CN115613369A - Heat-resistant polyurethane shoe upper coating, heat-resistant polyurethane coating shoe upper and preparation method thereof - Google Patents
Heat-resistant polyurethane shoe upper coating, heat-resistant polyurethane coating shoe upper and preparation method thereof Download PDFInfo
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- CN115613369A CN115613369A CN202211286838.2A CN202211286838A CN115613369A CN 115613369 A CN115613369 A CN 115613369A CN 202211286838 A CN202211286838 A CN 202211286838A CN 115613369 A CN115613369 A CN 115613369A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 57
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000007639 printing Methods 0.000 claims abstract description 59
- 238000007650 screen-printing Methods 0.000 claims abstract description 42
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 21
- 238000007731 hot pressing Methods 0.000 claims description 19
- 239000000080 wetting agent Substances 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 238000007603 infrared drying Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000005452 bending Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
- D06N2211/106—Footwear
Abstract
The invention relates to a heat-pressure resistant polyurethane shoe upper coating which comprises the following components in percentage by mass: 70-85% of waterborne polyurethane, 5-10% of end-capping crosslinking agent, 4-8% of fumed silica and 5-15% of water-based auxiliary agent. A heat and pressure resistant polyurethane coated vamp and a preparation method thereof comprise the following steps: pretreatment, primary printing, secondary printing and hot-press molding. Different from the prior art, the whole-face plate and screen printing are combined, so that the polyurethane coating is firmly adhered to the whole vamp material and a polyurethane plane is formed, and the multi-path screen printing is to perform screen printing on a polyurethane coating formed by the whole-face plate, and the preset part presents a pattern with certain thickness. Meanwhile, the formed coating film is tougher and has the property of being not easy to deform at high temperature.
Description
Technical Field
The invention relates to the field of shoe preparation, in particular to a heat-pressing-resistant polyurethane shoe upper coating, a heat-pressing-resistant polyurethane coating shoe upper and a preparation method thereof.
Background
At present, in the preparation of shoes, the shoe materials are usually pretreated by using aqueous PU slurry and then formed by adopting a TPU hot pressing process, and the TPU hot pressing can increase the strength and toughness of the vamp, increase the wear resistance and the waterproofness and the like. However, in the production process, due to the nature of the slurry, the hot pressing temperature exceeding 150 ℃ easily causes the hot pressing deformation of the slurry coating, and the conditions of coating melting, coating deformation or coating hardening can occur. Meanwhile, the screen surface is adopted to print the polyurethane coating pattern, and because the polyurethane coating is a convex part with a certain thickness, the conditions of peeling and cracking of the coating edge and falling off from the screen surface frequently occur in the subsequent use process.
Disclosure of Invention
In view of the above, the present application provides a heat-resistant polyurethane upper coating, a heat-resistant polyurethane coated upper, and a method of making the same. The polyurethane shoe-coating material can be used at 165 ℃ and 20Kg/cm 2 After 180s under the pressure of (2), the coating layer can not be deformed, melted or over-hardened, and the thickness of the coating layer is kept above 90%. The vamp is soft and has high bending resistance, and the polyurethane coating is not easy to fall off.
The invention provides a heat and pressure resistant polyurethane coating in a first aspect, and the heat and pressure resistant polyurethane coating comprises the following components in percentage by mass: 70-85% of waterborne polyurethane, 5-10% of end-capping crosslinking agent, 4-8% of fumed silica and 5-15% of water-based auxiliary agent.
Compared with the prior art, the heat-compression-resistant polyurethane coating provided by the technical scheme contains the end-capping crosslinking agent, and the addition of the end-capping crosslinking agent improves the reactivity and the thermal stability of the polyurethane coating at high temperature, promotes the crosslinking of the polyurethane coating at high temperature, so that the formed coating is tougher and has the property of difficult deformation at high temperature.
In certain embodiments, the aqueous adjuvant comprises the following components in parts by mass: 1-5 parts of water-based wetting agent, 1-5 parts of water-based defoaming agent and 1-5 parts of flatting agent.
The invention provides a printing method of a heat-resistant polyurethane coating vamp, which comprises the following steps:
pretreatment: adding 5-10 wt% of deblocking agent into the heat-pressure resistant polyurethane coating to obtain working slurry;
printing for the first time: printing working slurry on the mesh cloth by using a whole face plate and then drying;
and (3) secondary printing: performing multiple screen printing on a preset part on the dried primary printing coating by using a screen printing plate, and drying each screen printing plate after printing;
hot-press molding: and carrying out hot pressing on the vamp subjected to secondary printing and drying to obtain the vamp with the thickness of the heat-resistant polyurethane coating at the preset part being 0.7-1.2 mm.
In research and development, the polyurethane patterns are directly printed on the mesh cloth by using the screen printing plate in the prior art, and the material of the mesh cloth and the difference of polyurethane are large, so that the edge of a raised heat-resistant polyurethane coating has a large-angle water drop angle, and the edge is easily torn in the later use process.
Different from the prior art, the printing method of the heat-resistant polyurethane coating vamp, which is provided by the technical scheme, combines the whole-face plate and the screen printing, the whole-face plate is adopted to enable the polyurethane coating to be firmly adhered to the whole vamp material and form a polyurethane plane, the multi-channel screen printing is to perform the screen printing on the polyurethane coating formed by the whole-face plate, the preset part presents a pattern with a certain thickness, and the design enables the connection of the protruded polyurethane pattern and the vamp to be firmer. Meanwhile, the coating contains the end-capping crosslinking agent, so that the reactivity and the thermal stability of the polyurethane coating at high temperature are improved by adding the end-capping crosslinking agent, the crosslinking of the polyurethane coating in the final hot-press forming step is promoted, and the formed coating is tougher and has the property of difficult deformation at high temperature.
In some embodiments, in the first printing step, the drying is performed by drying in a treadmill dryer, the temperature of the dryer is set to be 50-80 ℃, and the movement speed of the dryer is 100-200mm/s.
In some embodiments, in the secondary printing step, infrared drying is adopted for drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min.
In some embodiments, in the second printing step, the mesh number of the screen printing plate is 60 meshes.
In some embodiments, the hot-press forming step is carried out at a hot-press temperature of 160-165 ℃ and a pressure of 15-20Kg/cm 2 。
In certain embodiments, the operation time of the first printing, the second printing and the hot press molding is controlled to be 2-4h.
In a third aspect, the invention provides a heat-resistant polyurethane-coated vamp, which is prepared by the method of the second aspect of the invention.
Different from the prior art, the heat-resistant polyurethane coating vamp provided by the technical scheme is prepared by adopting the process of combining the whole-face plate and the screen printing, the whole-face plate is adopted to enable the polyurethane coating to be firmly adhered to the whole vamp material and form a polyurethane plane, the multi-channel screen printing is to perform the screen printing on the polyurethane coating formed by the whole-face plate, the preset part presents a pattern with a certain thickness, and the design enables the preset pattern to be more firmly connected with the vamp. Meanwhile, the coating contains the end-capping crosslinking agent, so that the reactivity and the thermal stability of the polyurethane coating at high temperature are improved by adding the end-capping crosslinking agent, the crosslinking of the polyurethane coating in the final hot press forming step is promoted, and a formed coating is tougher and has the property of difficult deformation at high temperature.
In some embodiments, the number of bending times of the heat and pressure resistant polyurethane coating vamp is more than or equal to 50000 times.
The above description of the present invention is only an outline of the technical solution of the present application, and in order to make the technical solution of the present application more clearly understood by those skilled in the art, the present invention may be implemented based on the content of the text of the specification, and in order to make the above object and other objects, features, and advantages of the present application more easily understood, the following description will be given in conjunction with the detailed description of the present application.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
In order to explain in detail the possible application scenarios, technical principles, practical embodiments, and the like, the following detailed description is given with reference to the specific embodiments. The embodiments described herein are merely for more clearly illustrating the technical solutions of the present application, and therefore, the embodiments are only used as examples, and the scope of the present application is not limited thereby.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or related to other embodiments specifically defined. In principle, in the present application, the technical features mentioned in the embodiments can be combined in any manner to form a corresponding implementable technical solution as long as there is no technical contradiction or conflict.
Unless defined otherwise, technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the use of relational terms herein is intended only to describe particular embodiments and is not intended to limit the present application.
In the description of the present application, the term "and/or" is a expression for describing a logical relationship between objects, indicating that three relationships may exist, for example, a and/or B, indicating that: there are three cases of A, B, and both A and B. In addition, the character "/" herein generally indicates that the former and latter associated objects are in a logical relationship of "or".
In this application, terms such as "first" and "second" are used merely to distinguish one entity or operation from another entity or operation without necessarily requiring or implying any actual such relationship or order between such entities or operations.
Without further limitation, in this application, the use of "including," "comprising," "having," or other similar expressions in phrases and expressions of "including," "comprising," or "having," is intended to cover a non-exclusive inclusion, and such expressions do not exclude the presence of additional elements in a process, method, or article that includes the recited elements, such that a process, method, or article that includes a list of elements may include not only those elements but also other elements not expressly listed or inherent to such process, method, or article.
As is understood in the "review guidelines," in this application, the terms "greater than," "less than," "more than," and the like are to be understood as excluding the number; the expressions "above", "below", "within" and the like are understood to include the present numbers. In addition, in the description of the embodiments of the present application, "a plurality" means two or more (including two), and expressions related to "a plurality" similar thereto are also understood, for example, "a plurality of groups", "a plurality of times", and the like, unless specifically defined otherwise.
In the application, the blocked cross-linking agent is a blocked water-dispersible polyisocyanate curing agent, and the blocked water-dispersible polyisocyanate curing agent can be matched with a matched deblocking agent to obtain the polyisocyanate curing agent under the condition of high temperature. Generally, phenol, methanol, ethanol, acetone oxime, caprolactam, sodium bisulfite and the like are adopted to seal NCO groups of isocyanate curing agents to obtain closed isocyanate curing agents, and the NCO groups are deblocked after a deblocking agent is added under the condition of heating.
In the present application, the deblocking agent is a polyol, preferably propylene glycol.
In the present embodiment, a cyclic or branched isocyanate curing agent is preferably contained. The cyclic structural unit or the branched structure can form a higher crosslinking density structure with the polyurethane, so that the effect of resisting the heat pressure is further enhanced. Under the action of high temperature, the blocked isocyanate deblocking agent is matched with the deblocking agent, NCO groups are deblocked and are linked with polyurethane hydroxyl to form high-density crosslinking reaction, and the effect of heat pressure resistance is enhanced.
The application adopts a closed isocyanate curing agent, so that the formation of working slurry and the curing starting time can be controlled. The production problems that the isocyanate curing agent is directly added in the batching process, so that the working slurry forms a cured high-density cross-linked structure when being printed, the printing effect is influenced, and the screen printing plate is blocked are solved.
The invention provides a heat and pressure resistant polyurethane coating in a first aspect, and the heat and pressure resistant polyurethane coating comprises the following components in percentage by mass: 70-85% of waterborne polyurethane, 5-10% of end-capping crosslinking agent, 4-8% of fumed silica and 5-15% of water-based auxiliary agent.
Compared with the prior art, the heat-compression-resistant polyurethane coating provided by the technical scheme contains the end-capping crosslinking agent, and the addition of the end-capping crosslinking agent improves the reactivity and the thermal stability of the polyurethane coating at high temperature, promotes the crosslinking of the polyurethane coating at high temperature, so that the formed coating is tougher and has the property of difficult deformation at high temperature.
In certain embodiments, the mass ratio of the aqueous polyurethane to the blocked crosslinker is from 70 to 80:4-5. In research and development, the heat and pressure resistance is improved along with the increase of the end-capping crosslinking agent, but after the addition amount of the end-capping crosslinking agent reaches a certain value, the heat and pressure resistance is not obviously improved, and the effective construction time of the working fluid is shortened. Therefore, the amount of the end-capping crosslinking agent to be charged is controlled.
In certain embodiments, the mass ratio of the aqueous polyurethane to fumed silica is from 70 to 80. The silicon dioxide is added for modification, so that the temperature resistance of the coating can be improved, the surface of the prepared coating is better in dryness and softness, and the bending resistance is improved. An excessive amount of silica causes hardening of the coating film, and thus the amount thereof is controlled.
In certain embodiments, the aqueous adjuvant comprises the following components in parts by mass: 1-5 parts of water-based wetting agent, 1-5 parts of water-based defoaming agent and 1-5 parts of flatting agent.
The invention provides a printing method of a heat-resistant polyurethane coating vamp, which comprises the following steps:
pretreatment: adding 5-10 wt% of deblocking agent into the heat-pressure resistant polyurethane coating to obtain working slurry;
printing for the first time: printing working slurry on the mesh cloth by using a whole face plate and then drying;
and (3) secondary printing: performing multiple screen printing on a preset part on the dried primary printing coating by using a screen printing plate, and drying each screen printing plate after printing;
hot-press molding: and carrying out hot pressing on the vamp subjected to the secondary printing to obtain the vamp with the thickness of the heat-resistant polyurethane coating at the preset part being 0.7-1.2 mm.
The inventor finds that in the prior art, a screen printing plate is directly used for printing a polyurethane pattern on a mesh cloth, and due to the fact that the difference between materials of the mesh cloth and polyurethane is large, the edge of a raised heat-resistant polyurethane coating layer has a large-angle water drop angle, and the edge is prone to tearing in the later use process.
Different from the prior art, the printing method of the heat-resistant polyurethane coating vamp provided by the technical scheme combines full-face printing and screen printing, and the full-face printing is adopted to ensure that the polyurethane coating is firmly adhered to the whole vamp material and a polyurethane plane is formed; and the multi-pass screen printing is to perform screen printing on the polyurethane coating formed on the whole surface plate so that the preset part presents a pattern with a certain thickness. The process enables the polyurethane coating to be connected with the vamp more firmly. Meanwhile, the coating contains the end-capping crosslinking agent, so that the reactivity and the thermal stability of the polyurethane coating at high temperature are improved by adding the end-capping crosslinking agent, the crosslinking of the polyurethane coating in the final hot-press forming step is promoted, and the formed coating is tougher and quickly formed and has the property of difficult deformation at high temperature.
In some embodiments, in the first printing step, the drying is performed by drying in a treadmill dryer, the temperature of the dryer is set to be 50-80 ℃, and the movement speed of the dryer is 100-200mm/s.
In some embodiments, in the secondary printing step, infrared drying is adopted for drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min.
The first printing and the second printing steps adopt a drying mode with a relatively low temperature below 80 ℃, so that the heat-resistant polyurethane printed at each time is not cured, and only a relatively stable coating film is formed, so that the polyurethane covered in the next procedure can be superposed on the surface of the heat-resistant polyurethane and can reach a certain thickness.
In some embodiments, in the second printing step, the mesh number of the screen printing plate is 60 meshes. The mesh number of the screen is selected in relation to the viscosity of the working fluid and the molecular weight of the components it contains.
In some embodiments, the hot-press forming step is carried out at a hot-press temperature of 160-165 ℃ and a pressure of 15-20Kg/cm 2 And high-temperature rapid hot-press molding can be realized. In the prior art, due to the nature of slurry, the hot pressing temperature can only reach 130 ℃ generally, and the hot pressing pressure is 5Kg/cm 2 This results in a relatively long thermoforming time for the upper, which is likely to deform the polyurethane coating.
In certain embodiments, the operation time of the first printing, the second printing and the hot press molding is controlled to be 2 to 4 hours. Because the working fluid is added with the deblocking agent, the operation time needs to be controlled.
In a third aspect, the invention provides a heat-resistant polyurethane-coated vamp, which is prepared by the method of the second aspect of the invention.
Different from the prior art, the heat-resistant polyurethane coating vamp provided by the technical scheme is prepared by adopting the process of combining the whole-face plate and the screen printing, the whole-face plate is adopted to enable the polyurethane coating to be firmly adhered to the whole vamp material and form a polyurethane plane, the multi-channel screen printing is to perform the screen printing on the polyurethane coating formed by the whole-face plate, the preset part presents a pattern with a certain thickness, and the design enables the preset pattern to be more firmly connected with the vamp. Meanwhile, the coating contains the end-capping crosslinking agent, so that the reactivity and the thermal stability of the polyurethane coating at high temperature are improved by adding the end-capping crosslinking agent, the crosslinking of the polyurethane coating in the final hot-press forming step is promoted, and the formed coating is tougher and has the property of difficult deformation at high temperature.
In some embodiments, the heat and pressure resistant polyurethane coated upper has a number of bends of 50000 or more. As the process combines the whole plate and screen printing, the stress of the local bending area can be effectively decomposed and transferred to the whole vamp area, and the phenomenon that the local stress is too large to cause fracture is avoided.
Finally, it should be noted that, although the above embodiments have been described in the text of the specification of the present application, the scope of the patent protection of the present application is not limited thereby. All technical solutions which are generated by replacing or modifying the equivalent structure or the equivalent flow according to the content described in the specification of the present application based on the substantial idea of the present application, and which directly or indirectly implement the technical solutions of the above embodiments in other related technical fields, are included in the scope of patent protection of the present application.
In the embodiment, the modified waterborne polyurethane Kostew 1554 is selected, and the resin is formed by modifying waterborne polyurethane in the traditional shoe sizing agent.
In this embodiment, the selected end-capping crosslinking agent Imprafix 2794 is used as a (yellowing) crosslinking agent for improving reactivity and thermal stability, and the end-capping crosslinking agent is deblocked at a high temperature and can be added simultaneously when the slurry is prepared.
In the embodiment, the selected water-based wetting agent is BYK-346, the chemical component of the water-based wetting agent is polyether modified polydimethylsiloxane solution, and the water-based wetting agent is an organosilicon surfactant for a water-based system, so that the surface tension is strongly reduced, and the substrate wetting performance is obviously improved.
In the embodiment, the selected water-based defoamer is digao 825, which is an organic silicon defoamer and does not contain VOC, and the assistant has good defoaming performance and does not influence transparency.
In the present embodiment, the silica is a product of Degussa corporation model number A200, and the specific surface area is 200 + -25 m 2 The product has a primary particle size of 12nm, is hydrophilic fumed silica, and has the characteristics of good dispersibility, good thickening effect, high transparency, good weather resistance and the like.
In this embodiment, the screen printing plate needs to be cleaned after each printing process.
In this embodiment, the preparation of the polyurethane shoe upper coating with heat and pressure resistance comprises the following steps: adding waterborne polyurethane, a terminated cross-linking agent, fumed silica and a waterborne auxiliary agent into a dispersion cylinder according to a proportion, and dispersing by using a high-speed dispersion machine; and grinding the dispersed slurry by a three-roller grinder, and then subpackaging and discharging.
In the embodiment, the aqueous auxiliary agent is prepared from the following components in parts by mass: 5 parts of water-based wetting agent, 5 parts of water-based defoaming agent and 5 parts of flatting agent.
Example 1:
preparing a coating: adding 80% of modified waterborne polyurethane (Corsai Chun 1554), 5% of end-capping cross-linking agent (Imprafix 2794), 5% of fumed silica (Degussa company A200) and 10% of waterborne auxiliary agent (5 parts by mass of waterborne wetting agent, 5 parts by mass of waterborne defoaming agent and 5 parts by mass of leveling agent) into a dispersion cylinder according to the proportion, and dispersing by using a high-speed dispersion machine; grinding the dispersed slurry by a three-roller grinder, subpackaging and discharging to obtain the heat-pressing-resistant polyurethane shoe surface coating;
pretreatment: adding 5wt% of a propylene glycol deblocking agent into the heat-resistant polyurethane shoe surface coating, and uniformly stirring to obtain working slurry;
printing for the first time: printing paste on the mesh cloth by adopting a whole-face plate, and drying; drying is carried out by adopting a running platform dryer, the set temperature of the dryer is 70 ℃, and the movement speed of the dryer is 200mm/s
And (3) secondary printing: 5 steps of screen printing are carried out on a preset position by adopting a screen, and drying is carried out after each step of screen printing; the drying adopts infrared drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min;
hot-press molding: hot pressing the vamp printed and dried for the second time at 165 deg.C under 20Kg/cm 2 Hot pressing time 45s, the vamp of example 1 was obtained.
Example 2:
preparing a coating: adding 75% of waterborne polyurethane (Koska 1554), 10% of a terminated cross-linking agent (Imprafix 2794), 5% of fumed silica (Degussa A200) and 10% of a waterborne auxiliary agent (5 parts by mass of a waterborne wetting agent, 5 parts by mass of a waterborne defoaming agent and 5 parts by mass of a flatting agent) into a dispersion cylinder according to a proportion, and dispersing by using a high-speed dispersion machine; grinding the dispersed slurry by a three-roller grinder, and then subpackaging and discharging to obtain the heat-pressing-resistant polyurethane shoe surface coating
Pretreatment: adding 10wt% of a propylene glycol deblocking agent into the heat-resistant polyurethane shoe surface coating, and uniformly stirring to obtain working slurry;
printing for the first time: printing paste on the mesh cloth by adopting a whole-face plate, and drying; drying is carried out by adopting a running platform dryer, the set temperature of the dryer is 70 ℃, and the movement speed of the dryer is 200mm/s
And (3) secondary printing: 5 times of screen printing is carried out on a preset part by adopting a screen printing plate, and drying is carried out after each time of screen printing; the drying adopts infrared drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min;
hot-press molding: hot pressing the vamp printed and dried for the second time at 165 deg.C under 20Kg/cm 2 Hot pressing time 45s, the vamp of example 2 was obtained.
Example 3
Preparing a coating: adding 80% of waterborne polyurethane (40% of Coxichu 1554 and 40% of Heben 339A), 5% of a terminated cross-linking agent (Imprafix 2794), 5% of fumed silica (Degussa A200) and 10% of a waterborne auxiliary agent (5 parts by mass of a waterborne wetting agent, 5 parts by mass of a waterborne defoaming agent and 5 parts by mass of a flatting agent) into a dispersing cylinder according to a proportion, and dispersing by using a high-speed dispersing machine; grinding the dispersed slurry by a three-roller grinder, and then subpackaging and discharging to obtain the heat-pressing-resistant polyurethane shoe surface coating
Pretreatment: adding 5wt% of a propylene glycol deblocking agent into the heat-resistant polyurethane shoe surface coating, and uniformly stirring to obtain working slurry;
printing for the first time: printing paste on the mesh by adopting a full-face plate, and drying; the drying is carried out by adopting a running platform dryer, the set temperature of the dryer is 70 ℃, and the movement speed of the dryer is 200mm/s
And (3) secondary printing: 5 times of screen printing is carried out on a preset part by adopting a screen printing plate, and drying is carried out after each time of screen printing; the drying adopts infrared drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min;
hot-press molding: hot pressing the vamp after the secondary printing and dryingThe hot pressing temperature is 165 ℃ and the pressure is 20Kg/cm 2 Hot pressing time 45s, example 3 vamp was obtained.
Example 4
Preparing a coating: adding 80% of waterborne polyurethane (Heben 339A), 5% of end-capping cross-linking agent (Imprafix 2794), 5% of fumed silica (Degussa company A200) and 10% of waterborne auxiliary agent (5 parts by mass of waterborne wetting agent, 5 parts by mass of waterborne defoaming agent and 5 parts by mass of leveling agent) into a dispersion cylinder according to the proportion, and dispersing by using a high-speed disperser; the dispersed slurry is subjected to after-grinding by a three-roller grinding machine and then is subpackaged and discharged to obtain the polyurethane shoe upper coating with heat and pressure resistance
Pretreatment: adding 5wt% of a propylene glycol deblocking agent into the heat-resistant polyurethane shoe surface coating, and uniformly stirring to obtain working slurry;
printing for the first time: printing paste on the mesh cloth by adopting a whole-face plate, and drying; drying is carried out by adopting a running platform dryer, the set temperature of the dryer is 70 ℃, and the movement speed of the dryer is 200mm/s
And (3) secondary printing: 5 steps of screen printing are carried out on a preset position by adopting a screen, and drying is carried out after each step of screen printing; the drying adopts infrared drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min;
hot-press molding: hot pressing the vamp printed and dried for the second time at 165 deg.C under 20Kg/cm 2 Hot pressing for 45s to obtain the vamp of example 4.
The performance tests of the hot press resistant polyurethane shoe upper coating and shoe upper prepared in examples 1-4 were carried out, and the test items and test results are shown in the following table 1:
table 1 examples 1-4 table of test results
(Heat and pressure resistance test shows that the thickness is compared before and after the hot pressing step.)
As can be seen from examples 1-4, the type of the aqueous polyurethane and the amount of the blocked crosslinking agent added affect the heat and pressure resistance of the coated shoe upper and the working time of the working fluid. In this embodiment, the preferable waterborne polyurethane is koshichu 1554 modified waterborne polyurethane, the end-capping crosslinking agent is Imprafix 2794, and the mass ratio of the waterborne polyurethane to the end-capping crosslinking agent is preferably 80.
Claims (10)
1. The heat-pressing-resistant polyurethane shoe upper coating is characterized by comprising the following components in percentage by mass: 70-85% of waterborne polyurethane, 5-10% of end-capping crosslinking agent, 4-8% of fumed silica and 5-15% of water-based auxiliary agent.
2. The coating according to claim 1, wherein the aqueous auxiliary agent comprises the following components in parts by mass: 1-5 parts of water-based wetting agent, 1-5 parts of water-based defoaming agent and 1-5 parts of flatting agent.
3. A preparation method of a heat and pressure resistant polyurethane coating vamp is characterized by comprising the following steps: pretreatment: adding 5-10 wt% of deblocking agent into the polyurethane shoe upper coating material of claim 1 or 2, and uniformly stirring to obtain working slurry;
printing for the first time: printing working slurry on the mesh cloth by using a whole face plate and then drying;
and (3) secondary printing: performing multiple screen printing on a preset part on the dried first printing coating by using a screen printing plate, and drying each screen printing plate after printing;
hot-press molding: and carrying out hot pressing on the vamp subjected to the secondary printing to obtain the vamp with the preset part of the heat-resistant polyurethane coating with the thickness of 0.7-1.2 mm.
4. The method according to claim 3, wherein the first printing step, drying, is performed by drying with a treadmill dryer, the temperature of the dryer is set to 50-80 ℃, and the moving speed of the dryer is 100-200mm/s.
5. The method as claimed in claim 3, wherein in the secondary printing step, infrared drying is adopted for drying, the drying temperature is 60-70 ℃, and the drying speed is more than or equal to 80M/min.
6. The method of claim 3, wherein in the second printing step, the mesh number of the screen printing plate is 60 meshes.
7. The method as claimed in claim 3, wherein the hot press molding step is carried out at a hot press temperature of 160 to 165 ℃ and a pressure of 15 to 20Kg/cm 2 。
8. The method according to claim 3, wherein the operation time of the primary printing, the secondary printing and the hot press forming steps is controlled in a total of 2-4 hours.
9. A heat and pressure resistant polyurethane coated shoe upper, characterized in that it is produced by a method according to any one of claims 3 to 8.
10. The shoe upper according to claim 9, characterized in that the number of bending times of the heat and pressure resistant polyurethane coated shoe upper is more than or equal to 50000.
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| US5552496A (en) * | 1992-08-27 | 1996-09-03 | Herberts Gesellschaft Mit Beschrankter Haftung | Aqueous polyurethane resin dispersion, processes for its preparation, and its use in aqueous coating compositions |
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