking agent, 6% of foaming agent, 6% of foam stabilizer, 0.7% of isocyanate crosslinking agent and 0.6% of thickening agent according to the weight percentage of the aqueous polyurethane resin, and uniformly mixing and defoaming to obtain wet process slurry with viscosity of 22000cps for later use;
secondly, the woven fabric is dried after being treated by 1.2 percent oxalic acid aqueous solution, the wet slurry obtained in the first step is coated on the surface of the woven fabric for foaming by utilizing a waterborne polyurethane foaming machine, and the coating amount is 500g/m2Controlling the foaming density to be 0.70, then solidifying and washing in 1.5% tartaric acid/potassium chloride aqueous solution (by weight, 1.5 parts of tartaric acid and 1.5 parts of potassium chloride are dissolved in 100 parts of water and uniformly stirred), drying and rolling in different temperature regions with the temperature range of 80-170 ℃ and the temperature interval of 5-10 ℃ to obtain the waterborne polyurethane base for later use;
2) preparing a dry-process semi-finished product of the waterborne polyurethane:
③ the surface layer resin is waterborne polyurethane resin copolymerized by polyether and polycarbonate with the solid content of 30 percent and the modulus of 100 percent and the pressure of 5MPa, 0.7 percent of flatting agent, 8 percent of pigment, 0.7 percent of isocyanate cross-linking agent and 0.8 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is evenly mixed to obtain waterborne surface layer slurry with the viscosity of 4000 cps;
fourthly, the middle layer and the bonding layer are polyether type waterborne polyurethane resin with the solid content of 42 percent and the modulus of 100 percent of 3MPa, 0.7 percent of flatting agent, 8 percent of pigment and 0.8 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is uniformly mixed to obtain waterborne middle layer and waterborne bonding layer sizing agent with the viscosities of 4500cps and 6500cps respectively;
3) preparing a finished product by a release paper transfer film method:
fifthly, unreeling release paper; then the water-based surface layer sizing agent, the water-based middle layer sizing agent and the water-based bonding layer sizing agent in the third step and the fourth step are all coated according to the coating weight of 100g/m2Sequentially coating on release paper; the surface layer slurry and the middle layer slurry are dried for the first time after being coated, and the water-based bonding layer slurry can be wet-bonded or semi-dry-bonded with the water-based polyurethane base after being coated;
and sixthly, stripping the release paper, and then printing and embossing to obtain the finished product of the high-physical-property waterborne polyurethane synthetic leather.
The samples made in examples 1 and 2 were tested for abrasion resistance, peel and flex performance and the results are shown in table 1:
TABLE 1
Wherein the test standard for stripping is SA TRA TM 410;
the flexural test standard is ISO 5402-1.
According to the data in the table 1, the waterborne polyurethane synthetic leather manufactured by the invention has good wear resistance and good flexing resistance, particularly low-temperature flexing resistance, and meets the requirement of winter shaping shoes on weather resistance, particularly high low-temperature resistance.
The above-described embodiments are only preferred embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made by one skilled in the art, and any modification, equivalent replacement, and improvement made without departing from the spirit and principles of the invention should be included in the scope of the invention.
Claims (10)
1. A preparation method of high-physical-property waterborne polyurethane synthetic leather for low-temperature-resistant zigzag shaped shoes is characterized by comprising the following steps:
1) preparing the waterborne polyurethane base by an acid/salt solidification process:
firstly, taking aqueous polyurethane resin with solid content of 45-55%, adding 0.1-0.5% of calcium powder dispersant, 30-60% of calcium powder, 0.5-2.0% of anti-cracking agent, 1-10% of foaming agent, 1-10% of foam stabilizer, 0.2-1.0% of isocyanate cross-linking agent and 0.2-1.0% of thickening agent according to the weight percentage of the aqueous polyurethane resin, and uniformly mixing and defoaming to obtain wet-process slurry for later use;
secondly, the fabric is dried after being treated by 0.5 to 2.0 percent of oxalic acid/tartaric acid water solution, the wet slurry obtained in the step I is coated on the surface of the fabric for foaming by utilizing a waterborne polyurethane foaming machine, the foaming density is controlled to be 0.65 to 0.80, and then the fabric is solidified and washed by 0.5 to 3.0 percent of acid/salt water solution, and the fabric is dried and rolled by different temperature areas to obtain waterborne polyurethane base for later use;
2) preparing a dry-process semi-finished product of the waterborne polyurethane:
thirdly, the surface layer resin is water-based polyurethane resin copolymerized or mixed by polyether and polycarbonate, 0.2 to 1.0 percent of flatting agent, 2 to 10 percent of pigment, 0.2 to 1.0 percent of isocyanate cross-linking agent and 0.2 to 1.0 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is uniformly mixed to obtain water-based surface layer slurry;
fourthly, the middle layer and the bonding layer are polyether type waterborne polyurethane resin, 0.2 to 1.0 percent of flatting agent, 2 to 10 percent of pigment and 0.2 to 1.0 percent of thickening agent are added according to the weight percentage of the resin, and the mixture is uniformly mixed to obtain waterborne middle layer slurry and waterborne bonding layer slurry;
3) preparing a finished product by a release paper transfer film method:
fifthly, unreeling release paper; then coating the water-based surface layer slurry, the water-based middle layer slurry and the water-based bonding layer slurry on release paper in sequence; finally, the waterborne polyurethane base is attached to the bonding layer coated by the release paper, and the bonding layer is dried and cooled;
and sixthly, stripping the release paper, and then printing and embossing to obtain the high-physical-property waterborne polyurethane synthetic leather.
2. The method for preparing the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes as claimed in claim 1, wherein the viscosity of the wet slurry is 10000-30000cps, and the coating amount of the wet slurry coating operation is 400-800g/m2。
3. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes according to claim 1, wherein the fabric obtained in the step (II) is woven fabric, knitted fabric or non-woven fabric, the elongation at break of the 45-degree angle cut strip is 50% -90%, and the back side has a hairless or micro-hairless state.
4. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes according to claim 1, wherein the temperature range of the different temperature zones is 80-170 ℃, and the temperature interval is 5-10 ℃.
5. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes according to claim 1, wherein the solid content of the waterborne polyurethane resin copolymerized or mixed with the polyether and the polycarbonate is 28% -35%, and the 100% modulus is 4-6 MPa.
6. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes according to claim 1, wherein the solid content of the polyether waterborne polyurethane resin in the step (iv) is 40-50%, and the 100% modulus is 2-4 MPa.
7. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes as claimed in claim 1, wherein the viscosity of the waterborne surface layer slurry is 2000-5000 cps.
8. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoe as claimed in claim 1, wherein the viscosity of the aqueous middle layer slurry and the viscosity of the aqueous bonding layer slurry are 2000-5000cps and 4000-8000cps respectively.
9. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes according to claim 1, wherein the coating weights of the waterborne surface layer slurry, the waterborne middle layer slurry and the waterborne bonding layer slurry in the step (v) are all 60-150g/m2。
10. The preparation method of the high-physical-property waterborne polyurethane synthetic leather for the low-temperature-resistant zigzag shaped shoes according to claim 1, wherein the step (v) is to dry the waterborne surface layer slurry and the waterborne middle layer slurry after coating, and the waterborne bonding layer slurry can be bonded with waterborne polyurethane base wet or semi-dry after coating.
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| WO2023149799A1 (en) | 2022-02-03 | 2023-08-10 | Stahl International B.V. | Process for preparing a multi-layered composite suitable for making polyurethane synthetic leather |
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