WO2022127215A1 - 抗刮耐磨自修复的复合板及其制备方法和应用 - Google Patents

抗刮耐磨自修复的复合板及其制备方法和应用 Download PDF

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WO2022127215A1
WO2022127215A1 PCT/CN2021/117677 CN2021117677W WO2022127215A1 WO 2022127215 A1 WO2022127215 A1 WO 2022127215A1 CN 2021117677 W CN2021117677 W CN 2021117677W WO 2022127215 A1 WO2022127215 A1 WO 2022127215A1
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layer
resistant
thermoplastic polyurethane
scratch
polyurethane elastomer
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PCT/CN2021/117677
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English (en)
French (fr)
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杨飞虎
程先胜
孙健
李广琦
于猛
郑立军
李德宏
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浙江佳适逸宝板材有限公司
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Publication of WO2022127215A1 publication Critical patent/WO2022127215A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/0866—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements composed of several layers, e.g. sandwich panels or layered panels
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/22—Resiliently-mounted floors, e.g. sprung floors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels
    • B32B2607/02—Wall papers, wall coverings
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for

Definitions

  • the invention relates to the field of building ground and wall decoration materials, in particular to a scratch-resistant, wear-resistant and self-repairing composite board and a preparation method and application thereof.
  • elastic floor and wall panel products have been widely used in the market, and they are a kind of decorative products with very good development prospects.
  • elastic floor is a very popular new type of light-body floor decoration material in the world today, also known as "light-body floor material”. It is a popular product in Europe, America, Asia, Japan and South Korea. Entering the Chinese market, it has been widely recognized and widely used in large and medium-sized cities in China, such as families, hospitals, schools, office buildings, factories, public places, supermarkets, businesses and other places.
  • polyvinyl chloride and its copolymer resin are used as the main raw materials, and auxiliary materials such as fillers, plasticizers, stabilizers, and colorants are added. Process produced.
  • PVC-type wear-resistant layers which have the disadvantage of not being scratch-resistant, and permanent scratches are left after scratching, which greatly affects the use, and also has short service life and poor economy.
  • PVC contains a large amount of chlorine. In the fire, the PVC floor releases hydrochloric acid and other toxic gases during the combustion process, producing a large amount of smoke, which is the main cause of death in the fire.
  • Thermoplastic polyurethane elastomer rubber is a rigid block obtained by the reaction of diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) and a chain extender, or is made of diphenylmethane diisocyanate (MDI) or toluene diisocyanate.
  • Diisocyanate molecules such as isocyanate (TDI) and flexible segments obtained by the reaction of macromolecular polyols are alternately formed. It has the advantages of wide hardness range, scratch resistance, oil resistance, tear resistance, low temperature resistance, transparency and good elasticity.
  • the application of thermoplastic polyurethane elastomer rubber layers of different hardness into composite panels has not yet been reported.
  • the invention discloses a scratch-resistant and wear-resistant self-repairing composite board.
  • the composite board includes a substrate layer, a color filter layer, and a scratch-resistant and wear-resistant layer in sequence from bottom to top.
  • the scratch-resistant and wear-resistant layer includes at least Two layers of thermoplastic polyurethane elastomer rubber of different hardness.
  • the number of layers of the thermoplastic polyurethane elastomer rubber layer is 2, the thermoplastic polyurethane elastomer rubber layer is attached to the color filter layer, and the inner layer of thermoplastic polyurethane elastomer in contact with the color filter layer
  • the Shore D hardness of the rubber layer is 65-85, the Shore D hardness of the thermoplastic polyurethane elastomer rubber layer of the surface layer not in contact with the color filter layer is 30-45, and the hardness of the thermoplastic polyurethane elastomer rubber layer of the inner layer > the surface layer
  • the hardness of the thermoplastic polyurethane elastomer rubber layer is 60-85, the Shore D hardness of the thermoplastic polyurethane elastomer rubber layer of the surface layer not in contact with the color filter layer is 30-45, and the hardness of the thermoplastic polyurethane elastomer rubber layer of the inner layer > the surface layer The hardness of the thermoplastic polyurethane elastomer rubber layer.
  • the number of layers of the thermoplastic polyurethane elastomer rubber layer is greater than 2 layers, the thermoplastic polyurethane elastomer rubber layer is attached to the color filter layer, and the inner layer of thermoplastic polyurethane elastomer in contact with the color filter layer
  • the hardness of the rubber layer, Shore D is 75-85, and the hardness of the surface layer thermoplastic polyurethane elastomer rubber layer that is not in contact with the color filter layer is 30-45, which is between the inner layer thermoplastic polyurethane elastomer rubber layer and the surface layer thermoplastic polyurethane
  • the Shore D of the thermoplastic polyurethane elastomer rubber layers of several intermediate layers between the elastomer rubber layers is 65-75, and the hardness of the thermoplastic polyurethane elastomer rubber layers gradually decreases from the inner layer to the surface layer.
  • the number of layers of the thermoplastic polyurethane elastomer rubber layer is 2-5 layers.
  • the thickness of the anti-scratch and wear-resistant layer is 0.30-2.00 mm.
  • each layer of the thermoplastic polyurethane elastomer rubber layer has a thickness of 0.15-1.90 mm.
  • thermoplastic polyurethane elastomer rubber layer includes the following raw materials in parts by weight:
  • PVC resin 20-100 parts of PVC resin, 50-200 parts of TPU particles, 5-30 parts of plasticizer, 3-25 parts of UV absorber, 3-35 parts of antioxidant, 5-20 parts of calcium-zinc composite stabilizer, light stabilizer 5-20 parts, flame retardant 5-30 parts, internal lubricant 0.3-1.5 parts.
  • thermoplastic polyurethane elastomer rubber layer includes the following raw materials in parts by weight:
  • PVC resin 30-70 parts of PVC resin, 100-180 parts of TPU particles, 5-20 parts of plasticizer, 5-15 parts of UV absorber, 5-15 parts of antioxidant, 5-15 parts of calcium-zinc composite stabilizer.
  • thermoplastic polyurethane elastomer rubber layer further comprises the following raw materials in parts by weight:
  • the Shore D hardness of the TPU particles is 30-80.
  • the polyisocyanate of the TPU is a symmetric polyisocyanate, an asymmetric polyisocyanate or a mixture thereof.
  • the polyisocyanate of the TPU is one or a mixture of two or more of diphenylmethane 2,4-diisocyanate, toluene 2,4-diisocyanate or toluene 2,6-diisocyanate.
  • the chain extender of the TPU is a polyol, selected from polyether polyol, polyester polyol, polyether ester polyol or polycarbonate polyol, one or more polyols in combination.
  • the chain extender of the TPU is a diol with a molecular weight range of 60-600 g/mol.
  • the plasticizer is environmentally friendly dioctyl terephthalate (DOTP).
  • DBP dioctyl terephthalate
  • the UV absorber is one or a mixture of UV329, UV328, UV234 and UV360.
  • the antioxidant is one or a mixture of antioxidants 1010, 168 and 1076.
  • light stabilizer 770 Preferably, light stabilizer 770.
  • Internal lubricant G60 Preferably.
  • the composite board further comprises a UV coating, and the UV coating is attached to the scratch-resistant and wear-resistant layer;
  • the anti-scratch and wear-resistant layer is attached to the base material layer covered with the color filter layer, so that the color filter layer is interposed between the anti-scratch and wear-resistant layer and the base material layer.
  • the thickness of the base material layer is less than or equal to 10 mm;
  • the substrate layer is SPC board, WPC board, LVT board, PVC board or MDF board.
  • the substrate layer includes polyolefin, calcium carbonate, calcium zinc stabilizer, acrylate copolymer ACR, polyethylene wax (PE wax), lubricant, and recycled material.
  • the base material layer comprises the following raw materials in parts by weight:
  • Another object of the present invention is to provide a preparation method of the above-mentioned composite board, based on the transesterification between two or more thermoplastic polyurethane elastomer rubber layers side by side in a molten state, in the contact area, a first One layer of isocyanate and second layer of polyol react with polyurethane based on second layer of isocyanate and first layer of polyol, so that the thermoplastic polyurethane elastomer rubber layers of different layers can be strongly bonded together, so as to obtain scratch resistance and wear resistance and self-healing composite membrane.
  • the preparation method mainly comprises the following steps:
  • thermoplastic polyurethane elastomer rubber layers obtained in step (1) in a hot-melt state with different hardness are stacked from bottom to top in the order of gradually decreasing hardness, and heat-covered to synthesize a TPU scratch-resistant layer.
  • the base material is extruded through an extruder, and then rolled through a four-roll calender or a multi-roll calender.
  • the degree of polymerization of the PVC resin is 600-1500, and the hardness of the TPU particles is in the range of 35-120.
  • the temperature range is controlled at 45-130°C, and the rotational speed is 2000-4000 r/min.
  • the temperature is maintained at 160-230°C.
  • the Shore D hardness of the thermoplastic polyurethane elastomer rubber surface layer is 30-45, and the thickness thereof is 0.15-1.99 mm.
  • the four-roll calender or the cold-heat integrated machine performs the calendering process on the base material, and the temperature is maintained at 120-160°C.
  • the present invention further provides the application of the above-mentioned scratch-resistant and wear-resistant self-healing composite board in building decoration.
  • the building decoration mainly includes civil building decoration and public building decoration.
  • the self-healing composite board is mainly used for decoration of the ground or wall.
  • the self-healing composite panel is mainly used as a floor or wall covering.
  • the self-healing composite panel is mainly used as a floor.
  • the composite board product of the present invention has stable performance, greatly improves the anti-scratch and wear-resistant performance, and its anti-scratch and wear-resistant performance can reach more than 6,000 revolutions, while the existing traditional board using PVC film, its anti-scratch and wear-resistant performance It is about 4500 rpm, which is obviously better than the traditional sheet of PVC wear-resistant layer.
  • the surface layer of the composite board of the present invention is a thermoplastic polyurethane elastomer rubber layer, when scratches are generated on the surface of the composite board by external force, after a period of time, it can be repaired by itself, which prolongs the overall service life of the composite board and can reach 20 years.
  • the surface texture of the composite board of the present invention is obviously better than that of the stone-plastic board, and is closer to the effect of the surface of solid wood, which is easily accepted by consumers.
  • the composite board of the present invention has high comprehensive cost performance, and its cost is roughly equivalent to the cost of traditional boards, which is conducive to its popularization and popularization, and opens up the market space of elastic flooring.
  • thermoplastic polyurethane elastomer rubber layer of the present invention has very good compatibility with the substrate layer, and the substrate layer can be selected from SPC sheets covered with a color filter layer, WPC sheets covered with a color filter layer,
  • the LVT sheet with the color film layer or the MDF sheet covered with the color film layer can be laminated by the thermoplastic polyurethane elastomer rubber layer in the hot melt state, and the lamination process after gluing is omitted, and the production efficiency is high. , can be mass-produced, the production process is simple and stable.
  • the composite board of the present invention does not use adhesive in the preparation process, and is low in formaldehyde and environmentally friendly.
  • the formaldehyde test level of the composite board reaches the E0 level standard.
  • the composite board of the present invention has a wide range of applications, and can be used in areas with high requirements for scratch resistance and pollution resistance such as civil buildings and public buildings. It can replace ceramic tiles, traditional boards and other products, and can ensure the overall decoration style. .
  • FIG. 1 is a schematic structural diagram of the scratch-resistant and wear-resistant self-healing composite plate in the embodiment, 1 is a scratch-resistant and wear-resistant self-healing layer, 2 is a color filter layer, and 3 is a substrate layer.
  • FIG. 2 is a schematic structural diagram of the scratch-resistant and wear-resistant self-healing layer described in the embodiment, 101 is a thermoplastic polyurethane elastomer rubber inner layer, and 102 is a thermoplastic polyurethane elastomer rubber surface layer.
  • a preparation method of a scratch-resistant and wear-resistant self-healing composite plate mainly comprises the following steps:
  • thermoplastic polyurethane elastomer inner layer in the hot-melt state obtained in step (1) and the thermoplastic polyurethane elastomer outer layer in the hot-melt state obtained in step (2) are heat-coated to synthesize a TPU scratch-resistant layer.
  • a preparation method of a scratch-resistant and wear-resistant self-healing composite plate mainly comprises the following steps:
  • thermoplastic polyurethane elastomer rubber inner layer with a hardness of Shore D of 70 and a thickness of 0.20mm;
  • thermoplastic polyurethane elastomer rubber surface layer with a hardness of Shore D of 39 and a thickness of 0.20mm;
  • thermoplastic polyurethane elastomer inner layer in the hot-melt state obtained in step (1) and the thermoplastic polyurethane elastomer outer layer in the hot-melt state obtained in step (2) are heat-coated to synthesize a TPU scratch-resistant layer.
  • a preparation method of a scratch-resistant and wear-resistant self-healing composite plate mainly comprises the following steps:
  • thermoplastic polyurethane elastomer rubber surface layer with a hardness of Shore D of 41 and a thickness of 0.15mm;
  • thermoplastic polyurethane elastomer inner layer in the hot-melt state obtained in step (1) and the thermoplastic polyurethane elastomer outer layer in the hot-melt state obtained in step (2) are heat-coated to synthesize a TPU scratch-resistant layer.
  • a preparation method of a scratch-resistant and wear-resistant self-healing composite plate mainly comprises the following steps:
  • thermoplastic polyurethane elastomer rubber inner layer with a hardness of Shore D of 78 and a thickness of 0.15mm;
  • thermoplastic polyurethane elastomer rubber surface layer with a hardness of Shore D of 43 and a thickness of 0.15mm;
  • thermoplastic polyurethane elastomer inner layer in the hot-melt state obtained in step (1) and the thermoplastic polyurethane elastomer outer layer in the hot-melt state obtained in step (2) are heat-coated to synthesize a TPU scratch-resistant layer.
  • a preparation method of a scratch-resistant and wear-resistant self-healing composite plate mainly comprises the following steps:
  • thermoplastic polyurethane elastomer inner layer in the hot-melt state obtained in step (1) and the thermoplastic polyurethane elastomer outer layer in the hot-melt state obtained in step (2) are heat-coated to synthesize a TPU scratch-resistant layer with a thickness of 0.60 mm.
  • a preparation method of a wear-resistant composite plate mainly comprises the following steps:
  • step (2) Evenly coat the adhesive on one side of the anti-scratch and wear-resistant layer obtained in step (1), and then stick the adhesive-coated wear-resistant layer on the SPC sheet covered with the color filter layer (thickness is 4.5mm). ), and finally press the above-mentioned composite plate with a hot and cold integrated press, keep the temperature at 145 ° C, the pressure is 50 tons, and the time is 14 h to obtain the wear-resistant composite plate.
  • a preparation method of a wear-resistant composite plate mainly comprises the following steps:
  • step (2) Evenly coat the adhesive on one side of the anti-scratch and wear-resistant layer obtained in step (1), and then stick the adhesive-coated wear-resistant layer on the SPC sheet covered with the color filter layer (thickness is 4.5mm). ), and finally press the above-mentioned composite plate with a hot and cold integrated press, keep the temperature at 145 ° C, the pressure is 50 tons, and the time is 14 h to obtain the wear-resistant composite plate.
  • a preparation method of a wear-resistant composite plate mainly comprises the following steps:
  • step (2) Evenly coat the adhesive on one side of the anti-scratch and wear-resistant layer obtained in step (1), and then stick the adhesive-coated wear-resistant layer on the SPC sheet covered with the color filter layer (thickness is 4.5mm). ), and finally press the above-mentioned composite board with a hot and cold integrated press, keep the temperature at 145 ° C, the pressure is 50 tons, and the time is 14 h to obtain the wear-resistant composite board.
  • the anti-scratch performance test of the composite boards prepared in Examples 1-5 and Comparative Examples 1-3 was tested according to Section 4.39 of the GB17657-2013 standard. After the test was completed, the above-mentioned composite boards were placed for 0 days and 5 days. and 10 days, and then observe the scratches on the surface of the plate; the anti-wear performance test of the composite plates prepared in Examples 1-5 and Comparative Examples 1-3 is tested according to the method 2 of Section 4.39 in the standard of GB17657-2013; The formaldehyde content in the composite boards prepared in Examples 1-5 and Comparative Examples 1-3 was tested according to the method in the standard GB18580-2017.
  • Test method 400 volunteers aged 20-60 were selected from different regions (region A and region B) and randomly divided into 8 groups with 50 people in each group. Five groups of volunteers stood on the composite boards of Examples 1-5, and 3 groups of volunteers stood on the composite boards of Comparative Examples 1-3, respectively, for 30 minutes, and the degree of foot fatigue of each volunteer was recorded.
  • the floor prepared by the process of the present invention has a good foot feel, is not easily fatigued after standing for a long time, and is easily accepted by consumers.
  • the invention adopts the SPC base material in the hot-melting state to heat-laminate to prepare the scratch-resistant and wear-resistant self-healing composite board, saves the process of laminating after applying glue in the traditional process, and has high production efficiency.
  • the process of the invention and the traditional process The specific time is as follows.

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本发明公开了抗刮耐磨自修复的复合板及其制备方法和应用，属于建筑用地面和墙面装饰材料领域。本发明公开的复合板从下到上依次包括基材层、彩膜层、以及抗刮耐磨层，抗刮耐磨层包括至少两层不同硬度的热塑性聚氨酯弹性体橡胶层。本发明通过将不同硬度的热熔融状态下的制备的热塑性聚氨酯弹性体橡胶层，通过在线热覆合的方法，不同硬度的热塑性聚氨酯弹性体橡胶层的贴合顺序按照硬度由内层向表面层逐渐减小的顺序与熔融的SPC基材进行热覆合，获得抗刮耐磨自修复的复合板，可作为地板或墙面盖板，用于地面或者墙面的装修装饰。

Description

抗刮耐磨自修复的复合板及其制备方法和应用 技术领域
本发明涉及一种建筑用地面和墙面装饰材料领域，具体涉及抗刮耐磨自修复的复合板及其制备方法和应用。
背景技术
目前，弹性地板和墙板产品在市场上应用已经日益广泛，是一类具有非常好发展前景的装饰产品。其中，弹性地板是当今世界上非常流行的一种新型轻体地面装饰材料，也称为“轻体地材”，是一种在欧美及亚洲日韩广受欢迎的产品，从80年代初开始进入中国市场，至今在国内的大中城市已经得到普遍认可，使用非常广泛，比如家庭、医院、学校、办公楼、工厂、公共场所、超市、商业等各种场所。具体就是以聚氯乙烯及其共聚树脂为主要原料，加入填料、增塑剂、稳定剂、着色剂等辅料，在片状连续基材上，经涂敷工艺或经压延、挤出或挤压工艺生产而成。
传统弹性地板和墙板一般采用PVC类的耐磨层，存在不耐刮划的缺点，且刮划后留下永久划痕，很大程度影响使用，还存在使用寿命短，经济性不佳等问题，并且，PVC中含有大量的氯，火灾中PVC类地板燃烧过程中释放出盐酸和其他有毒气体，产生大量的浓烟，是火灾的主要致死原因。
热塑性聚氨酯弹性体橡胶(TPU)是由二苯甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)和扩链剂反应得到的刚性嵌段，或者是由二苯甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)等二异氰酸酯分子和大分子多元醇反应得到的柔性链段交替构成的，具有硬度范围宽、抗刮耐磨、耐油、耐撕裂、耐低温、透明、弹性好等优势，将不同硬度的热塑性聚氨酯弹性体橡胶层应用到复合板中，获得具有抗刮耐磨自修复功能的复合板的相关研究还未见报道。
发明内容
本发明公开了一种抗刮耐磨自修复的复合板，所述复合板从下到上依次包括基材层、彩膜层、以及抗刮耐磨层，所述抗刮耐磨层包括至少两层不同硬度的热塑性聚氨酯弹性体橡胶层。
优选地，所述热塑性聚氨酯弹性体橡胶层的层数为2层，所述热塑性聚氨酯弹性 体橡胶层贴合在所述彩膜层上，与所述彩膜层接触的内层热塑性聚氨酯弹性体橡胶层硬度Shore D为65～85，不与所述彩膜层接触的表面层热塑性聚氨酯弹性体橡胶层硬度Shore D为30-45，内层所述热塑性聚氨酯弹性体橡胶层的硬度＞表面层热塑性聚氨酯弹性体橡胶层的硬度。
优选地，所述热塑性聚氨酯弹性体橡胶层的层数＞2层，所述热塑性聚氨酯弹性体橡胶层贴合在所述彩膜层上，与所述彩膜层接触的内层热塑性聚氨酯弹性体橡胶层硬度Shore D为75～85，不与所述彩膜层接触的表面层热塑性聚氨酯弹性体橡胶层硬度Shore D为30-45，介于内层热塑性聚氨酯弹性体橡胶层与表面层热塑性聚氨酯弹性体橡胶层之间的若干个中间层热塑性聚氨酯弹性体橡胶层硬度Shore D为65～75，所述热塑性聚氨酯弹性体橡胶层的硬度由内层向表面层逐渐减小。
优选地，所述热塑性聚氨酯弹性体橡胶层的层数为2-5层。
优选地，所述抗刮耐磨层的厚度为0.30-2.00mm。
优选地，每层所述热塑性聚氨酯弹性体橡胶层的厚度为0.15-1.90mm。
优选地，所述热塑性聚氨酯弹性体橡胶层包括以下重量份的原料：
PVC树脂20～100份，TPU颗粒50～200份，增塑剂5～30份，紫外吸收剂3～25份，抗氧化剂3～35份，钙锌复合稳定剂5～20份，光稳定剂5～20份，阻燃剂5～30份，内部润滑剂0.3～1.5份。
优选地，所述热塑性聚氨酯弹性体橡胶层包括以下重量份的原料：
PVC树脂30～70份，TPU颗粒100～180份，增塑剂5～20份，紫外吸收剂5～15份，抗氧化剂5～15份，钙锌复合稳定剂5～15份。
优选地，所述热塑性聚氨酯弹性体橡胶层还包括以下重量份的原料：
光稳定剂5～10份，内部润滑剂0.4～1.0份。
优选地，所述TPU颗粒的硬度Shore D为30～80。
优选地，所述TPU的多异氰酸酯是对称多异氰酸酯、不对称多异氰酸酯或其混合物。
优选地，所述TPU的多异氰酸酯是二苯基甲烷2,4-二异氰酸酯、甲苯2,4-二异氰酸酯或甲苯2,6-二异氰酸酯中的一种或两种以上的混合物。
优选地，所述TPU的扩链剂为多元醇，选自聚醚多元醇、聚酯多元醇、聚醚酯多元醇或聚碳酸酯多元醇中一种或两种以上组合的多元醇。
优选地，所述TPU的扩链剂为二醇，分子量范围60～600g/mol。
优选地，所述增塑剂为环保型对苯二甲酸二辛酯(DOTP)。
优选地，所述紫外吸收剂为UV329、UV328、UV234和UV360中的一种或两种的混合物。
优选地，所述抗氧化剂为抗氧剂1010、抗氧剂168和抗氧剂1076中的一种或两种的混合物。
优选地，光稳定剂770。
优选地。内部润滑剂G60。
优选地，所述复合板还包括UV涂层，所述UV涂层贴合在抗刮耐磨层上；
优选地，所述抗刮耐磨层贴合在覆有彩膜层的基材层上，使所述彩膜层介于抗刮耐磨层与基材层之间。
优选地，所述基材层的厚度≤10mm；
优选地，所述基材层为SPC板材、WPC板材、LVT板材、PVC板材或MDF板材。
优选地，所述基材层包括聚烯烃、碳酸钙、钙锌稳定剂、丙烯酸酯类共聚物ACR、聚乙烯蜡(PE蜡)、润滑剂、和回收料。
优选地，所述基材层包含以下重量份原料：
PVC80～120份、碳酸钙200～400份、钙锌稳定剂4.0～8.0份、ACR 4.0～12份、聚乙烯蜡0.3～1.2份、内润滑剂G60 0.4～1.1份、回收料30～100份。
本发明另一目的是提供一种上述复合板的制备方法，基于熔融状态的两个或多个并排的热塑性聚氨酯弹性体橡胶层之间，由于转酯化作用，在接触区中能够形成基于第一层异氰酸酯和第二层多元醇和基于第二层异氰酸酯和第一层多元醇的聚氨酯反应，使得不同层的热塑性聚氨酯弹性体橡胶层能够强有力的结合在一起，从而获得抗刮耐磨自修复复合膜。
所述制备方法主要包括以下步骤：
1)按照配方分别称取不同配比的PVC树脂、TPU颗粒、增塑剂、紫外吸收剂、抗氧化剂和钙锌复合稳定剂，添加到混合搅拌机中，搅拌均匀，将搅拌均匀的物料送 入密炼机中进行初步塑化，然后将初步塑化的物料输送到压延机中进行压延，压延过程保持加热温度高于物料的玻璃化转变温度，获得两种或两种以上不同硬度的热熔状态下的热塑性聚氨酯弹性体橡胶层；
2)将步骤(1)获得的两种或两种以上不同硬度的热熔状态下的热塑性聚氨酯弹性体橡胶层按照硬度逐渐减小的顺序由下到上堆叠，热覆合成TPU耐刮层。
3)在线挤出基材层，将熔融状态下的基材层、彩膜层与步骤(2)制备的TPU耐刮层由下到上依次堆叠，热覆合，温度保持170～180℃，获得抗刮耐磨自修复复合板。
优选地，基材层是通过混料后，将基材原料通过挤出机挤出，再经过四辊压延机或多辊压延机进行压延。
优选地，所述PVC树脂聚合度600～1500、TPU颗粒硬度范围为35～120。
优选地，所述搅拌过程，温度范围控制在45～130℃，转速为2000～4000r/min。
优选地，所述密炼机中初步塑化过程，温度保持在160～230℃。
优选地，所述热塑性聚氨酯弹性体橡胶表面层的硬度Shore D为30～45，且其厚度为0.15～1.99mm。
优选地，所述四辊压延机或冷热一体机对基材进行压延过程，温度保持120～160℃。
本发明进一步提供上述抗刮耐磨自修复复合板在建筑装修装饰中的应用。
优选地，所述建筑装饰主要包括民用建筑装修装饰和公用建筑装修装饰装饰。
优选地，所述自修复复合板主要用于地面或者墙面的装修装饰。
优选地，所述自修复复合板主要用作地板或墙面盖板。
优选地，所述自修复复合板主要用作地板。
本发明取得的有益效果如下：
1.本发明所述的复合板产品性能稳定，大幅提高了抗刮耐磨性能，其抗刮耐磨性能可达到6000转以上，而现有采用PVC膜的传统板材，其抗刮耐磨性能为4500转左右，明显优于PVC耐磨层的传统板材。
2.当本发明所述复合板表面层为热塑性聚氨酯弹性体橡胶层，受到外力在其表面上产生划痕时，经过一段时间后，可自行修复，延长了复合板的整体使用寿命，可达20年。
3.本发明所述复合板的表面质感明显优于石塑板材，更接近于实木表面的效果，容易被消费者接受。
4.本发明所述复合板的综合性价比高，其成本与传统板材的成本大体相当，有利于其普及和大众化，开拓了弹性地板的市场空间。
5.本发明所述热塑性聚氨酯弹性体橡胶层和基材层的相容性非常好，基材层可选自采用覆有彩膜层的SPC板材、覆有彩膜层的WPC板材、覆有彩膜层的LVT板材或覆有彩膜层的MDF板材，本发明采用热熔融状态下的热塑性聚氨酯弹性体橡胶层进行贴合即可，省去了涂胶后进行压合工艺，生产效率高，可大批量生产，生产工艺简单并且稳定。
6.本发明所述复合板在制备过程中未使用胶黏剂，低醛环保，该复合板甲醛测试等级达到E0级标准。
7.本发明所述复合板应用领域广泛，可以用于民用建筑和公用建筑等抗刮耐磨要求高、耐污染要求高的区域，可替代瓷砖、传统板材等产品，并且能够保证整体装修风格。
附图说明
图1为实施例中所述抗刮耐磨自修复复合板的结构示意图，1为抗刮耐磨自修复层，2为彩膜层，3为基材层。
图2为实施例中所述抗刮耐磨自修复层的结构示意图，101为热塑性聚氨酯弹性体橡胶内层，102为热塑性聚氨酯弹性体橡胶表面层。
具体实施方式
下面结合实施例对本发明进行详细的说明，但本发明的实施方式不限于此，显而易见地，下面描述中的实施例仅是本发明的部分实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，获得其他的类似的实施例均落入本发明的保护范围。
实施例1
一种抗刮耐磨自修复复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为73)170g、增塑剂DOTP 8g、紫外吸收剂UV329 5g、抗氧化剂1010 6g、钙锌复合稳定剂10g，添加 到高速混合搅拌机中，升温到110℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在180℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为68的热塑性聚氨酯弹性体橡胶内层，且其厚度为0.20mm；
2)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为40)170g、增塑剂DOTP 5g、紫外吸收剂UV329 8g、抗氧化剂1010 10g、钙锌复合稳定剂12g，添加到高速混合搅拌机中，升温到108℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在170℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为36的热塑性聚氨酯弹性体橡胶表面层，且其厚度为0.20mm；
3)将步骤(1)获得的热熔状态下的热塑性聚氨酯弹性体内层和步骤(2)获得的热熔状态下的热塑性聚氨酯弹性体外层热覆合成TPU耐刮层。
4)在线挤出SPC基材(厚度为4.5mm)，将熔融状态下的SPC基材、彩膜层与步骤(3)制备的TPU耐刮层依次堆叠，通过热覆合，温度保持168℃，获得抗刮耐磨自修复复合板。
实施例2
一种抗刮耐磨自修复复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为73)160g、增塑剂DOTP 8g、紫外吸收剂UV329 5g、抗氧化剂1010 6g、钙锌复合稳定剂9.5g，添加到高速混合搅拌机中，升温到110℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在180℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为70的热塑性聚氨酯弹性体橡胶内层，且其厚度为0.20mm；
2)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为40)160g、增塑剂DOTP 5g、紫外吸收剂UV329 8g、抗氧化剂1010 10g、钙锌复合稳定剂11.5g，添加到高速混合搅拌机中，升温到108℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在170℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度 Shore D为39的热塑性聚氨酯弹性体橡胶表面层，且其厚度为0.20mm；
3)将步骤(1)获得的热熔状态下的热塑性聚氨酯弹性体内层和步骤(2)获得的热熔状态下的热塑性聚氨酯弹性体外层热覆合成TPU耐刮层。
4)在线挤出SPC基材(厚度为4.5mm)，将熔融状态下的SPC基材、彩膜层与步骤(3)制备的TPU耐刮层依次堆叠，通过热覆合，温度保持168℃，获得抗刮耐磨自修复复合板。
实施例3
一种抗刮耐磨自修复复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为73)150g、增塑剂DOTP 8g、紫外吸收剂UV329 5g、抗氧化剂1076 6g、钙锌复合稳定剂9g，添加到高速混合搅拌机中，升温到110℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在185℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为74的热塑性聚氨酯弹性体橡胶内层，且其厚度为0.15mm；
2)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为40)150g、增塑剂DOTP 5g、紫外吸收剂UV329 8g、抗氧化剂1076 10g、钙锌复合稳定剂10.0g，添加到高速混合搅拌机中，升温到108℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在175℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为41的热塑性聚氨酯弹性体橡胶表面层，且其厚度为0.15mm；
3)将步骤(1)获得的热熔状态下的热塑性聚氨酯弹性体内层和步骤(2)获得的热熔状态下的热塑性聚氨酯弹性体外层热覆合成TPU耐刮层。
4)在线挤出SPC基材(厚度为4.5mm)，将熔融状态下的SPC基材、彩膜层与步骤(3)制备的TPU耐刮层依次堆叠，通过热覆合，温度保持170℃，获得抗刮耐磨自修复复合板。
实施例4
一种抗刮耐磨自修复复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为73)140g、增塑 剂DOTP 8g、紫外吸收剂UV329 5g、抗氧化剂1076 6g、钙锌复合稳定剂8.5g，添加到高速混合搅拌机中，升温到110℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在185℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为78的热塑性聚氨酯弹性体橡胶内层，且其厚度为0.15mm；
2)准确称量PVC树脂(聚合度1000)50g、TPU颗粒(硬度为40)140g、增塑剂DOTP 5g、紫外吸收剂UV329 8g、抗氧化剂1076 10g、钙锌复合稳定剂9.5g，添加到高速混合搅拌机中，升温到108℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在175℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为43的热塑性聚氨酯弹性体橡胶表面层，且其厚度为0.15mm；
3)将步骤(1)获得的热熔状态下的热塑性聚氨酯弹性体内层和步骤(2)获得的热熔状态下的热塑性聚氨酯弹性体外层热覆合成TPU耐刮层。
4)在线挤出SPC基材(厚度为4.5mm)，将熔融状态下的SPC基材、彩膜层与步骤(3)制备的TPU耐刮层依次堆叠，通过热覆合，温度保持170℃，获得抗刮耐磨自修复复合板。
实施例5
一种抗刮耐磨自修复复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)100g、TPU颗粒(硬度为73)260g、增塑剂DOTP 16g、紫外吸收剂UV329 10g、抗氧化剂1076 12g、钙锌复合稳定剂16g，添加到高速混合搅拌机中，升温到110℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在185℃，然后将初步塑化的物料输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为83的热塑性聚氨酯弹性体橡胶内层，且其厚度为0.30mm；
2)准确称量PVC树脂(聚合度1000)100g、TPU颗粒(硬度为40)260g、增塑剂DOTP 10g、紫外吸收剂UV329 16g、抗氧化剂1076 20g、钙锌复合稳定剂18g，添加到高速混合搅拌机中，升温到108℃，转速为3000r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在175℃，然后将初步塑化的物料 输送到压延机中压延，压延过程保持加热温度稍高于物料的玻璃化转变温度，获得硬度Shore D为45的热塑性聚氨酯弹性体橡胶表面层，且其厚度为0.30mm；
3)将步骤(1)获得的热熔状态下的热塑性聚氨酯弹性体内层和步骤(2)获得的热熔状态下的热塑性聚氨酯弹性体外层热覆合成其厚度为0.60mm的TPU耐刮层。
4)在线挤出SPC基材(厚度为4.5mm)，将熔融状态下的SPC基材、彩膜层与步骤(3)制备的TPU耐刮层依次堆叠，通过热覆合，温度保持170℃，获得抗刮耐磨自修复复合板。
对比例1
一种耐磨复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)200g、增塑剂DOTP 8g、紫外吸收剂UV329 5g、抗氧化剂1010 6g、钙锌复合稳定剂9g添加到高速混合搅拌机中，升温到115℃，转速为3200r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在150℃，然后将初步塑化的物料输送到压延机中压延，冷却后获得耐磨层，且其厚度为0.30mm。
2)将步骤(1)获得抗刮耐磨层一侧均匀涂布胶黏剂，然后将涂布胶黏剂的耐磨层贴合在覆有彩膜层的SPC板材上(厚度为4.5mm)，最后使用冷热一体压机对上述复合板进行压合，温度保持145℃，压力50吨，时间14h，获得耐磨复合板。
对比例2
一种耐磨复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1200)200g、增塑剂DOTP 12g、紫外吸收剂UV329 6g、抗氧化剂1010 6g、钙锌复合稳定剂12g添加到高速混合搅拌机中，升温到115℃，转速为3200r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在150℃，然后将初步塑化的物料输送到压延机中压延，冷却后获得耐磨层，且其厚度为0.30mm。
2)将步骤(1)获得抗刮耐磨层一侧均匀涂布胶黏剂，然后将涂布胶黏剂的耐磨层贴合在覆有彩膜层的SPC板材上(厚度为4.5mm)，最后使用冷热一体压机对上述复合板进行压合，温度保持145℃，压力50吨，时间14h，获得耐磨复合板。
对比例3
一种耐磨复合板的制备方法，所述制备方法主要包括以下步骤：
1)准确称量PVC树脂(聚合度1000)200g、增塑剂DOTP 5g、紫外吸收剂UV329 8g、抗氧化剂1076 10g、钙锌复合稳定剂10g添加到高速混合搅拌机中，升温到115℃，转速为3200r/min，混合搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，温度保持在150℃，然后将初步塑化的物料输送到压延机中压延，冷却后获得耐磨层，且其厚度为0.30mm。
2)将步骤(1)获得抗刮耐磨层一侧均匀涂布胶黏剂，然后将涂布胶黏剂的耐磨层贴合在覆有彩膜层的SPC板材上(厚度为4.5mm)，最后使用冷热一体压机对上述复合板进行压合，温度保持145℃，压力50吨，时间14h，获得耐磨复合板。
实施例6
实施例1-5和对比例1-3中制备的复合板的抗划痕性能测试按照GB17657-2013的标准中的4.39部分进行测试，测试完成后，将上述的复合板放置0天、5天和10天，然后观察板材表面的划痕情况；实施例1-5和对比例1-3中制备的复合板的抗磨损性能测试按照GB17657-2013的标准中的4.39部分的方法2进行测试；实施例1-5和对比例1-3中制备的复合板中的甲醛含量检测按照GB18580-2017的标准中方法进行测试。
表1 实施例1-5和对比例1-3的产品性能结果
Figure PCTCN2021117677-appb-000001
Figure PCTCN2021117677-appb-000002
实施例7
实施例1-5和对比例1-3中制备的复合板的脚感评价试验
试验方法：在不同地区(A地区和B地区)分别选择400例志愿者，年龄20-60岁；并随机分为8组，每组50人。5组志愿者分别站立在实施例1-5的复合板上、3组志愿者分别站立在对比例1-3的复合板上，站立时间为30min，记录每位志愿者的脚部疲劳程度。
评判标准：
轻度：脚部无痛感
中度：脚部稍有痛感
重度：脚部有明显痛感，并稍有麻木感
表2 试验结束后各组志愿者的脚感评估结果；
Figure PCTCN2021117677-appb-000003
由上表可知，本发明的工艺制备得到的地板脚感良好，久站后不易疲劳，容易被消费者接受。
实施例8
本发明采用热熔融状态下的SPC基材热覆合制备抗刮耐磨自修复复合板，省去了传统工艺涂胶后进行压合的过程，生产效率高，本发明所述工艺和传统工艺具体用时如下。
表3 本发明制备工艺和现有工艺的生产效率对比结果
  本发明工艺 传统工艺
涂胶 —— 0.15h
组胚压合 —— 14h
产量/天 1600m 2 28m 2
由上表可知，本发明的工艺的各设备之间联动性能强，工作效率高，节约能源，节省劳动成本。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种抗刮耐磨自修复的复合板，其特征在于，所述复合板由下到上依次包括基材层、彩膜层和抗刮耐磨层，所述抗刮耐磨层贴合在所述彩膜层上；
    所述抗刮耐磨层为两层不同硬度的热塑性聚氨酯弹性体橡胶层，与所述彩膜层接触的内层热塑性聚氨酯弹性体橡胶层的硬度Shore D为65～85，未与所述彩膜层接触的表面层热塑性聚氨酯弹性体橡胶层的硬度Shore D为30-45；
    或者，所述抗刮耐磨层为3层以上不同硬度的热塑性聚氨酯弹性体橡胶层，与所述彩膜层接触的内层热塑性聚氨酯弹性体橡胶层硬度Shore D为75～85，未与所述彩膜层接触的表面层热塑性聚氨酯弹性体橡胶层硬度Shore D为30-45，介于内层热塑性聚氨酯弹性体橡胶层与表面层热塑性聚氨酯弹性体橡胶层之间的若干个中间层热塑性聚氨酯弹性体橡胶层硬度Shore D为65～75，所述热塑性聚氨酯弹性体橡胶层的硬度由内层向表面层逐渐减小。
  2. 根据权利要求1所述的复合板，其特征在于，所述抗刮耐磨层的厚度为0.30-2.00mm；每层热塑性聚氨酯弹性体橡胶层的厚度为0.15-1.90mm。
  3. 根据权利要求2所述的复合板，其特征在于，所述热塑性聚氨酯弹性体橡胶层包括以下重量份的原料：
    PVC树脂20～100份，TPU颗粒50～200份，增塑剂5～30份，紫外吸收剂3～25份，抗氧化剂3～35份，钙锌复合稳定剂5～20份。
  4. 根据权利要求2所述的复合板，其特征在于，所述热塑性聚氨酯弹性体橡胶层包括以下重量份的原料：
    PVC树脂30～70份，TPU颗粒100～180份，增塑剂5～20份，紫外吸收剂5～15份，抗氧化剂5～15份，钙锌复合稳定剂5～15份。
  5. 根据权利要求4所述的复合板，其特征在于，所述TPU颗粒的硬度Shore D为30～80；所述增塑剂为对苯二甲酸二辛酯；所述紫外吸收剂为UV329、UV328、UV234和UV360中的一种或两种的混合物；所述抗氧化剂为抗氧剂1010、抗氧剂168和抗氧剂1076中的一种或两种的混合物。
  6. 根据权利要求1-5任一项所述的复合板，其特征在于，所述基材层为SPC板材、WPC板材、LVT板材、PVC板材或MDF板材；所述基材层的厚度≤10mm。
  7. 权利要求1-6所述的复合板的制备方法，其特征在于，包括以下步骤：
    1)分别称取不同配比的PVC树脂、TPU颗粒、增塑剂、紫外吸收剂、抗氧化剂和钙锌复合稳定剂，添加到混合搅拌机中，搅拌均匀，将搅拌均匀的物料送入密炼机中进行初步塑化，然后将初步塑化的物料输送到压延机中进行压延，获得两种或两种以上不同硬度的热熔状态下的热塑性聚氨酯弹性体橡胶层；
    2)将步骤(1)制备的两种或两种以上不同硬度的热熔状态下的热塑性聚氨酯弹性体橡胶层按照硬度逐渐减小的顺序由下到上依次堆叠，热覆合成TPU抗刮耐磨自修复层；
    3)将熔融状态下的基材层、彩膜层与步骤(2)制备的TPU抗刮耐磨自修复层由下到上依次堆叠，热覆合，获得抗刮耐磨自修复复合板。
  8. 根据权利要求7所述的制备方法，其特征在于，步骤(1)中所述搅拌过程的温度范围为45～130℃，转速为2000～4000r/min；所述初步塑化过程的温度保持在160～230℃；步骤(3)中热覆合过程的温度保持170～180℃。
  9. 权利要求1-6所述的抗刮耐磨自修复的复合板在建筑装修装饰中的应用。
  10. 根据权利要求9所述的应用，其特征在于，所述抗刮耐磨自修复的复合板用作地板或墙面盖板。
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