WO2020244449A1 - 具有透光特性的tpo组合物及含有该组合物的tpo人造革 - Google Patents

具有透光特性的tpo组合物及含有该组合物的tpo人造革 Download PDF

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WO2020244449A1
WO2020244449A1 PCT/CN2020/093152 CN2020093152W WO2020244449A1 WO 2020244449 A1 WO2020244449 A1 WO 2020244449A1 CN 2020093152 W CN2020093152 W CN 2020093152W WO 2020244449 A1 WO2020244449 A1 WO 2020244449A1
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Prior art keywords
tpo
weight
parts
light
composition
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PCT/CN2020/093152
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English (en)
French (fr)
Inventor
张翠美
刘海洋
滕大勇
Original Assignee
贝内克-长顺汽车内饰材料（张家港）有限公司
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Publication of WO2020244449A1 publication Critical patent/WO2020244449A1/zh

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    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2251—Oxides; Hydroxides of metals of chromium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)

Definitions

  • the present invention relates to a thermoplastic polyolefin elastomer (also called TPO) composition with light-transmitting properties, and a TPO artificial leather made from the TPO composition.
  • TPO thermoplastic polyolefin elastomer
  • TPO artificial leather is widely used in automotive interiors. Its advantages are that it has good thermodynamic properties, is halogen-free, low emission, no plasticizers, and so on.
  • CN106393890A discloses an ultra-soft environmentally friendly TPO automotive interior material, which uses a soft TPO skin and soft sponge formula to enhance the soft feel of the interior material, and uses soft water-based polyurethane paint for surface coating. The three-layer structure improves the softness of the material and reduces the density of the product.
  • CN102367318A discloses the preparation of a polystyrene transparent color masterbatch, which contains polystyrene and a solvent-based transparent dye accounting for 0.01-10% of the total weight of the polystyrene.
  • polystyrene is a polar material. Due to its poor compatibility with non-polar TPO, it will cause uneven mixing and poor softness. In addition, a lower content of transparent dye is not enough to provide sufficient color hiding power. . Therefore, such polystyrene translucent masterbatches are not suitable for use in TPO automotive interiors.
  • DE102015101331A1 describes the improvement of the light transmittance of polyurethane (PU) or polyvinyl chloride (PVC) artificial leather.
  • the structure of these artificial leathers generally includes a base fabric, a skin light-transmitting layer and a paint layer.
  • the document roughly mentions that the factors affecting the light transmittance of artificial leather mainly include the thickness, number and type of the layer, the color content in the layer, and the type and density of the base fabric.
  • the article does not specifically describe and analyze the above-mentioned influencing factors, nor does it specifically improve the performance of each type of artificial leather.
  • the object of the present invention is to provide a TPO composition with light-transmitting properties and a TPO artificial leather manufactured from the TPO composition.
  • the TPO artificial leather can be applied to car interiors, which can achieve good light transmittance while meeting the desired color coverage.
  • the present invention proposes a TPO composition with light-transmitting properties, which includes polyolefin resin, rubber and light-transmitting masterbatch, wherein, based on the total weight of the light-transmitting masterbatch is 100 parts by weight, the Translucent masterbatch includes
  • -50-70 parts by weight such as 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight Parts, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, or between any two of these values
  • Non-polar resins in the range and
  • -30-50 parts by weight such as 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight Parts, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, or between any two of these values Toner in the range.
  • Polyolefin resin and rubber particles are usually blended with an extruder, such as a twin-screw extruder. If the toner is directly added during the processing process, the flying of the toner will cause difficulties in feeding and poor dispersion. In this way, the toner and the non-polar resin are blended into a masterbatch, thereby improving the dispersibility of the toner in the TPO, and making the toner more uniform.
  • an extruder such as a twin-screw extruder
  • the present invention improves the light transmittance of TPO mainly by adjusting the color density of masterbatch.
  • the present invention found that when the toner is blended with the non-polar resin, the amount of the non-polar resin is increased when the toner is unchanged, or the amount of the toner is reduced when the non-polar resin is unchanged.
  • the amount that is to say, by increasing the relative content of the non-polar resin in the composition of the masterbatch or reducing the relative content of the toner in the composition of the masterbatch, the color concentration of the masterbatch can be reduced, thereby obtaining the Transparent masterbatch.
  • reducing the amount of masterbatch during processing can further improve the light transmission effect.
  • the content of the non-polar resin in the light-transmitting masterbatch is less than 50 parts by weight, the color concentration of the masterbatch is not low enough, and therefore, the light transmittance cannot be sufficiently improved. If the content of non-polar resin in the translucent masterbatch is higher than 70 parts by weight, it will cause insufficient color hiding power when applied to TPO materials.
  • the non-polar resin in the translucent masterbatch can be fully compatible and uniformly mixed with the non-polar TPO matrix material, so as to realize the uniform dispersion of the color in the TPO.
  • the non-polar resin in the transparent masterbatch is selected from PP and/or PE, which helps to improve the softness of the composition.
  • the toner contains
  • -10-20 parts by weight such as 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight
  • Auxiliary toner within the range between any two of these values.
  • the main toner can realize the desired base color of the TPO composition.
  • carbon black is selected for the main toner, so that the TPO composition generally presents a black base color.
  • the main toner can also choose organic red, organic yellow, phthalocyanine blue, titanium white, etc.
  • auxiliary toners are usually added for adjustment.
  • the TPO composition can transmit a light color different from the base color of the composition when irradiated with light, especially white light.
  • a light color different from the base color of the composition when irradiated with light, especially white light.
  • the resulting TPO composition presents a black primary color when not exposed to light, and when irradiated with white light, it can transmit Purple light.
  • different light-transmitting colors can be adjusted by adding auxiliary toners of different colors.
  • adding titanium dioxide, chrome green, and iron red as auxiliary toners can emit purple light when white light is irradiated on the back; and when adding titanium dioxide, chrome green, and indigo as auxiliary toners
  • blue light can be transmitted when white light is irradiated on the back side.
  • different light-transmitting color concentrations can be adjusted by adjusting the ratio of different auxiliary toners.
  • the content of the auxiliary toner increases correspondingly, the density of the light-transmitting color can be deepened, as long as the ratio of auxiliary toners is not High to hinder the color of the main toner.
  • the TPO composition further comprises a polyolefin elastomer POE.
  • the polyolefin elastomer POE in the TPO composition is a copolymer of ethylene and alpha olefin, in which the linear polyethylene PE obtained by polymerization serves as the hard segment, and the alpha olefin becomes the branched soft segment.
  • the polyolefin elastomer is a copolymer of ethylene and octene. The polyolefin elastomer POE thus obtained can effectively improve the softness of the material.
  • the polyolefin resin in the TPO composition can be selected from various conventional polyolefins, preferably aliphatic polyolefins, such as low density polyethylene LDPE, especially linear low density polyethylene LLDPE, medium density polyethylene MDPE, polypropylene PP, polybutene PB, etc.
  • Polyolefin resin helps to improve the physical and mechanical properties and heat resistance of the material.
  • the rubber in the TPO composition can be selected from various conventional rubbers, such as thermoplastic dynamic vulcanized rubber TPV, EPDM rubber, SEBS, ethylene octene rubber, ethylene butene rubber, ethylene propylene rubber, etc.
  • the rubber in the TPO composition uses TPV.
  • Conventional EPDM is vulcanized and PP is added. The resulting TPV can further effectively improve the toughness of the material.
  • TPO base material particles such as POE raw material particles, polyolefin raw material particles, and rubber raw material particles
  • raw material particles with a relatively transparent color are preferred, so that the TPO raw material particles themselves are transparent.
  • additional additives may be added to the TPO composition, such as antioxidants, light stabilizers, flame retardants, etc., and conventional materials well known to those skilled in the art can be selected as required.
  • the present invention only uses a light stabilizer as an additional auxiliary agent, which is beneficial to improve the light resistance stability of the material.
  • the TPO composition of the present invention includes
  • 40-50 parts by weight such as 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight Or a POE in the range between any two of these values;
  • 20-30 parts by weight such as 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight Or polyolefin resin in the range between any two of these values;
  • 20-40 parts by weight such as 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight , 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, or a range between any two of these values Rubber inside
  • 1-4 parts by weight for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, or a masterbatch in the range between any two of these values.
  • the TPO composition further contains 1 to 3 parts by weight, for example, 1 part by weight, 2 parts by weight, 3 parts by weight, or a light stabilizer in the range between any two of these values.
  • the TPO composition when used in the manufacture of artificial leather for automotive interiors, in order to ensure that the product has sufficient color hiding power while ensuring light transmittance, thereby ensuring the color quality of the finished artificial leather, it is preferably based on the TPO composition
  • the total amount of POE, polyolefin resin, and rubber is 100 parts by weight containing 2-4 parts by weight of masterbatch. This is because less than 2 parts by weight of masterbatch may not be enough to achieve the desired base color of the finished product.
  • the present invention also proposes a TPO artificial leather, which includes a TPO skin layer formed from the above-mentioned TPO composition according to the present invention.
  • a light-transmitting TPO skin layer can be obtained.
  • all the features and corresponding effects of the aforementioned TPO composition are applicable to the TPO skin layer formed by the TPO composition, and the description will not be repeated here.
  • a paint layer is provided on the TPO skin layer.
  • the paint layer also has light transmittance.
  • Conventional paints known in the art can be used for surface coating.
  • water-based polyurethane paint is preferably used for coating.
  • the formulation of the water-based polyurethane paint contains 70-80 parts by weight of the water-based polyurethane modified resin and 8-20 parts by weight of auxiliary agents.
  • Surface treatment by printing paint on the surface of the TPO material can advantageously improve the gloss, hand feel, light resistance, heat resistance, dirt resistance, abrasion resistance, scratch resistance and other functionalities of the obtained TPO artificial leather surface.
  • the paint layer is colorless and transparent, which can reduce the influence on the light transmittance of the TPO material.
  • the paint can also contain an appropriate amount of colorant to meet different requirements for the surface color of artificial leather, as long as the color of the paint does not cover the color of the TPO skin layer.
  • a pattern is provided on the paint layer.
  • the high temperature embossing on the paint layer is to make the final TPO artificial leather have the same appearance and feel as real leather.
  • the pattern produced by embossing on the paint layer will affect the light transmission effect of the material. Therefore, in order to minimize the impact on the light transmission performance of the material, the texture of the pattern should be designed to be as thin and shallow as possible.
  • the depth of the pattern of the paint layer is less than or equal to 0.05 mm, and the width of the pattern is less than or equal to 0.05 mm.
  • a base cloth is provided under the TPO skin layer.
  • the base fabric has light transmittance.
  • the present invention preferably uses a base fabric woven with long and short fibers.
  • the material of the base fabric in the present invention is not limited, and conventional natural or chemical fibers, such as polyamide fibers, polyester fibers, glass fibers, etc., may be used as base fabrics woven.
  • the TPO skin layer and the base fabric can be composited together by hot pressing, or can be bonded together by glue.
  • the TPO skin layer and the base fabric are composited together by hot pressing.
  • the TPO artificial leather with a base fabric structure according to the present invention is more suitable for stitching due to the existence of the base fabric, and can be used for manual wrapping, so that the TPO artificial leather is attached to the car interior skeleton, making the operation more convenient.
  • the light-permeable TPO artificial leather of the present invention may also contain no base fabric.
  • the artificial leather without base fabric is easy to tear when stitched, it usually needs to be vacuum suction, female mold forming or low pressure The injection molding and the car interior frame are bonded.
  • TPO skin layer contains polyolefin elastomer POE, polyolefin resin, rubber, light-transmitting masterbatch, and optional other additives, such as light stabilizers,
  • the various raw materials of the TPO skin layer can be stirred, mixed and coated in a conventional manner.
  • the polyolefin elastomer POE, polyolefin resin, rubber, transparent color masterbatch and other additives are mixed and extruded into a film in an extruder, preferably a twin-screw extruder.
  • the light-transmitting TPO artificial leather according to the present invention can be used in car interiors, such as car seats, armrests, door panels, dashboards and other parts.
  • the TPO composition according to the present invention and the TPO artificial leather formed therefrom can not only meet customer requirements for color, but also achieve light transmittance, and the light can be transmitted through the area where the lamp source is laid;
  • the formulation of the TPO composition, especially the toner formulation of the masterbatch, can achieve different light-transmitting colors; due to the combination of the base fabric, the TPO artificial leather of the present invention is in addition to the conventional vacuum adsorption, female mold molding, low-pressure injection molding and other processes.
  • the TPO artificial leather of the present invention has a soft feel, so it can be applied to parts directly in contact with the human body, and can meet the needs of car interiors. Application of other mechanical properties and processing requirements.
  • the first step add the non-polar resin, main toner and auxiliary toner to the twin-screw extruder according to the transparent masterbatch formula in Table 1, extrude and cut to obtain the masterbatch;
  • the polyolefin elastomer, polyolefin resin, rubber and the masterbatch prepared in the first step are added to the twin-screw extruder in the form of a composition. Heat and melt the components at 200°C and mix them evenly. Then extrude the obtained mixture to prepare a TPO skin layer with a thickness of 0.5 mm;
  • the third step is to uniformly coat a layer of water-based polyurethane paint with a thickness of about 0.2 ⁇ m on one side of the TPO skin layer by gravure printing to improve the surface feel and wear and scratch resistance;
  • the obtained TPO skin layer and the base fabric are directly hot-pressed and compounded on an embossing machine at 180°C, and the finished TPO artificial leather is formed in one step, so that the final TPO skin has the same appearance and texture as the leather. No adhesive is added in the hot pressing compound.
  • Step 5 Finish the finished product cutting according to customer requirements.
  • Test content testing method Test Results Tensile Strength GMW3010-2014 Vertical: 417N Horizontal: 388N Tear strength ISO13937-2-2000 Vertical: 65N Horizontal: 35N Softness GMW3390 Vertical: 77mm Horizontal: 75mm Flexibility ISO 5402-1:2017 No cracking Transmittance * 3.9% (transmitting purple light)
  • Transmittance detection method use datacolor tools plus software, use a small blackboard to calibrate the light source in the light transmittance detection mode, that is, the white light source with a wavelength in the range of 360-700nm, and place the TPO artificial leather on the light source port after the calibration is completed Click on the US datacolor850 color measurement analyzer to start the test.
  • the datacolor tools plus software processes the amount of white light transmitted by the material, and finally obtains the light transmittance data. The larger the value, the better the light transmittance.
  • TPO artificial leather was prepared by the same method as in Example 1, and the light transmittance of TPO artificial leather was detected by the same light transmittance detection method as in Example 1. The results of light transmittance are also shown in Table 3.
  • TPO artificial leather was prepared by the same method as in Example 1, and the light transmittance of TPO artificial leather was detected by the same light transmittance detection method as in Example 1. The results of light transmittance are also shown in Table 4.
  • TPO artificial leather was prepared by the same method as in Example 1, and the light transmittance of TPO artificial leather was detected by the same light transmittance detection method as in Example 1. The results of light transmittance are also shown in Table 5.
  • the TPO artificial leather was prepared by the same method as in Example 1, and the light transmittance of TPO artificial leather was detected by the same light transmittance detection method as in Example 1.
  • the light transmittance results are also shown in Table 6.
  • the TPO artificial leather was prepared by the same method as in Example 1, and the same light transmittance detection method as in Example 1 was used to observe the color of the light. The results are also shown in Table 7.
  • the TPO artificial leather was prepared by the same method as in Example 1, and the same light transmittance detection method as in Example 1 was used to observe the color of the light. The results are also shown in Table 8.
  • Table 8 TPO formula (unit: parts by weight) and transmittance color of Example 7
  • TPO artificial leather was prepared by the same method as in Example 1, and the light transmittance of TPO artificial leather was detected by the same light transmittance detection method as in Example 1. The results of light transmittance are also shown in Table 9.
  • TPO artificial leather was prepared by the same method as in Example 1, and the light transmittance of TPO artificial leather was detected by the same light transmittance detection method as in Example 1. The results of light transmittance are also shown in Table 10.
  • the translucent masterbatch conforming to the present invention is used, and the formula of the masterbatch and the content of the masterbatch in the skin layer conform to the limitation of the present invention.
  • the TPO skin layers obtained from Examples 1-3 all have good light transmittance.
  • Comparative Example 2 uses the same translucent masterbatch formula, but the content of the masterbatch in the skin layer in Comparative Example 2 exceeds the upper limit of the limit of the present invention, resulting in The light transmittance of the TPO skin layer obtained from Comparative Example 2 was significantly decreased.
  • the translucent masterbatch formulations of Examples 6 and 7 all use carbon black as the main toner, so that the TPO skin layer exhibits a black base color when it is not exposed to back light. Due to the addition of different auxiliary toners, the TPO skin layer shows different colors of light when the backside is illuminated.

Abstract

本发明涉及一种具有透光特性的TPO组合物，其包括聚烯烃弹性体POE、聚烯烃树脂、橡胶以及透光色母粒，其中，基于透光色母粒总重量为100重量份，该透光色母粒包括50-70重量份的非极性树脂以及30-50重量份的色粉。本发明还涉及一种TPO人造革，其包括上述TPO组合物形成的TPO表皮层。根据本发明的TPO人造革能够应用于汽车内饰中，其在满足期望的颜色覆盖同时能够实现良好的透光性。

Description

具有透光特性的TPO组合物及含有该组合物的TPO人造革 技术领域
本发明涉及一种具有透光特性的热塑性聚烯烃弹性体(也可以称TPO)组合物，以及由该TPO组合物制造的TPO人造革。
背景技术
在汽车内饰中广泛使用TPO人造革，其优点在于，具有良好的热力学性能，不含卤素，低散发，无增塑剂等等。例如CN106393890A公开了一种超软质环保型TPO汽车内饰材料，其中用软质TPO表皮、软质海绵配方，提升了内饰材料的柔软手感，并且用软质水性聚氨酯油漆进行表面涂覆，三层结构均提高了材料的柔软性能，降低了产品的密度。
随着社会的发展，人们在购买汽车时不仅关注性能，而且对汽车内饰提出了更高的要求，希望汽车内饰更加酷炫，更有科技感。对此，汽车的灯光效果无疑是提高科技感和外观效果的一种手段。目前市面上已有的汽车内饰产品通常采用透光硬质塑料来实现灯光效果，其缺陷在于，质感太硬不柔软，不易用在座椅、扶手、拐角等对柔软度要求高的地方，并且不能大面积应用，也不能和骨架材料很好地贴合；同时这样的材料成本较高，生产效率低。
CN102367318A公开了制备一种聚苯乙烯透光色母粒，其包含聚苯乙烯以及占聚苯乙烯总重0.01-10％的溶剂型透明染料。然而聚苯乙烯是极性材料，由于其与非极性TPO的相容性不好，会导致混合不均匀以及柔软度不佳，另外，较低含量的透明染料不足以提供足够的颜色遮盖力。因此这样的聚苯乙烯透光色母粒不适合用于TPO汽车内饰中。
另外，DE102015101331A1中描述了聚氨酯(PU)或聚氯乙烯(PVC)人造革的透光性改进，这些人造革的结构一般包含基布、表 皮透光层和油漆层。该文献中大致地提到了对人造革透光性的影响因素主要包括层的厚度、数量和种类以及层中的色料含量以及基布的种类和密度都会影响。然而，文中没有对上述各个影响因素进行具体描述和分析，也没有具体针对各个人造革种类进行性能的改进。
发明内容
基于上述现有技术，本发明的目的在于提供一种具有透光特性的TPO组合物，以及由该TPO组合物制造的TPO人造革。所述TPO人造革能够应用于汽车内饰中，其在满足期望的颜色覆盖同时能够实现良好的透光性。
为实现上述技术目的，本发明提出一种具有透光特性的TPO组合物，其包括聚烯烃树脂、橡胶以及透光色母粒，其中，基于透光色母粒总重量为100重量份，该透光色母粒包括
-50-70重量份，例如50重量份、51重量份、52重量份、53重量份、54重量份、55重量份、56重量份、57重量份、58重量份、59重量份、60重量份、61重量份、62重量份、63重量份、64重量份、65重量份、66重量份、67重量份、68重量份、69重量份、70重量份或者这些数值中任两者之间范围内的非极性树脂，以及
-30-50重量份，例如30重量份、31重量份、32重量份、33重量份、34重量份、35重量份、36重量份、37重量份、38重量份、39重量份、40重量份、41重量份、42重量份、43重量份、44重量份、45重量份、46重量份、47重量份、48重量份、49重量份、50重量份或者这些数值中任两者之间范围内的色粉。
聚烯烃树脂和橡胶粒子通常采用挤出机、例如双螺杆挤出机共混而成，在加工过程中如果直接加入色粉，因为色粉飞扬而会造成加料困难和分散差的问题。由此，将色粉与非极性树脂共混制造成色母粒，从而提高色粉在TPO中的分散性，使得色粉分散地更均匀。
本发明主要通过调整色母粒的色浓度来改进TPO的透光性。对此，本发明发现，当色粉与非极性树脂共混时，在色粉不变的情况下增加 非极性树脂的用量，或者在非极性树脂不变的情况下降低色粉的用量，也就是说，通过增加非极性树脂在色母粒组成中的相对含量或者减少色粉在色母粒组成中的相对含量，可以降低色母粒的色浓度，从而获得根据本发明的透光色母粒。另外，在加工时降低色母粒的用量，可以进一步改进透光的效果。
如果非极性树脂在透光色母粒中的含量低于50重量份，则色母粒的色浓度不够低，因而无法实现透光度的充分提高。如果非极性树脂在透光色母粒中的含量高于70重量份，则会导致应用到TPO材料上时不具备足够的颜色遮盖力。
透光色母粒中的非极性树脂能够与非极性的TPO基体材料充分相容且均匀混合，从而实现TPO中颜色的均匀分散。根据本发明的一个优选实施方式，透光色母粒中的非极性树脂选自PP和/或PE，其有助于改进组合物的柔软度。
根据本发明的一个优选的实施方式，色粉中包含
-20-40重量份，例如20重量份、21重量份、22重量份、23重量份、24重量份、25重量份、26重量份、27重量份、28重量份、29重量份、30重量份、31重量份、32重量份、33重量份、34重量份、35重量份、36重量份、37重量份、38重量份、39重量份、40重量份或者这些数值中任两者之间范围内的主色粉，以及
-10-20重量份，例如10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份或者这些数值中任两者之间范围内的辅色粉。
主色粉能够实现期望TPO组合物呈现的基色，例如主色粉选择炭黑，使得TPO组合物总体呈现黑色的基色。当然，主色粉也能够选择有机红、有机黄、酞青蓝、钛白等。为了在主要颜色的基础上调配出更符合期望的颜色，通常还加入辅色粉进行调节。
根据本发明，通过调整色粉的配方实现不同的透光颜色。根据本发明一个优选的实施方式，TPO组合物在经光照、尤其白光照射时能够透射出不同于组合物基色的光颜色。例如，当采用炭黑作为主色粉， 并加入钛白粉、铬绿、铁红作为辅色粉时，得到的TPO组合物在不受光照时呈现黑色的基色，经白光照射时，则能够透射出紫色的光。
根据本发明另一个优选的实施方式，根据用户对于透光颜色的不同需求，通过加入不同颜色的辅色粉能够调节不同的透光颜色。例如在炭黑为主色粉的情况下，加入钛白粉、铬绿、铁红作为辅色粉时能够在背面照射白光时透出紫色的光；而当加入钛白粉、铬绿、靛蓝作为辅色粉时则能够在背面照射白光时透出蓝色的光。
根据本发明另一个优选的实施方式，通过调整不同的辅色粉比例能够调节不同的透光颜色浓度，当辅色粉含量相应增大时能够加深透色光的浓度，只要辅色粉的比例没有高至阻碍主色粉的颜色。
根据本发明另一个优选的实施方式，TPO组合物还包含聚烯烃弹性体POE。TPO组合物中的聚烯烃弹性体POE为乙烯和α烯烃的共聚物，其中，聚合而得的直链上的聚乙烯PE作为硬段，而α烯烃则成为支链软段。根据本发明的一个优选的实施方式，聚烯烃弹性体为乙烯和辛烯的共聚物。由此得到的聚烯烃弹性体POE能够有效地提高材料的柔软度。
根据本发明，TPO组合物中的聚烯烃树脂可以选用常规的各种聚烯烃，优选脂肪族聚烯烃，例如低密度聚乙烯LDPE、尤其线性低密度聚乙烯LLDPE，中密度聚乙烯MDPE，聚丙烯PP，聚丁烯PB等。聚烯烃树脂有助于提高材料的物理机械性能以及耐热性。
原则上，TPO组合物中的橡胶可以选用常规的各种橡胶，例如热塑性动态硫化橡胶TPV、三元乙丙橡胶EPDM、SEBS、乙烯辛烯橡胶、乙烯丁烯橡胶、乙烯丙烯橡胶等。根据本发明的一个优选的实施方式，TPO组合物中的橡胶采用TPV。常规EPDM进行硫化并添加PP，由此得到的TPV能够进一步有效地提高材料的韧性。
为了实现良好的透光性，在选择各种TPO基础材料粒子，例如POE原料粒子、聚烯烃原料粒子、橡胶原料粒子时，优选颜色较透明的原料粒子，从而使得TPO原料粒子本身是透明的。
另外，在TPO组合物中还可能添加额外助剂，例如抗氧剂、光稳 定剂、阻燃剂等，均可根据需要选择本领域技术人员熟知的常规材料。优选地，本发明仅采用光稳定剂作为额外助剂，其有利于提高材料的耐光稳定性。
根据本发明的一个实施方式，基于POE、聚烯烃树脂、橡胶的总量为100重量份，本发明的TPO组合物包含
40-50重量份，例如40重量份、41重量份、42重量份、43重量份、44重量份、45重量份、46重量份、47重量份、48重量份、49重量份、50重量份或者这些数值中任两者之间范围内的POE；
20-30重量份，例如20重量份、21重量份、22重量份、23重量份、24重量份、25重量份、26重量份、27重量份、28重量份、29重量份、30重量份或者这些数值中任两者之间范围内的聚烯烃树脂；
20-40重量份，例如20重量份、21重量份、22重量份、23重量份、24重量份、25重量份、26重量份、27重量份、28重量份、29重量份、30重量份、31重量份、32重量份、33重量份、34重量份、35重量份、36重量份、37重量份、38重量份、39重量份、40重量份或者这些数值中任两者之间范围内的橡胶；
1-4重量份，例如1重量份、2重量份、3重量份、4重量份或者这些数值中任两者之间范围内的色母粒。
根据本发明的一个有利的实施方式，TPO组合物中还包含1-3重量份，例如1重量份、2重量份、3重量份或者这些数值中任两者之间范围内的光稳定剂。
其中，当该TPO组合物应用于制造作为汽车内饰的人造革时，为了在保证透光率的同时确保产品具有足够的颜色遮盖力，进而保证人造革的成品颜色质量，优选在TPO组合物中基于POE、聚烯烃树脂、橡胶的总量为100重量份含有2-4重量份的色母粒。这是因为，低于2重量份的色母粒可能不足以达到期望的成品基色。
为了实现开头所述的技术目的，本发明还提出一种TPO人造革，其包括由上述根据本发明所述的TPO组合物形成的TPO表皮层。
通过采用前述透光的TPO组合物，能够获得透光的TPO表皮层。在本发明中，前述TPO组合物的所有特征以及相应效果均适用于由该TPO组合物形成的TPO表皮层，在此不再重复描述。
根据本发明的一个优选的实施方式，在TPO表皮层上设有油漆层。为了保证整体TPO人造革的透光性，优选该油漆层也具有透光性。可以采用本领域已知的常规油漆进行表面涂覆。本发明中优选采用水性聚氨酯油漆进行涂覆。所述水性聚氨酯油漆的配方包含70-80重量份的水性聚氨酯改性树脂以及8-20重量份的助剂。通过在TPO材料表面印刷油漆而进行表面处理，能够有利地改善获得的TPO人造革表面的光泽、手感以及耐光、耐热、耐脏、耐磨、耐刮擦及其他功能性。
为了改进该油漆层的透光性进而提高整体TPO人造革的透光性，优选该油漆层是无色透明的，这样能够减小对TPO材料透光性的影响。当然，在油漆中也能够含有适量的色料，从而满足对于人造革表面颜色的不同需求，只要该油漆的颜色不会遮盖TPO表皮层的颜色。
根据本发明的优选实施方式，在油漆层上设有花纹。在油漆层上进行的高温压花是为了使得最终的TPO人造革具有和真皮一样的外观花纹和手感。然而油漆层上通过压花产生的花纹会影响材料的透光效果。因此，为了尽可能减小对材料透光性能的影响，该花纹的纹理应当设计地尽可能细且浅。根据本发明的一个优选实施方式，油漆层花纹的深度≤0.05mm，花纹的宽度≤0.05mm。
根据本发明的一个优选的实施方式，在TPO表皮层下方设有基布。为了保证整体TPO人造革的透光性，同样优选该基布具有透光性。为了减小基布对透光性的影响并进而提高整体TPO人造革的透光性，优选采用布纹表面平整的基布，其对于透光性的影响较小；同时，基布表面具有适当的粗糙度以便于提供足够大的摩擦力，从而保证基布与TPO表皮在热贴合情况下的粘结力。为了同时兼顾透光性和粘结性，本发明优选采用长短纤梭织的基布。本发明中基布的材料不受限制，可以采用常规的天然或化学纤维，如聚酰胺纤维、聚酯纤维、玻璃纤维等纺织得到的基布。
根据本发明，TPO表皮层与基布可以通过热压复合在一起，也可以是通过胶水粘合在一起。根据本发明的一个优选的实施方式，TPO表皮层与基布通过热压复合在一起。根据本发明的含基布结构的TPO人造革由于基布的存在而更加适合缝合，可用于手工包覆，从而将TPO人造革贴合至汽车内饰骨架，使得操作更方便。
当然，本发明所述的透光的TPO人造革也可以不含基布，在这种情况下，由于不含基布的人造革缝合时易撕裂，因此通常需要通过真空吸附、阴模成型或者低压注塑与汽车内饰骨架进行贴合。
为了制备根据本发明所述的透光的TPO人造革，可以采用包含下述步骤的制备方法：
A)制备透光色母粒，其中将色粉与非极性树脂、例如PE和/或PP共混，制造成透光色母粒，
B)制备TPO表皮层，该TPO表皮层包含聚烯烃弹性体POE、聚烯烃树脂、橡胶、透光色母粒以及可选的其他助剂、例如光稳定剂，
TPO表皮层的各种原材料能够以常规的方式搅拌混合并进行涂布。根据本发明方法的一个优选实施方式，将聚烯烃弹性体POE、聚烯烃树脂、橡胶、透明色母料以及其他助剂在挤出机、优选双螺杆挤出机中混合并挤出成膜。
在本发明中，前述TPO组合物以及相应TPO人造革的所有特征以及相应效果均适用于制造该TPO人造革的方法，在此不再重复描述。
根据本发明所述的透光的TPO人造革能够应用在汽车内饰中，例如汽车座椅、扶手、门板、仪表盘等部位。
本发明的优点在于：根据本发明的TPO组合物以及由其形成的TPO人造革既能满足客户对颜色的要求，又能实现透光性，在铺设灯源的区域可以将灯光透射出来；通过调整TPO组合物的配方，尤其其中色母粒的色粉配方，能够实现不同的透光颜色；由于结合了基布，本发明的TPO人造革除了常规的真空吸附、阴模成型、低压注塑等工艺，还能够通过手工包覆应用到汽车座椅、扶手、门板、仪表盘等部位；同时，本发明的TPO人造革具有柔软的手感，因而能够应用到直 接与人体接触的部位，而且能够满足汽车内饰应用的其他机械性能和加工方面的要求。
具体实施方式
为使本领域的技术人员更好地理解本发明的技术方案，下面结合实施例和对比例对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
按照下述方法制备TPO人造革：
第一步，根据表1中的透光色母粒配方将非极性树脂、主色粉和辅色粉加入到双螺杆挤出机中，挤出并切割获得色母粒；
第二步，根据表1中的TPO表皮层配方将聚烯烃弹性体、聚烯烃树脂、橡胶和由第一步制得的色母粒以组合物的形式加入到双螺杆挤出机中，在200℃将各组分加热熔融、混合均匀。然后将得到的混合物挤出，制备得到0.5mm厚度的TPO表皮层；
第三步，在TPO表皮层的一侧通过凹版印刷的方式，均匀涂覆一层厚度约为0.2μm的水性聚氨酯体系油漆，以改善表层的手感和耐磨、耐刮擦性能；
第四步，将得到的TPO表皮层与基布在压花机上在180℃直接热压复合，一步成型制得TPO人造革成品，使得最终TPO表皮具有和真皮一样的外观花纹、手感。热压复合中没有外加任何粘合剂。
第五步：按照客户要求完成成品切割。
表1：实施例1的TPO配方(单位：重量份)
Figure PCTCN2020093152-appb-000001
Figure PCTCN2020093152-appb-000002
检测由此获得的TPO人造革的拉伸强度、撕裂强度、柔软度、耐折曲性(Bally Flex)以及透光率，结果显示在如下表2中：
表2：根据实施例1获得的TPO人造革性能
测试内容 测试方法 测试结果
拉伸强度 GMW3010-2014 纵向：417N 横向：388N
撕裂强度 ISO13937-2-2000 纵向：65N 横向：35N
柔软度 GMW3390 纵向：77mm 横向：75mm
耐折曲性 ISO 5402-1:2017 无开裂
透光率 * 3.9％(透紫光)
*透光率的检测方法：采用datacolor tools plus软件，使用小黑板对透光率检测模式的光源，即波长在360-700nm范围内的白光光源进行校正，校正完成后将TPO人造革放在光源口处，点击美国datacolor850测色分析仪开始测试，datacolor tools plus软件将材料透过的白光的量进行数据处理，最终得到透光率的数据，数值越大透光效果越好。
实施例2：
根据表3中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法检测TPO人造革的透光率，透光率的结果也展示在表3中。
表3：实施例2的TPO配方(单位：重量份)及透光性
Figure PCTCN2020093152-appb-000003
Figure PCTCN2020093152-appb-000004
实施例3：
根据表4中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法检测TPO人造革的透光率，透光率的结果也展示在表4中。
表4：实施例3的TPO配方(单位：重量份)及透光性
Figure PCTCN2020093152-appb-000005
实施例4：
根据表5中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法检测TPO人造革的透光率，透光率的结果也展示在表5中。
表5：实施例4的TPO配方(单位：重量份)及透光性
Figure PCTCN2020093152-appb-000006
实施例5：
根据表6中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法检测TPO人造革的透光率，透光率的结果也展示在表6中。
表6：实施例5的TPO配方(单位：重量份)及透光性
Figure PCTCN2020093152-appb-000007
实施例6：
根据表7中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法，观测透光的颜色，结果也展示在表7中。
表7：实施例6的TPO配方(单位：重量份)及透光颜色
Figure PCTCN2020093152-appb-000008
实施例7：
根据表8中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率 检测方法，观测透光的颜色，结果也展示在表8中。
表8：实施例7的TPO配方(单位：重量份)及透光颜色
Figure PCTCN2020093152-appb-000009
对比例1：
根据表9中的普通色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法检测TPO人造革的透光率，透光率的结果也展示在表9中。
表9：对比例1的TPO配方(单位：重量份)及透光性
Figure PCTCN2020093152-appb-000010
对比例2：
根据表10中的透光色母粒配方以及TPO表皮层配方，采用与实施例1相同的方法制备TPO人造革，并采用与实施例1中相同的透光率检测方法检测TPO人造革的透光率，透光率的结果也展示在表10中。
表10：对比例2的TPO配方(单位：重量份)及透光性
Figure PCTCN2020093152-appb-000011
结果比较：
-实施例1-3中均采用符合本发明的透光色母粒，色母粒的配方以及色母粒在表皮层中的含量均符合本发明的限定。由实施例1-3获得的TPO表皮层均具有良好的透光性。
-与实施例1-3相比，对比例1中采用的是常规配方的普通色母粒，尽管色母粒在表皮层中的含量符合本发明的限定，但最终获得的TPO表皮层是不透光的。
-对比例2与实施例4、5相比，虽然采用相同的透光色母粒配方，然而对比例2中色母粒在表皮层中的含量超过了本发明限定范围的上限，由此导致由对比例2获得的TPO表皮层的透光率显著下降。
-实施例6、7的透光色母粒配方中均采用炭黑为主色粉，使得TPO表皮层在不受背面光照时均呈现黑色的基色。由于添加了不同的辅色粉，使得TPO表皮层在背面光照时透出不同颜色的光。
可以理解的是，以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。

Claims (11)

  1. 一种具有透光特性的TPO组合物，所述TPO组合物包含聚烯烃树脂、橡胶以及透光色母粒，其特征在于，
    基于透光色母粒总重量为100重量份，所述透光色母粒包括50-70重量份的非极性树脂以及30-50重量份的色粉。
  2. 根据权利要求1所述的具有透光特性的TPO组合物，其特征在于，所述色粉中包含20-40重量份的主色粉以及10-20重量份的辅色粉。
  3. 根据权利要求2所述的具有透光特性的TPO组合物，其特征在于，所述TPO组合物在经光照、尤其白光照射时能够透射出不同于组合物基色的光颜色。
  4. 根据权利要求2所述的具有透光特性的TPO组合物，其特征在于，通过加入不同颜色的辅色粉能够调节不同的透光颜色。
  5. 根据权利要求2所述的具有透光特性的TPO组合物，其特征在于，通过调整不同的辅色粉比例能够调节不同的透光颜色浓度。
  6. 根据权利要求1至5中任一项所述的具有透光特性的TPO组合物，其特征在于，所述TPO组合物还包含聚烯烃弹性体POE。
  7. 根据权利要求6所述的具有透光特性的TPO组合物，其特征在于，基于POE、聚烯烃树脂、橡胶的总量为100重量份，所述TPO组合物包含
    40-50重量份的POE、
    20-30重量份的聚烯烃树脂、
    20-40重量份的橡胶、和
    1-4重量份的色母粒。
  8. 一种TPO人造革，所述TPO人造革包括由根据权利要求1至7中任一项所述的TPO组合物形成的TPO表皮层。
  9. 根据权利要求8所述的TPO人造革，其特征在于，在所述TPO表皮层上设有油漆层，所述油漆层具有透光性，优选所述油漆层是无色透明的。
  10. 根据权利要求9所述的TPO人造革，其特征在于，在所述油漆层上设有花纹，优选所述花纹的深度≤0.05mm，所述花纹的宽度≤0.05mm。
  11. 根据权利要求8至9中任意一项所述的TPO人造革，其特征在于，在所述TPO表皮层下方设有基布，所述基布具有透光性，优选长短纤梭织的基布。
PCT/CN2020/093152 2019-06-03 2020-05-29 具有透光特性的tpo组合物及含有该组合物的tpo人造革 WO2020244449A1 (zh)

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