Leather matting transfer film and method of making same

Abstract

The application discloses a kind of leather with dull transfer film and preparation method thereof, it is related to leather transfer film technical field.A kind of leather with dull transfer film is sequentially composed of upper surface layer, core layer and lower surface layer, the upper surface layer includes the following weight parts raw materials: high-density polyethylene 40-70 parts, polyolefin elastomer 10-15 parts, modified molybdenum / silicon dioxide composite material 2-5 parts, polybutylene terephthalate 2-10 parts, dispersing agent 1-3 parts, antioxidant 0.1-1 part.The application further discloses a kind of preparation method of leather with dull transfer film.The dull transfer film prepared in the application has multilayer network structure, micro surface is concave-convex structure, has good dull effect, and has good toughness.

Description

Technical Field

[0001] This invention relates to the field of leather transfer film technology, and in particular to a matte transfer film for leather and its preparation method. Background Technology

[0002] With the rapid development of the times, early single-style leather products could no longer meet people's personalized needs for leather goods. Therefore, diverse leather transfer films emerged. The transfer film, printed with patterns, is bonded to the leather. After heat pressing and cooling, the backing paper of the transfer film is peeled off. The areas on the leather surface with transfer ink will firmly adhere the colored patterns on the transfer film to the leather surface. However, in areas without transfer ink, because the color on the transfer film has not adhered to the leather surface, when the transfer film is peeled off, the unadhesive color is removed along with the film, detaching from the leather surface. This process transfers the color from the transfer film to the leather surface.

[0003] In recent years, people have increasingly favored low-gloss leather products, which have a softer visual appeal and offer good value for money. Low-gloss leather products involve applying a matte finish to the existing leather. Matte transfer films not only apply a matte finish to the leather surface but can also simultaneously transfer personalized patterns, achieving a combination of rich colors and low gloss. However, existing matte transfer films suffer from uneven matte effects and poor toughness, limiting their application. Summary of the Invention

[0004] Based on the technical problems existing in the background art, the present invention proposes an matting transfer film for leather and its preparation method.

[0005] The present invention proposes a matte transfer film for leather, which consists of an upper surface layer, a core layer and a lower surface layer in sequence.

[0006] The upper surface layer comprises the following raw materials in parts by weight: 40-70 parts of high-density polyethylene, 10-15 parts of polyolefin elastomer, 2-5 parts of modified molybdenum oxide / silica composite material, 2-10 parts of polybutylene terephthalate, 1-3 parts of dispersant, and 0.1-1 parts of antioxidant.

[0007] Preferably, the preparation method of the modified molybdenum oxide / silica composite material is as follows:

[0008] S1. Mix 5-8 parts by weight of silica powder, 4-6 parts by weight of ammonium molybdate tetrahydrate and 60-80 parts by weight of solvent evenly and pour into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 180-200℃ and the reaction time is 20-24h. After cooling, washing and drying, molybdenum oxide / silica composite material is obtained.

[0009] S2. The molybdenum oxide / silica composite material is mixed evenly with silane coupling agent and ethanol, and then cooled and dried to obtain the modified molybdenum oxide / silica composite material.

[0010] More preferably, in S1, the particle size of the silica powder is 3-8 μm.

[0011] More preferably, in S1, the solvent is selected from one or more of ethanol and ethylene glycol.

[0012] More preferably, in S2, the silane coupling agent is selected from one or more of γ-ureidopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0013] More preferably, in S2, the mass ratio of molybdenum oxide / silica composite material: ethanol: silane coupling agent is 1:(2-3):(0.5-1).

[0014] Preferably, the density of the high-density polyethylene is 0.940-0.955 g / cm³. 3 Its melt flow index at 230℃ and 2.16kg is 0.2-0.4g / 10min.

[0015] Preferably, the polyolefin elastomer has a hardness of 70-74 Shore D and a melt index of 5-7 g / 10 min at 230°C and 2.16 kg.

[0016] Preferably, the dispersant is selected from one or more of PSI-500 or SP-1013.

[0017] Preferably, the antioxidant is selected from one or more of antioxidant 1010 or antioxidant 168.

[0018] Preferably, the core layer comprises the following raw materials in parts by weight: 49-51 parts polypropylene, 40-48 parts polyethylene, 1-6 parts antistatic agent, and 0.2-0.5 parts slip agent.

[0019] More preferably, the antistatic agent is selected from one or more of erucamide and ethoxyamine.

[0020] More preferably, the slip agent is oleamide.

[0021] Preferably, the lower surface layer comprises the following raw materials in parts by weight: 48-65 parts polypropylene and 1-3 parts silica.

[0022] More preferably, the polypropylene has a melt index of 1.9-2.2 g / 10 min at 230°C and 2.16 kg.

[0023] The present invention provides a method for preparing an matte transfer film for leather, comprising the following steps:

[0024] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately and plasticized using different extruders. The resulting melt is then subjected to compounding, longitudinal stretching, and transverse stretching to obtain a matte transfer film for leather.

[0025] Preferably, the plasticizing temperature is 235-250℃.

[0026] Preferably, the longitudinal drawing process temperature is 120-130℃.

[0027] Preferably, the cross-stretching process temperature is 150-170℃.

[0028] The beneficial effects of this invention are as follows:

[0029] This invention optimizes the formulation of the surface layer of the matting transfer film by introducing a molybdenum oxide / silica composite material as an inorganic matting agent. The petal-like nanostructure of molybdenum oxide is combined with micron-sized silica to further enhance surface roughness. When a light source illuminates the surface of the matting transfer film, diffuse reflection occurs, achieving a matting effect. The silane coupling agent introduces amino groups onto the surface of the molybdenum oxide / silica composite material, improving its dispersibility and effectively enhancing the uniformity of matting when applied to leather products. Furthermore, the silane coupling agent further enhances the uniformity of matting on the molybdenum oxide / silica composite material. A "bridge" is built between the molybdenum oxide / silica composite material and high-density polyethylene (HDPE), improving the compatibility between the two. This allows HDPE and HDPE to combine to form a multi-layered network structure, further enhancing the matting effect of the matting transfer film. The invention also incorporates a polyolefin elastomer with similar polarity to HDPE, exhibiting good thermodynamic compatibility. The elastomer's good flowability improves the dispersion of the modified molybdenum oxide / silica composite material. Furthermore, the synergistic effect of HDPE and the polyolefin elastomer enhances the overall toughness of the matting transfer film. The matting transfer film prepared by this invention possesses a multi-layered network structure with an uneven microstructure, exhibiting excellent matting effect and good toughness. Detailed Implementation

[0030] The technical solution of the present invention will be described in detail through specific embodiments.

[0031] In the following examples and comparative examples, high-density polyethylene is a product of ExxonMobil Chemical Company; polyolefin elastomer is a product of Mitsui Chemicals Company; PSI-500 dispersant is a product of Shanghai Yinghe Chemical Co., Ltd.; and polypropylene is a product of ExxonMobil Chemical Company.

[0032] Example 1

[0033] The present invention proposes a matte transfer film for leather, which consists of an upper surface layer, a core layer and a lower surface layer in sequence.

[0034] The upper surface layer comprises the following raw materials in parts by weight: 40 parts high-density polyethylene, 10 parts polyolefin elastomer, 2 parts modified molybdenum oxide / silica composite material, 2 parts polybutylene terephthalate, 1 part PSI-500 dispersant, and 0.2 parts antioxidant 10100.

[0035] The preparation method of the modified molybdenum oxide / silica composite material is as follows: S1, 5 parts by mass of silica powder with a particle size of 6μm, 5 parts by mass of ammonium molybdate tetrahydrate and 70 parts by mass of ethylene glycol are mixed evenly and poured into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 190℃ and the reaction time is 22h. After cooling, washing and drying, the molybdenum oxide / silica composite material is obtained; S2, the molybdenum oxide / silica composite material is mixed evenly with γ-ureidopropyltriethoxysilane and ethanol at a mass ratio of 1:3:0.8. After cooling and drying, the modified molybdenum oxide / silica composite material is obtained.

[0036] The core layer comprises the following raw materials in parts by weight: 50 parts polypropylene, 41 parts polyethylene, 1.1 parts erucamide, and 0.3 parts oleamide.

[0037] The lower layer comprises the following raw materials in parts by weight: 48 parts polypropylene and 1 part silica.

[0038] The density of high-density polyethylene is 0.954 g / cm³. 3 The melt flow index of the polyolefin elastomer at 230℃ and 2.16 kg is 0.35 g / 10 min. The hardness of the polyolefin elastomer is 73 Shore D, and its melt flow index at 230℃ and 2.16 kg is 6.7 g / 10 min. The melt flow index of the polypropylene at 230℃ and 2.16 kg is 1.9 g / 10 min.

[0039] A method for preparing a matte transfer film for leather includes the following steps:

[0040] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately using different extruders and plasticized at temperatures of 235℃, 250℃, and 240℃ respectively. The resulting melt is then composited and subjected to longitudinal stretching at 125℃ and transverse stretching at 160℃ to obtain a matte transfer film for leather.

[0041] Example 2

[0042] The present invention proposes a matte transfer film for leather, which consists of an upper surface layer, a core layer and a lower surface layer in sequence.

[0043] The upper surface layer comprises the following raw materials in parts by weight: 70 parts high-density polyethylene, 15 parts polyolefin elastomer, 5 parts modified molybdenum oxide / silica composite material, 10 parts polybutylene terephthalate, 3 parts PSI-500 dispersant, and 1 part antioxidant 1010.

[0044] The preparation method of the modified molybdenum oxide / silica composite material is as follows: S1, 5 parts by mass of silica powder with a particle size of 6μm, 5 parts by mass of ammonium molybdate tetrahydrate and 70 parts by mass of ethylene glycol are mixed evenly and poured into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 190℃ and the reaction time is 22h. After cooling, washing and drying, the molybdenum oxide / silica composite material is obtained; S2, the molybdenum oxide / silica composite material is mixed evenly with γ-ureidopropyltriethoxysilane and ethanol at a mass ratio of 1:3:0.8. After cooling and drying, the modified molybdenum oxide / silica composite material is obtained.

[0045] The core layer comprises the following raw materials in parts by weight: 51 parts polypropylene, 48 parts polyethylene, 6 parts erucamide, and 0.5 parts oleamide.

[0046] The lower layer comprises the following raw materials in parts by weight: 65 parts polypropylene and 3 parts silica.

[0047] The density of high-density polyethylene is 0.954 g / cm³. 3 The melt flow index of the polyolefin elastomer at 230℃ and 2.16 kg is 0.35 g / 10 min. The hardness of the polyolefin elastomer is 73 Shore D, and its melt flow index at 230℃ and 2.16 kg is 6.7 g / 10 min. The melt flow index of the polypropylene at 230℃ and 2.16 kg is 1.9 g / 10 min.

[0048] A method for preparing a matte transfer film for leather includes the following steps:

[0049] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately using different extruders and plasticized at temperatures of 235℃, 250℃, and 240℃ respectively. The resulting melt is then composited and subjected to longitudinal stretching at 125℃ and transverse stretching at 160℃ to obtain a matte transfer film for leather.

[0050] Example 3

[0051] The present invention proposes a matte transfer film for leather, which consists of an upper surface layer, a core layer and a lower surface layer in sequence.

[0052] The upper surface layer comprises the following raw materials in parts by weight: 55 parts high-density polyethylene, 12 parts polyolefin elastomer, 4 parts modified molybdenum oxide / silica composite material, 6 parts polybutylene terephthalate, 2 parts PSI-500 dispersant, and 0.5 parts antioxidant 10100.

[0053] The preparation method of the modified molybdenum oxide / silica composite material is as follows: S1, 5 parts by mass of silica powder with a particle size of 6μm, 5 parts by mass of ammonium molybdate tetrahydrate and 70 parts by mass of ethylene glycol are mixed evenly and poured into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 190℃ and the reaction time is 22h. After cooling, washing and drying, the molybdenum oxide / silica composite material is obtained; S2, the molybdenum oxide / silica composite material is mixed evenly with γ-ureidopropyltriethoxysilane and ethanol at a mass ratio of 1:3:0.8. After cooling and drying, the modified molybdenum oxide / silica composite material is obtained.

[0054] The core layer comprises the following raw materials in parts by weight: 50 parts polypropylene, 44 parts polyethylene, 3 parts erucamide, and 0.3 parts oleamide.

[0055] The lower layer comprises the following raw materials in parts by weight: 57 parts polypropylene and 2 parts silica.

[0056] The density of high-density polyethylene is 0.954 g / cm³. 3 The melt flow index of the polyolefin elastomer at 230℃ and 2.16 kg is 0.35 g / 10 min. The hardness of the polyolefin elastomer is 73 Shore D, and its melt flow index at 230℃ and 2.16 kg is 6.7 g / 10 min. The melt flow index of the polypropylene at 230℃ and 2.16 kg is 1.9 g / 10 min.

[0057] A method for preparing a matte transfer film for leather includes the following steps:

[0058] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately using different extruders and plasticized at temperatures of 235℃, 250℃, and 240℃ respectively. The resulting melt is then composited and subjected to longitudinal stretching at 125℃ and transverse stretching at 160℃ to obtain a matte transfer film for leather.

[0059] Comparative Example 1

[0060] A matte transfer film for leather, comprising an upper surface layer, a core layer, and a lower surface layer.

[0061] The upper surface layer comprises the following raw materials in parts by weight: 55 parts high-density polyethylene, 12 parts polyolefin elastomer, 6 parts polybutylene terephthalate, 2 parts PSI-500 dispersant, and 0.5 parts antioxidant 1010.

[0062] The core layer comprises the following raw materials in parts by weight: 50 parts polypropylene, 44 parts polyethylene, 3 parts erucamide, and 0.3 parts oleamide.

[0063] The lower layer comprises the following raw materials in parts by weight: 57 parts polypropylene and 2 parts silica.

[0064] The density of high-density polyethylene is 0.954 g / cm³. 3 The melt flow index of the polyolefin elastomer at 230℃ and 2.16 kg is 0.35 g / 10 min. The hardness of the polyolefin elastomer is 73 Shore D, and its melt flow index at 230℃ and 2.16 kg is 6.7 g / 10 min. The melt flow index of the polypropylene at 230℃ and 2.16 kg is 1.9 g / 10 min.

[0065] A method for preparing a matte transfer film for leather includes the following steps:

[0066] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately using different extruders and plasticized at temperatures of 235℃, 250℃, and 240℃ respectively. The resulting melt is then composited and subjected to longitudinal stretching at 125℃ and transverse stretching at 160℃ to obtain a matte transfer film for leather.

[0067] Comparative Example 2

[0068] A matte transfer film for leather, comprising an upper surface layer, a core layer, and a lower surface layer.

[0069] The upper surface layer comprises the following raw materials in parts by weight: 55 parts high-density polyethylene, 12 parts polyolefin elastomer, 4 parts molybdenum oxide / silica composite material, 6 parts polybutylene terephthalate, 2 parts PSI-500 dispersant, and 0.5 parts antioxidant 1010.

[0070] The preparation method of the molybdenum oxide / silica composite material is as follows: 5 parts by mass of silica powder with a particle size of 6μm, 5 parts by mass of ammonium molybdate tetrahydrate and 70 parts by mass of ethylene glycol are mixed evenly and poured into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 190℃ and the reaction time is 22h. After cooling, washing and drying, the molybdenum oxide / silica composite material is obtained.

[0071] The core layer comprises the following raw materials in parts by weight: 50 parts polypropylene, 44 parts polyethylene, 3 parts erucamide, and 0.3 parts oleamide.

[0072] The lower layer comprises the following raw materials in parts by weight: 57 parts polypropylene and 2 parts silica.

[0073] The density of high-density polyethylene is 0.954 g / cm³. 3 The melt flow index of the polyolefin elastomer at 230℃ and 2.16 kg is 0.35 g / 10 min. The hardness of the polyolefin elastomer is 73 Shore D, and its melt flow index at 230℃ and 2.16 kg is 6.7 g / 10 min. The melt flow index of the polypropylene at 230℃ and 2.16 kg is 1.9 g / 10 min.

[0074] A method for preparing a matte transfer film for leather includes the following steps:

[0075] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately using different extruders and plasticized at temperatures of 235℃, 250℃, and 240℃ respectively. The resulting melt is then composited and subjected to longitudinal stretching at 125℃ and transverse stretching at 160℃ to obtain a matte transfer film for leather.

[0076] Comparative Example 3

[0077] A matte transfer film for leather, comprising an upper surface layer, a core layer, and a lower surface layer.

[0078] The upper surface layer comprises the following raw materials in parts by weight: 55 parts high-density polyethylene, 4 parts modified molybdenum oxide / silica composite material, 6 parts polybutylene terephthalate, 2 parts PSI-500 dispersant, and 0.5 parts antioxidant 1010;

[0079] The preparation method of the modified molybdenum oxide / silica composite material is as follows: S1, 5 parts by mass of silica powder with a particle size of 6μm, 5 parts by mass of ammonium molybdate tetrahydrate and 70 parts by mass of ethylene glycol are mixed evenly and poured into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 190℃ and the reaction time is 22h. After cooling, washing and drying, the molybdenum oxide / silica composite material is obtained; S2, the molybdenum oxide / silica composite material is mixed evenly with γ-ureidopropyltriethoxysilane and ethanol at a mass ratio of 1:3:0.8. After cooling and drying, the modified molybdenum oxide / silica composite material is obtained.

[0080] The core layer comprises the following raw materials in parts by weight: 50 parts polypropylene, 44 parts polyethylene, 3 parts erucamide, and 0.3 parts oleamide.

[0081] The lower layer comprises the following raw materials in parts by weight: 57 parts polypropylene and 2 parts silica.

[0082] The density of high-density polyethylene is 0.954 g / cm³. 3 Its melt index at 230℃ and 2.16kg is 0.35g / 10min. The melt index of polypropylene at 230℃ and 2.16kg is 1.9g / 10min.

[0083] A method for preparing a matte transfer film for leather includes the following steps:

[0084] The raw materials for the upper surface layer, core layer, and lower surface layer are fed separately using different extruders and plasticized at temperatures of 235℃, 250℃, and 240℃ respectively. The resulting melt is then composited and subjected to longitudinal stretching at 125℃ and transverse stretching at 160℃ to obtain a matte transfer film for leather.

[0085] The transfer membranes prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests, and the results are shown in Table 1.

[0086] Haze: Performed according to GB / T2410-2008 method; Tensile strength: Performed according to GB / T10004-2008 method.

[0087] Table 1. Performance test results of transfer membranes in Examples 1-3 and Comparative Examples 1-3

[0088]

[0089] As shown in Table 1, the matting transfer film for leather prepared by this invention has good physical properties. Data from Comparative Example 1 and Examples 1-3 show that the matting effect of the transfer film without the modified molybdenum oxide / silica composite material is significantly weaker than that with the modified molybdenum oxide / silica composite material. Data from Comparative Example 2 and Examples 1-3 show that without the addition of a silane coupling agent to modify the molybdenum oxide / silica composite material, the transfer film surface has many bright spots, resulting in uneven matting effect. Data from Comparative Example 3 and Examples 1-3 show that without the addition of a polyolefin elastomer, the high-density polyethylene does not synergize with the polyolefin elastomer, leading to a decrease in the overall toughness of the matting transfer film, and bright spots on the surface. Furthermore, the modified molybdenum oxide / silica composite material is not uniformly dispersed in the high-density polyethylene, resulting in uneven matting effect. This invention optimizes the formulation of the upper surface layer of the matting transfer film by introducing a molybdenum oxide / silica composite material as an inorganic matting agent to enhance the matting effect; and adds a silane coupling agent to improve matting uniformity. Furthermore, this invention combines a polyolefin elastomer with polarity similar to high-density polyethylene, which not only further improves matting uniformity but also enhances the overall toughness of the matting transfer film. The matting transfer film prepared by this invention has a multi-layered network structure and a micro-surface with an uneven texture, exhibiting excellent matting effect and good toughness.

[0090] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A matte transfer film for leather, comprising an upper surface layer, a core layer and a lower surface layer, wherein the upper surface layer comprises the following raw materials in parts by weight: 40-70 parts of high-density polyethylene, 10-15 parts of polyolefin elastomer, 2-5 parts of modified molybdenum oxide / silica composite material, 2-10 parts of polybutylene terephthalate, 1-3 parts of dispersant, and 0.1-1 parts of antioxidant; The preparation method of the modified molybdenum oxide / silica composite material is as follows: S1. Mix 5-8 parts by weight of silica powder, 4-6 parts by weight of ammonium molybdate tetrahydrate and 60-80 parts by weight of solvent evenly and pour into a reaction vessel lined with polytetrafluoroethylene. The reaction temperature is 180-200℃ and the reaction time is 20-24h. After cooling, washing and drying, molybdenum oxide / silica composite material is obtained. S2. The molybdenum oxide / silica composite material is mixed evenly with silane coupling agent and ethanol, and then cooled and dried to obtain the modified molybdenum oxide / silica composite material. In S1, the particle size of the silica powder is 3-8 μm; the solvent is selected from one or more of ethanol and ethylene glycol. In S2, the silane coupling agent is selected from one or more of γ-ureidopropyltriethoxysilane and 3-aminopropyltrimethoxysilane; the mass ratio of molybdenum oxide / silica composite material: ethanol: silane coupling agent is 1:(2-3):(0.5-1).

2. The matte transfer film for leather according to claim 1, characterized in that, The density of the high-density polyethylene is 0.940-0.955 g / cm³. 3 The melt index of the polyolefin elastomer at 230℃ and 2.16kg is 0.2-0.4g / 10min; the hardness of the polyolefin elastomer is 70-74 Shore D, and the melt index of the polyolefin elastomer at 230℃ and 2.16kg is 5-7g / 10min.

3. The matte transfer film for leather according to claim 1, characterized in that, The dispersant is selected from one or more of PSI-500 or SP-1013; the antioxidant is selected from one or more of antioxidant 1010 or antioxidant 168.

4. The matte transfer film for leather according to claim 1, characterized in that, The core layer comprises the following raw materials in parts by weight: 49-51 parts polypropylene, 40-48 parts polyethylene, 1-6 parts antistatic agent, and 0.2-0.5 parts slip agent.

5. The matte transfer film for leather according to claim 1, characterized in that, The lower surface layer comprises the following raw materials in parts by weight: 48-65 parts polypropylene and 1-3 parts silica.

6. A method for preparing a matte transfer film for leather according to any one of claims 1-5, characterized in that, The process includes the following steps: feeding the raw materials for the upper surface layer, core layer, and lower surface layer separately using different extruders and plasticizing them; then, through compounding, longitudinal stretching, and transverse stretching, the resulting melt is processed to obtain a matte transfer film for leather.

7. The method for preparing a matte transfer film for leather according to claim 6, characterized in that, The plasticizing temperature is 235-250℃; the longitudinal stretching temperature is 120-130℃; and the transverse stretching temperature is 150-170℃.

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