CN-122011730-A - TPU composite film for integrally forming and preparing sole and preparation method thereof

CN122011730ACN 122011730 ACN122011730 ACN 122011730ACN-122011730-A

Abstract

The application relates to the field of shoe materials, and in particular discloses a TPU composite film for integrally forming and preparing soles and a preparation method thereof, wherein the TPU composite film comprises TPU particles, SEBS leftover materials, an antioxidant, an ultraviolet absorbent, a light stabilizer, a lubricant, reinforcing filler, an adhesion promoter and a heat-resistant modifier; the heat-resistant modifier is a mixture of polycarbonate diol and graphene oxide-hydroxyl organic silicon modifier composite filler, and the graphene oxide-hydroxyl organic silicon modifier composite filler is prepared by adding hydroxyl-terminated polydimethylsiloxane into an ethanol water solution added with a silane coupling agent and graphene oxide for reaction and then drying; the preparation method comprises the following steps of fully and uniformly mixing the raw materials, and then carrying out melt blending and tape casting to form a film to prepare the TPU composite film. The TPU composite film with excellent heat resistance and yellowing resistance is prepared by the method, so that the requirement of integrally forming to prepare the sole is met.

Inventors

Bin Jiachuo
Bin Jiaqi
BIN XUECHENG
WEN SHENG
HE JUXIANG
ZHANG YUCHENG
Zhou Hujuan

Assignees

清远齐汇新材料有限公司

Dates

Publication Date: 20260512
Application Date: 20260211
Priority Date: 20250702

Claims (10)

1. The TPU composite film for integrally forming and preparing the sole is characterized by comprising the following raw materials in parts by weight: 60-80 parts of TPU particles, 15-30 parts of SEBS leftover materials, 1-3 parts of antioxidants, 0.5-2 parts of ultraviolet absorbers, 0.5-2 parts of light stabilizers, 0.5-2 parts of lubricants, 5-15 parts of reinforcing fillers, 1-3 parts of adhesion promoters and 8-15 parts of heat-resistant modifiers; The heat-resistant modifier is a mixture of polycarbonate diol and graphene oxide-hydroxyl organic silicon modifier composite filler, and the graphene oxide-hydroxyl organic silicon modifier composite filler is prepared by adding hydroxyl-terminated polydimethylsiloxane into an ethanol water solution added with a silane coupling agent and graphene oxide for reaction and then drying.
2. The TPU composite film for integrally forming shoe soles according to claim 1, wherein the graphene oxide-hydroxyl organosilicon modifier composite filler is prepared by the following method: dissolving graphene oxide in water, performing ultrasonic dispersion to obtain graphene oxide solution, adding an ethanol water solution of a silane coupling agent, and mixing and dispersing to obtain primary mixed solution; And (3) dissolving hydroxyl-terminated polydimethylsiloxane in carbon tetrachloride to prepare an organosilicon solution, adding the organosilicon solution into the primary mixed solution, heating to 60-80 ℃, adjusting the pH to 4-6, stirring for reaction for 2-3 hours, then carrying out reduced pressure distillation, carrying out vacuum drying, carrying out heat treatment at 120-130 ℃ for 1-2 hours, and washing and drying to prepare the graphene oxide-hydroxyl organosilicon modifier composite filler.
3. The TPU composite film for integrally forming and preparing soles according to claim 2 is characterized in that in the preparation process of graphene oxide-hydroxyl organosilicon modifier composite filler, the addition amount of a silane coupling agent is 1-3wt% of graphene oxide, the addition mass ratio of graphene oxide to water is 1 (5-6), the addition amount of an ethanol aqueous solution is 3-4 times of the addition amount of the silane coupling agent, and the ethanol aqueous solution is obtained by mixing ethanol and water according to the volume ratio of 1 (1-1.2); the adding mass ratio of the hydroxyl-terminated polydimethylsiloxane to the graphene oxide is 1 (1.2-1.3), and the hydroxyl-terminated polydimethylsiloxane is dissolved in carbon tetrachloride with the mass multiple of 1-2.
4. The TPU composite film for integrally forming shoe soles according to claim 2, wherein during the preparation process of the graphene oxide-hydroxyl organic silicon modifier composite filler, PAMAM is added after the aqueous ethanol solution added with a silane coupling agent is mixed and dispersed, the initial mixed solution is prepared after the dispersion, and the addition amount of the PAMAM is 3-5wt% of the addition amount of the graphene oxide.
5. The TPU composite film for integrally forming the sole according to claim 1, wherein the SEBS leftover material is added after modification treatment, and the specific operation is as follows: washing and drying SEBS leftover materials, adding the SEBS leftover materials into a toluene solvent, heating to 90-110 ℃, firstly dripping an initiator and isocyanate ethyl acrylate, reacting for 40-60min, heating to 110-130 ℃, dripping maleic anhydride, stirring under the protection of nitrogen for reacting for 1-2h, adding the SEBS leftover materials into ethanol for precipitation, washing the precipitate with alcohol, and then drying in vacuum to obtain the modified SEBS leftover materials.
6. The TPU composite film for integrally forming shoe soles according to claim 5, wherein the mass ratio of the SEBS leftover materials to the toluene solvent is 1 (3-4), the addition amount of the initiator is 0.5-2wt% of the SEBS leftover materials, and the addition mass ratio of the isocyanate ethyl acrylate, the maleic anhydride and the SEBS leftover materials is 1 (2-3): 6-8.
7. The TPU composite membrane for integrally forming shoe soles according to claim 5, wherein during the preparation process of the modified SEBS leftover material, before the initiator and the isocyanate ethyl acrylate are added dropwise, the hindered phenol antioxidant is firstly added, and the adding amount of the hindered phenol antioxidant is 0.1-0.5wt% of the adding amount of the SEBS leftover material.
8. The TPU composite film for integrally forming a sole according to claim 1, wherein the ultraviolet absorber is benzophenone ultraviolet absorber; The light stabilizer is a hindered amine light stabilizer; the lubricant is calcium stearate, and the reinforcing filler is nano silicon dioxide or calcium carbonate.
9. A TPU composite film for integrally molded shoe soles according to claim 1, characterized in that the adhesion promoter is a mixture of KH-550 and L-75 in a mass ratio of 1 (1-1.2).
10. A process for the preparation of TPU composite films for the integrated formation of shoe soles according to any one of claims 1 to 9, characterized in that it comprises the following steps: and (3) fully and uniformly mixing the raw materials, and then carrying out melt blending and casting to form a film to prepare the TPU composite film.

Description

TPU composite film for integrally forming and preparing sole and preparation method thereof Technical Field The application relates to the field of shoe materials, in particular to a TPU composite film for integrally forming and preparing soles and a preparation method thereof. Background In the field of footwear manufacturing, soles are used as key components, the properties of which directly affect the comfort, durability and functionality of the footwear. Conventional soles are typically comprised of an outsole that is loaded with wear and traction resistance and a midsole that provides cushioning and support. However, in the traditional sole preparation process, the outsole and the midsole are required to be bonded through glue after being manufactured respectively, the process is complex, the energy consumption is high, and defects such as bubbles, pits and the like are easy to occur at the bonding interface. And the wear resistance and flexibility of the traditional sole material such as rubber are difficult to be compatible, so that the service life of the product is short or the comfort is poor, for example, the rubber outsole is wear-resistant but has insufficient flexibility, and the EVA midsole is soft but has poor wear resistance. With increasing demands of consumers for performance, comfort and environmental protection of footwear products, development of novel materials and preparation processes are urgently needed in the footwear manufacturing industry. TPU (thermoplastic polyurethane) is an ideal choice of sole material as a high performance elastomer due to its excellent wear resistance, flexibility, chemical resistance and biocompatibility, and in order to solve the above problems, the related art has begun to study the preparation of soles by integrally molding TPU materials. At present, the outsole and midsole of the sole are combined together in the same mold through a specific process to form a complete sole structure, for example, a TPU composite film is paved at the bottom of the mold to be tightly attached to the surface of the mold in the related art, then PU foaming material is injected into the mold to cover the TPU composite film, foaming and forming are carried out in the mold, heat and pressure generated in the foaming process enable the PU foaming material to be tightly attached to the TPU composite film, the shape and texture of the sole are formed at the same time, and the mold is cooled and the mold is released after the foaming material is solidified and formed to obtain the sole which is integrally formed. When the TPU composite film is used for preparing integrally formed soles, the TPU composite film and PU foaming materials need to have good heat resistance, the TPU composite film and PU foaming materials are synchronously formed in a die in the forming process, the TPU composite film with excellent heat resistance can avoid material deformation or performance degradation caused by high temperature, the stability of a forming process and the consistency of products are ensured, in addition, the TPU composite film needs to be further improved in yellowing resistance, the original color and appearance of shoes can be ensured to be kept under long-term wearing and daily illumination, and the attractive service life of the shoes is prolonged. Disclosure of Invention In order to prepare the TPU composite film with excellent heat resistance and yellowing resistance so as to meet the requirement of integrally forming and preparing the sole, the application provides the TPU composite film for integrally forming and preparing the sole and a preparation method thereof. In a first aspect, the application provides a TPU composite film for integrally forming and preparing soles, which adopts the following technical scheme: the TPU composite film for integrally forming and preparing the sole comprises the following raw materials in parts by weight: 60-80 parts of TPU particles, 15-30 parts of SEBS leftover materials, 1-3 parts of antioxidants, 0.5-2 parts of ultraviolet absorbers, 0.5-2 parts of light stabilizers, 0.5-2 parts of lubricants, 5-15 parts of reinforcing fillers, 1-3 parts of adhesion promoters and 8-15 parts of heat-resistant modifiers; The heat-resistant modifier is prepared from polycarbonate diol and graphene oxide-hydroxyl organic silicon modifier composite filler, wherein the graphene oxide-hydroxyl organic silicon modifier composite filler is prepared by adding hydroxyl-terminated polydimethylsiloxane into ethanol aqueous solution added with a silane coupling agent and graphene oxide for reaction and then drying. By adopting the technical scheme, the TPU composite film of the application takes TPU particles as a main material, modified SEBS leftover materials are added in an auxiliary way, the SEBS is prepared by saturating double bonds through hydrogenation of special linear SBS, wherein carbon-carbon double bonds of butadiene sections are saturated through hydr