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CN-122013553-A - Application of self-hydrophobic mildew-proof modified leather in shoe material and preparation process thereof

CN122013553ACN 122013553 ACN122013553 ACN 122013553ACN-122013553-A

Abstract

The invention discloses a self-hydrophobic mildew-proof modified leather material and a preparation process thereof, wherein the self-hydrophobic mildew-proof modified leather material is prepared by coating, curing and attaching a base cloth to modified polyurethane slurry, wherein the slurry comprises a bio-based single-component polyurethane resin solution, amphiphilic functional carrier liquid, biomass waste functional filler, a latent metal crosslinked prefabricated liquid and an organic solvent, and the latent metal crosslinked prefabricated liquid is used for shielding metal ion activity by utilizing a volatile amine ligand, so that the slurry is effectively prevented from gelling in the storage period. The preparation process includes coating the slurry to form wet film, heating to cure, inducing the amphiphilic carrier to carry stuffing to migrate to the surface for enrichment with the high boiling point solvent volatilizing gradient in low temperature stage, and the ligand volatilizing to release metal ion to form in-situ coordination cross-linking with the surface polyphenol and siloxane. The invention constructs a firm surface metal-organic micro-nano structure, solves the problem that biomass filler is easy to fall off, and remarkably improves the hydrophobic, wear-resistant and mildew-proof performances of the material.

Inventors

  • ZHAO LAN
  • WANG YUYAN
  • WANG XIANGJUN

Assignees

  • 广东爱森林新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260324

Claims (10)

  1. 1. The self-hydrophobic mildew-proof modified element leather material is characterized by being prepared from modified polyurethane slurry through coating, curing and attaching to base cloth, wherein the modified polyurethane slurry is prepared from the following raw materials in parts by weight: 100.0 parts of bio-based single-component polyurethane resin solution; 4.0-10.0 parts of amphiphilic functional carrier liquid; 3.0-10.0 parts of biomass waste functional filler; 2.0-5.0 parts of latent metal crosslinking prefabricated liquid; an organic solvent for adjusting the viscosity.
  2. 2. The self-hydrophobic mildew-resistant modified element leather material according to claim 1, wherein the latent metal cross-linking preformed liquid is prepared from raw materials comprising metal salts, volatile amine ligands and alcohol solvents; wherein the molar ratio of the metal salt to the volatile amine ligand is 1 (2.0-6.5).
  3. 3. The self-hydrophobic mildew-resistant modified plain leather material according to claim 1, wherein the amphiphilic functional transport carrier fluid is prepared by dispersing raw materials comprising a plant polyphenol extract, a side chain amino modified polysiloxane and a high boiling point cosolvent; Wherein the mass ratio of the plant polyphenol extract to the side chain amino modified polysiloxane to the high boiling point cosolvent is (1.0-2.0) (1.5-3.0) (3.0-5.0).
  4. 4. A self-hydrophobic mildew-resistant modified cellulose leather material according to any of claims 1 to 3, wherein the specific selection of the raw materials comprises: The solid content of the bio-based single-component polyurethane resin solution is 30% +/-2%; the biomass waste functional filler is selected from modified coffee grounds micro powder, bagasse nanocellulose or tea grounds micro powder; the metal salt is selected from anhydrous zinc acetate or anhydrous ferric trichloride; the volatile amine ligand is selected from ethylenediamine or n-butylamine; the plant polyphenol extract is selected from tea polyphenol, citrus peel extract or tannic acid; The high boiling point cosolvent is selected from dipropylene glycol methyl ether or ethylene glycol monobutyl ether, and the boiling point of the high boiling point cosolvent is higher than the boiling point of the volatile amine ligand.
  5. 5. The process for preparing the self-hydrophobic mildew-proof modified element leather material according to claim 1, which is characterized by comprising the following steps: S1, preparing modified slurry, namely adding the amphiphilic functional conveying carrier liquid into a single-component polyurethane resin solution for uniform dispersion, then adding the biomass waste functional filler for dispersion until no granular feel, then adding the latent metal cross-linking prefabricated liquid, adding an organic solvent for viscosity adjustment and defoaming to obtain modified polyurethane slurry; S2, coating, namely coating the modified polyurethane slurry obtained in the step S1 on pattern release paper to form a wet film; s3, programmed heating and curing, namely heating and drying the release paper coated with the wet film in the step S2 in a staged manner, and inducing functional components to carry biomass waste functional fillers to migrate to the surface by utilizing a solvent volatilization gradient, and performing in-situ crosslinking anchoring to form a cured film; and S4, post-treatment, namely attaching the solidified film obtained in the step 3 to the base cloth in a semi-molten state, curing, cooling and stripping release paper to obtain the self-hydrophobic mildew-proof modified element leather material.
  6. 6. The process for preparing the self-hydrophobic mildew-proof modified element leather material according to claim 5, wherein the preparation method of the latent metal crosslinking prefabrication liquid comprises the following steps: Dissolving metal salt in absolute ethyl alcohol, dropwise adding volatile amine ligand under the stirring condition of 5-30 ℃, and sealing, stirring and reacting after the dropwise adding is completed within 15-45 minutes to obtain clear transparent or colored transparent liquid.
  7. 7. The process for preparing the self-hydrophobic mildew-proof modified element leather material according to claim 5, wherein the preparation method for the amphiphilic functional carrier fluid comprises the following steps: Dissolving plant polyphenol extract in high boiling point cosolvent heated to 40-50deg.C, adding side chain amino modified polysiloxane, and dispersing with high speed dispersing machine to obtain homogeneous liquid.
  8. 8. The process for preparing the self-hydrophobic mildew-proof modified leather material according to claim 5, wherein the temperature programming and curing of the step S3 is specifically to sequentially pass the release paper coated with the wet film in the step S2 through two drying stages: A first drying stage: Setting a first heating temperature to be 65-90 ℃ and a residence time to be 2-4 minutes, wherein the first heating temperature is set to be lower than the boiling point of the volatile amine ligand so as to induce the amphiphilic functional transport carrier liquid and the biomass waste functional filler to migrate and enrich towards the surface of the wet film by utilizing the solvent volatilization gradient while preventing the release of metal ions; and a second drying stage: Setting the second heating temperature to be 120-150 ℃ and the residence time to be 2-3 minutes, wherein the second heating temperature is set to be higher than the boiling point of the volatile amine ligand so as to promote the volatilization of the volatile amine ligand and release the coordination shielding on metal ions, thereby triggering the in-situ crosslinking of the metal ions and polyphenol compounds.
  9. 9. The process for preparing a self-hydrophobic mildew-proof modified cellulose leather material according to claim 5, wherein in the step S2, the viscosity of the modified polyurethane slurry is controlled to 2500-4000 mPa S, and the thickness of a coating wet film is 100-150 μm.
  10. 10. The self-hydrophobic mildew-proof modified cellulose leather material according to claim 1, wherein the self-hydrophobic mildew-proof modified cellulose leather material is applied to the preparation of vamp materials, shoe lining materials or insole fabrics so as to improve the surface contamination resistance and the fungal breeding resistance of a shoe product in a wet environment.

Description

Application of self-hydrophobic mildew-proof modified leather in shoe material and preparation process thereof Technical Field The invention relates to the technical field of polymer composite materials, in particular to application of self-hydrophobic mildew-proof modified element leather in shoe materials and a preparation process thereof. Background The natural leather has a good physical and mechanical properties and a similar appearance and hand feeling to those of natural leather, and is widely used in the fields of shoe materials, bags, furniture and the like. However, the conventional plain leather surface usually lacks sufficient hydrophobicity, and polar groups in polyurethane molecular chains are easy to adsorb moisture, so that the polyurethane molecular chains are very easy to become a temperature bed for mold growth in a high-temperature and high-humidity environment, mold spots, discoloration and even degradation occur on the material surface, and the service life and the sanitary performance of the product are seriously affected. At present, the method for endowing the plain leather with the hydrophobic and mildew-proof functions mainly comprises a surface finishing method and a bulk blending method. The surface finishing method is to spray or roll-coat a hydrophobic agent or a mildew preventive on the surface of the material after the raw leather is molded. Although the method is flexible in process, the functional layer is mainly attached to the surface of the substrate by means of physical adsorption, the bonding fastness is poor, and functional components are easy to peel off and fall off after repeated friction or water washing in the actual use process, so that the functional failure is caused. However, metal ions with high-efficiency mildew-proof effect or functional auxiliary agents with high surface activity tend to have higher chemical activity, and the direct addition of the metal ions is easy to induce premature crosslinking or agglomeration of a resin system, so that the viscosity of the slurry is greatly increased in a short time and even gelled, the pot life of the slurry is greatly shortened, and the requirement of industrial continuous coating production is difficult to adapt. In addition, the functional components of the material prepared by the blending method are uniformly distributed, and the components embedded in the resin cannot play the role of surface hydrophobicity or contact sterilization, so that the waste of raw materials is caused. Therefore, developing a modified element leather technology which can ensure the production and processing stability and realize the enrichment and firm anchoring of functional components on the surface is a problem to be solved in the field at present. Disclosure of Invention The technical problems solved by the invention are that the existing bio-based polyurethane synthetic leather material is generally poor in surface hydrophobicity, insufficient in wear resistance and easy to grow mold in a humid environment, and the conventional surface physical coating modification process has the defects of weak interlayer binding force and easy falling, and the direct addition of the functional auxiliary agent often causes the requirements of poor storage stability of resin slurry or incapability of effectively enriching functional components on the surface. In order to solve the problems, the invention provides the following technical scheme: In a first aspect, the invention provides a self-hydrophobic mildew-proof modified element leather material, which adopts the following technical scheme: the self-hydrophobic mildew-proof modified leather material is prepared from modified polyurethane slurry through coating, curing and attaching to base cloth, wherein the modified polyurethane slurry is prepared from the following raw materials, by weight, 100.0 parts of bio-based single-component polyurethane resin solution, 4.0-10.0 parts of amphiphilic functional conveying carrier liquid, 3.0-10.0 parts of biomass waste functional filling, 2.0-5.0 parts of latent metal crosslinked prefabricated liquid and an organic solvent for adjusting viscosity. By adopting the technical scheme, the invention realizes hydrophobic, wear-resistant and mildew-proof functional modification of the surface of the plain leather. The latent metal cross-linking prefabricated liquid forms a complex with metal ions through volatile amine ligands, inhibits the catalysis and cross-linking activity of the metal ions at normal temperature, and ensures the storage stability of the modified slurry. The amphiphilic functional conveying carrier liquid utilizes the volatilization rate difference of the high-boiling point cosolvent and the main solvent to convey plant polyphenol, side chain amino modified polysiloxane and biomass waste functional filler to the surface of the coating in the drying process. In the high-temperature curing stage, the amine ligand volatilizes, metal ions