WO2017201802A1 - 非卤表面材料及其制造方法 - Google Patents

非卤表面材料及其制造方法 Download PDF

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Publication number
WO2017201802A1
WO2017201802A1 PCT/CN2016/087383 CN2016087383W WO2017201802A1 WO 2017201802 A1 WO2017201802 A1 WO 2017201802A1 CN 2016087383 W CN2016087383 W CN 2016087383W WO 2017201802 A1 WO2017201802 A1 WO 2017201802A1
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WIPO (PCT)
Prior art keywords
parts
particles
tpu
layer
halogen
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PCT/CN2016/087383
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English (en)
French (fr)
Inventor
游雄铁
张小平
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上海劲嘉建材科技有限公司
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Publication of WO2017201802A1 publication Critical patent/WO2017201802A1/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
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • 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
    • E04F13/072—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of specially adapted, structured or shaped covering or lining elements
    • E04F13/077—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of specially adapted, structured or shaped covering or lining elements composed of several layers, e.g. sandwich panels
    • 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
    • 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
    • E04F13/0871—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 having an ornamental or specially shaped visible surface
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0278—Polyester particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0292—Polyurethane particles
    • 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

Definitions

  • the invention relates to a surface material used in the field of interior and exterior decoration and a manufacturing method thereof, in particular to an environment-friendly non-halogen surface material and a manufacturing method thereof.
  • PVC polyvinyl chloride
  • CN102733581A discloses a non-PVC floor tile which uses PETG (polyethylene terephthalate-1,4-cyclohexanedimethanol ester) as a raw material to produce a floor tile which meets environmental protection requirements.
  • PETG polyethylene terephthalate-1,4-cyclohexanedimethanol ester
  • PETG cannot be added with inorganic fillers, which is costly, and PETG has very good heat shrinkage properties and poor dimensional stability, although it has an easy-to-print property. PETG transparent wear layer, scratch resistance cross.
  • the experiment also found that the non-PVC floor tiles prepared by using PETG as the printing film can not overcome the defects of warpage deformation after tempering.
  • the present invention provides an environmentally friendly non-halogen surface material and a method of manufacturing the same.
  • the non-halogen surface material provided by the invention comprises a base layer, a decorative layer and a wear layer, wherein the wear layer is a TPU transparent sheet, the decorative layer is a TPU printing film, and the base layer is a non-halogen polymer sheet,
  • the material of the wear layer includes TPU and an additive, and the material of the base layer includes a non-halogen polymer material and a filler, and the non-halogen polymer material is a mixture of at least two of TPU or TPU, NBR, ABS, and PETG.
  • the material of the wear layer comprises 100 parts of TPU particles and 1-15 parts of the additive, the additive being a mixture of a stabilizer or a stabilizer and at least one of an antioxidant and a smoke suppressant.
  • the material of the base layer comprises 100 parts of non-halogen polymer material particles, 100-300 parts of filler, and 1-15 parts of additives, and the additive is a stabilizer or a stabilizer and a flame retardant and smoke elimination. a mixture of at least one of the agents, the filler being at least one of stone powder, calcite and kaolin.
  • 100 parts of the mixture comprises: 75-95 parts of TPU particles and 5-25 parts of NBR particles, or 80-95 parts of TPU particles and 5-20 parts of PETG particles, or 55 - 90 parts of TPU particles, 5-25 parts of NBR particles and 5-20 parts of PETG particles, or 70-90 parts of TPU particles and 10-30 parts of ABS particles, or 85-95 parts of ABS particles and 5 -15 parts of NBR particles, or 80-95 parts of PETG particles and 5-20 parts of NBR particles, or 20-40 parts of TPU particles, 10-30 parts of ABS particles, 10-20 parts of NBR particles, and 15 -30 parts of PETG particles.
  • the method for producing a non-halogen surface material comprises: preparing a mixture of a non-halogen polymer material and a filler, preparing a base layer by an extrusion molding method or a calender molding method; preparing a decorative layer, comprising: preparing a TPU film; preparing The support film; the TPU film and the support film are pseudo-bonded together to start printing, and the pattern is printed on the side of the TPU film facing away from the support film; after printing, the two films are separated to obtain a TPU printed film; and a mixture of TPU and additives is prepared.
  • the wear-resistant layer is prepared by a suitable process; the base layer, the decorative layer and the wear-resistant layer are bonded together by hot pressing or online bonding to obtain a non-halogen surface material.
  • the calendering temperature is 120-170 ° C
  • the extrusion temperature is 150-190 °C.
  • the step of thermocompression bonding comprises: stacking the prepared base layer, the decorative layer and the wear layer in sequence; and passing the stacked film layer through a hot press at 100-170
  • the thermosetting pressure is applied at a temperature of °C and a pressure of 25-180 MPa to form a non-halogen surface material.
  • the step of in-line bonding comprises: sequentially placing the base layer, the decorative layer and the wear layer in the hanging roller; simultaneously feeding the base layer, the decorative layer and the wear layer into the online bonding
  • the apparatus is laminated to form a non-halogenated surface material, and the in-line bonding apparatus includes a plurality of sets of press rolls disposed in a horizontal direction, and each set of press rolls includes press rolls that are vertically symmetric.
  • the support film used in the preparation of the decorative layer is one of a plant fiber paper, a PP film, a PET film, a PA film, a PC film, a PS film, a PETG film, and a POM film.
  • the non-halogen polymer material is a mixture of at least two of TPU or TPU, NBR, ABS, PETG, and 100 parts of the mixture comprises: 75-95 parts of TPU particles and 5-25 parts.
  • the non-halogen surface material of the present invention uses TPU as a material of the decorative layer and the wear-resistant layer, and uses an environmentally-friendly non-halogen polymer material as a material of the base layer, so that the obtained surface material does not contain halogen. Therefore, no harmful substances are generated during the incineration process, and environmental protection requirements are met; and since the base layer material does not contain PVC, the non-halogen surface material of the present invention does not require the addition of a plasticizer (phthalic acid ester). Therefore, human harm caused by the introduction of phthalates can be avoided.
  • a plasticizer phthalic acid ester
  • the TPU film and the supporting film thereof are fixed and printed together by the pseudo-bonding printing method, and the elastic deformation of the decorative layer base layer (ie, the TPU film) can be reduced, and the printed pattern can be prevented from being sampled.
  • the use of a TPU printing film in place of the PETG printing film can effectively reduce the product cost and product deformation problems caused by shrinkage of the printing film itself.
  • FIG. 1 is a schematic view showing the structure of a non-halogen surface material of the present invention.
  • FIG. 2 is a schematic flow chart of a method for producing a non-halogen surface material of the present invention.
  • FIG. 3 is a schematic illustration of step S13 of Figure 2.
  • FIG. 4 is a schematic flow chart showing another manufacturing method of the non-halogen surface material of the present invention.
  • FIG. 5 is a schematic illustration of step J14 of Figure 4.
  • the non-halogen surface material of the present invention is a composite material which can be used not only for laying the ground but also for laying ceilings, walls, wardrobes and the like.
  • the non-halogen surface material is preferably a composite floor.
  • the non-halogenated surface material 100 includes a base layer 10, a decorative layer 20, and a wear layer 30 in this order from bottom to top.
  • the base layer 10 is a TPU sheet comprising a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may not include the intermediate layer 12.
  • the material of the primer layer 11 includes TPU particles, fillers, and additives.
  • the material of the primer layer 11 is composed of TPU particles, a filler, and an additive.
  • the composition of each component of the material of the primer layer 11 For example: 100 parts of TPU (thermoplastic polyurethane) particles, 100-300 parts of filler, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant) .
  • the intermediate layer 12 includes TPU particles, fillers, and additives.
  • the material of the intermediate layer 12 is composed of TPU particles, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of TPU particles, 200-300 parts of filler, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, smoke elimination) 0-1 parts).
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide or aluminum hydroxide.
  • the hydrated zinc borate and the hydrotalcite, the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the substrate of the base layer 10 is TPU.
  • the substrate of the base layer 10 may also be other non-halogen polymer materials, such as TPU, NBR (nitrile rubber), A mixture of at least two of ABS (acrylonitrile-butadiene-styrene copolymer) and PETG (polyethylene terephthalate-1,4-cyclohexanedimethanol ester).
  • the decorative layer 20 is a TPU printed film which is prepared by a pseudo-bonding printing method. Due to the high elasticity and good flexibility of the TPU, the TPU printing film is easy to "walk the plate” (printing is inaccurate) when printing, and printing cannot be realized. In order to solve the problem of "walking" in the printing of TPU film, the present invention proposes a pseudo-fitting printing method.
  • the pseudo-bonding printing method is to falsely bond the supporting film on one side surface of the TPU film, and print a pattern on the side surface of the TPU film facing away from the supporting film during printing, and separate the two layers after the printing is completed, that is, A TPU printed film was produced.
  • the support film used may be vegetable fiber paper, PP (polypropylene) film, PET (polyethylene terephthalate) film, PA (polyamide) film, PC (poly) One of a carbonate) film, a PS (polystyrene) film, a PETG (polyethylene terephthalate-1,4-cyclohexanedimethanol ester) film, and a POM (polyoxymethylene) film.
  • PP polypropylene
  • PET polyethylene terephthalate
  • PA polyamide
  • PC poly) One of a carbonate
  • PS polystyrene
  • PETG polyethylene terephthalate-1,4-cyclohexanedimethanol ester
  • POM polyoxymethylene
  • the wear resistant layer 30 is a TPU transparent sheet, and the material of the wear resistant layer 30 includes TPU particles and an additive.
  • the material of the wear layer 30 is composed of TPU particles and additives.
  • the components of the material of the wear-resistant layer 30 are as follows: 100 parts of TPU particles, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-10 parts of antioxidant, 0-1 parts of smoke suppressant) ).
  • the additives or additives in the wear layer 30 may be omitted as appropriate.
  • the stabilizer of the wear layer 30 may be a polycarbodiimide (Model: UN-03), and the antioxidant may be an antioxidant 1010 (four [ ⁇ -(3,5-di-tert-butyl-4-hydroxybenzene) Base) propionic acid] pentaerythritol ester), smoke suppressant is a special smoke suppressant for transparent materials, such as ferrocene, molybdenum smoke suppressant.
  • a method of manufacturing the above non-halogen surface material is described below.
  • the method is called hot press bonding. Referring to FIG. 2, the method includes the following steps:
  • Step S11 The primer layer 11 is prepared.
  • the specific method comprises: weighing each material according to the material composition and ratio of the bottom layer 11, mixing them at high speed, and then putting them into a kneading machine for mixing for 3-15 minutes to form a mixture; and passing the prepared mixture through a calender
  • the primer layer 11 is obtained by calender molding.
  • the calendering temperature is 135-150 °C.
  • Step S12 The intermediate layer 12 is prepared.
  • the specific method comprises: weighing each material according to the material composition and ratio of the intermediate layer 12, stirring them at a high speed, placing them in a kneading machine for 3-15 minutes to form a mixture; and rolling the prepared mixture through a calender
  • the intermediate layer 12 is formed by molding.
  • the calendering temperature is 135-150 °C.
  • Step S13 preparing the decorative layer 20, the specific method comprises: using a TPU film as a surface film; preparing the supporting film, the supporting film may be plant fiber paper, PP film, PET film, PA film, PC film, PS film, PETG film and POM One of the films; the TPU film and the support film are pseudo-bonded and then printed, and the printed surface is the surface of the TPU film facing away from the support film; after printing, the two films are separated to obtain a TPU printed film. In the case of a false fit, the TPU film and the support film are pseudo-fitting together by the surface tension between the two films. As shown in FIG.
  • the TPU film 21 and the support film 22 are fixed to a fixing jig 24 on the conveying roller 23 or the conveying belt, and the fixing jig 24 is sequentially passed through a plurality of printing rollers 25 for each printing.
  • the roller 25 is coated with a pigment which is printed on the surface of the TPU film 21 after the fixing jig 24 passes through all of the printing rollers 25.
  • Step S14 A wear layer 30 is prepared.
  • the specific method comprises: preparing each material according to the material composition and ratio of the wear-resistant layer 30; and obtaining the wear-resistant layer 30 by a suitable process such as calendering, casting, or blow molding.
  • Step S15 stacking the primer layer 11, the intermediate layer 12, the decorative layer 20 and the wear layer 30 prepared in steps S11-S14 in this order, and hot-pressing at a temperature of 100-170 ° C and a pressure of 25-180 MPa. Combined 10-20 min, a non-halogenated surface material 100 is formed.
  • the method includes the following steps:
  • Step J11 The primer layer 11 is prepared.
  • the specific method comprises: weighing each material according to the material composition and ratio of the bottom layer 11, mixing them at a high speed, and then putting them into a kneading machine for mixing for 3-15 minutes to form a mixture; and extruding the prepared mixture through extrusion
  • the bottom layer 11 is obtained by extrusion molding.
  • the extrusion temperature is 160-180 °C.
  • Step J12 preparing the decorative layer 20, the specific method is the same as step S13.
  • Step J13 A wear layer 30 is prepared.
  • the specific method comprises: preparing each material according to the material composition and ratio of the wear-resistant layer 30; and obtaining the wear-resistant layer 30 by a suitable process such as calendering, casting, or blow molding.
  • Step J14 As shown in FIG. 5, the primer layer 11, the decorative layer 20, and the wear layer 30 obtained in the steps J11-J13 are sequentially placed in the hanging roller 40, and are bonded by an in-line bonding device to form Non-halogenated surface material 100.
  • the in-line bonding device comprises a plurality of sets of vertically symmetrical pressure rollers 50 arranged along a horizontal line. When the bottom layer 11, the decorative layer 20 and the wear layer 30 pass together between the upper and lower symmetrical pressure rollers 50, the pressure roller 50 functions. Fit together.
  • the in-line bonding apparatus is further provided with a guide roll 60.
  • the press rolls 50 are heated as needed, and the temperature of each set of press rolls 50 is sequentially increased in the direction in which the materials are moved, so that the passed materials can be more easily pressed together.
  • the temperatures of the last two sets of pressure rollers 50 should be relatively close.
  • the linear velocity of each set of press rolls 50 should also gradually increase along the direction in which the material is to be carried.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and a substrate 11 above. Intermediate layer 12. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes a TPU/NBR mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of a TPU/NBR mixture, a filler, and an additive.
  • the composition of each component in the material of the primer layer 11 is as follows: 100 parts of the TPU/NBR mixture (including 75-95 parts of TPU particles, 5-25 parts of NBR particles), 100-300 parts of filler, and 1-15 parts of additives. (This includes 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • the material of the intermediate layer 12 includes a TPU/NBR mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of a TPU/NBR mixture, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of the TPU/NBR mixture (including 75-95 parts of TPU particles, 5-25 parts of NBR particles), 200-300 parts of filler, and 1-15 parts of additives ( These include 1-10 parts of stabilizer, 0-5 parts of flame retardant, and 0-1 parts of smoke suppressant.
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the change of processing temperature is due to the addition of NBR in the base layer material.
  • the compatibility of NBR and TPU is very good, and the addition of NBR can improve the flexibility of TPU and effectively broaden the molding processing temperature of the base layer, but it is easy to add too much.
  • the TPU becomes soft, so the content of the controlled NBR is 5-25%.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes a TPU/PETG mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of a TPU/PETG mixture, a filler, and an additive.
  • the composition of each component in the material of the primer layer 11 is as follows: 100 parts of TPU/PETG mixture (including 80-95 parts of TPU particles, 5-20 parts of PETG particles), 100-300 parts of filler, 1-15 parts of additives (This includes 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • the material of the intermediate layer 12 includes a TPU/PETG mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of a TPU/PETG mixture, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of the TPU/PETG mixture (including 80-95 parts of TPU particles, 5-20 parts of PETG particles), 200-300 parts of filler, and 1-15 parts of additives ( These include 1-10 parts of stabilizer, 0-5 parts of flame retardant, and 0-1 parts of smoke suppressant.
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the compatibility of PETG with TPU is very good, and the addition of PETG can also affect the molding processing temperature of the base layer.
  • the addition of PETG can significantly increase the hardness of the base layer material, but if too much PETG is added, the base layer material is brittle. Therefore, the content of the controlled PETG is 5-20%.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes a TPU/NBR/PETG mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of a TPU/NBR/PETG mixture, a filler, and an additive.
  • the composition of each component in the material of the primer layer 11 is as follows: 100 parts of the TPU/NBR/PETG mixture (including 55-90 parts of TPU particles, 5-25 parts of NBR particles, 5-20 parts of PETG particles), filler 100 -300 parts, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • the material of the intermediate layer 12 includes a TPU/NBR/PETG mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of a TPU/NBR/PETG mixture, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of the TPU/NBR/PETG mixture (including 55-90 parts of TPU particles, 5-25 parts of NBR particles, 5-20 parts of PETG particles), filler 200- 300 parts, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes a TPU/ABS mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of a TPU/ABS mixture, a filler, and an additive.
  • the composition of each component in the material of the primer layer 11 is as follows: 100 parts of the TPU/ABS mixture (including TPU particles 70-90) Parts, 10-30 parts of ABS particles), 100-300 parts of filler, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • the material of the intermediate layer 12 includes a TPU/ABS mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of a TPU/ABS mixture, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of the TPU/ABS mixture (including 70-90 parts of TPU particles, 10-30 parts of ABS particles), 200-300 parts of filler, and 1-15 parts of additives ( These include 1-10 parts of stabilizer, 0-5 parts of flame retardant, and 0-1 parts of smoke suppressant.
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the processing temperature can also be controlled within the above range by adjusting the content of ABS in the base layer material.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes an ABS/NBR mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of an ABS/NBR mixture, a filler, and an additive.
  • the components of the material of the primer layer 11 are as follows: 100 parts of the ABS/NBR mixture (including 85-95 parts of ABS particles, 5-15 parts of NBR particles), 100-300 parts of filler, 1-15 parts of additives. (This includes 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • the material of the intermediate layer 12 includes an ABS/NBR mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of an ABS/NBR mixture, a filler, and an additive.
  • the components of the material of the intermediate layer 12 are as follows: 100 parts of the ABS/NBR mixture (including 85-95 parts of ABS particles, 5-15 parts of NBR particles), 200-300 parts of filler, and 1-15 parts of additives ( These include 1-10 parts of stabilizer, 0-5 parts of flame retardant, and 0-1 parts of smoke suppressant.
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the processing temperature can also be controlled within the above range by the ratio of ABS to NBR in the base layer material.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes a PETG/NBR mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of a PETG/NBR mixture, a filler, and an additive.
  • the composition of each component in the material of the primer layer 11 is as follows: 100 parts of PETG/NBR mixture (including 80-95 parts of PETG particles, 5-20 parts of NBR particles), 100-300 parts of filler, 1-15 parts of additives (This includes 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • the material of the intermediate layer 12 includes a PETG/NBR mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of a PETG/NBR mixture, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of the PETG/NBR mixture (including 80-95 parts of PETG particles, 5-20 parts of NBR particles), 200-300 parts of filler, and 1-15 parts of additives ( among them Including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant.
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the processing temperature can also be controlled within the above range by the ratio of PETG to NBR in the base layer material.
  • the decorative layer 20 and the wear-resistant layer 30 of the non-halogen surface material of the present embodiment are identical to the non-halogenated surface material of the first embodiment, and the present embodiment is different from the first embodiment in the base layer 10.
  • the base layer 10 also includes a primer layer 11 and an intermediate layer 12 above the primer layer 11. In another embodiment of the invention, the base layer 10 may also not include the intermediate layer 12.
  • the material of the primer layer 11 includes a TPU/ABS/NBR/PETG mixture, a filler, and an additive.
  • the material of the primer layer 11 is composed of a TPU/ABS/NBR/PETG mixture, a filler, and an additive.
  • the composition of each component in the material of the primer layer 11 is as follows: 100 parts of the TPU/ABS/NBR/PETG mixture (including 20-40 parts of TPU particles, 10-30 parts of ABS particles, 10-20 parts of NBR particles, PETG) 15-30 parts of granules, 100-300 parts of filler, 1-15 parts of additive (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 part of smoke suppressant).
  • the material of the intermediate layer 12 includes a TPU/ABS/NBR/PETG mixture, a filler, and an additive.
  • the material of the intermediate layer 12 is composed of a TPU/ABS/NBR/PETG mixture, a filler, and an additive.
  • the composition of each component in the material of the intermediate layer 12 is as follows: 100 parts of the TPU/ABS/NBR/PETG mixture (including 20-40 parts of TPU particles, 10-30 parts of ABS particles, 10-20 parts of NBR particles, PETG particles) 15-30 parts), 200-300 parts of filler, 1-15 parts of additives (including 1-10 parts of stabilizer, 0-5 parts of flame retardant, 0-1 parts of smoke suppressant).
  • some of the additives or additives in the base layer 10 may be omitted as appropriate.
  • the filler of the primer layer 11 and the intermediate layer 12 may be stone powder, calcite or kaolin
  • the stabilizer may be polycarbodiimide (model: UN-03)
  • the flame retardant may be magnesium hydroxide, aluminum hydroxide or hydrated boric acid.
  • Zinc and hydrotalcite the smoke suppressant may be a ferrocene or molybdenum smoke suppressant.
  • the method for producing the non-halogen surface material of the present embodiment is basically the same as that of the first embodiment except for the processing temperature.
  • the calendering temperature in steps S11 and S12 is 120 to 170 °C.
  • the extrusion molding temperature in the step J11 is 150 to 190 °C.
  • the present invention has at least one of the following advantages:
  • the non-halogen surface material of the present invention uses TPU as a material for the decorative layer and the wear-resistant layer, and uses an environmentally-friendly non-halogen polymer material as a material of the base layer, so that the obtained surface material contains no halogen, and thus No harmful substances are produced during the incineration process, and environmental protection requirements are met.
  • the TPU film and its supporting film are fixed together for printing, which can reduce the elastic deformation of the decorative layer base layer (ie, TPU film), avoiding the printing pattern to be sampled; further, using the TPU printing film instead of PETG printing film can effectively reduce product cost and product deformation caused by shrinkage of the printing film itself.
  • the non-halogen surface material of the present invention does not need to add a plasticizer (phthalic acid ester), thereby avoiding human harm caused by the introduction of phthalic acid esters. .
  • Both the base layer and the wear-resistant layer can be directly mixed and then calendered, and the molding is fast, the size is accurate, and mass production is possible.
  • the substrate of the base layer is one of a TPU/NBR mixture, a TPU/PETG mixture and a TPU/NBR/PETG mixture.
  • the processing temperature can be extended to 120-170 °C when it is prepared by calender molding. The processing temperature can be extended to 150-190 °C by extrusion molding.
  • the non-halogen surface material of the invention adopts TPU as the material of the decorative layer and the wear layer, and uses the environment-friendly non-halogen polymer material as the material of the base layer, so that the obtained surface material does not contain halogen, and thus is incinerated. No harmful substances are generated in the process to meet environmental protection requirements; and since the base layer material does not contain PVC, the non-halogen surface material of the present invention does not need to be added with a plasticizer (phthalate), thereby avoiding Human hazards caused by the introduction of phthalates.
  • a plasticizer phthalate
  • the TPU film and the supporting film thereof are fixed and printed together by the pseudo-bonding printing method, and the elastic deformation of the decorative layer base layer (ie, the TPU film) can be reduced, and the printed pattern can be prevented from being sampled.
  • the use of a TPU printing film in place of the PETG printing film can effectively reduce the product cost and product deformation problems caused by shrinkage of the printing film itself.

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Abstract

提供一种非卤表面材料及其制造方法。该非卤表面材料包括基体层、装饰层及耐磨层，该耐磨层为TPU透明片材，该装饰层为TPU印刷膜，该基体层为非卤高分子片材，该耐磨层的材料包括TPU和添加剂，该基体层的材料包括非卤高分子材料和填料，该非卤高分子材料为TPU或TPU、NBR、ABS、PETG中至少两种的混合物。该非卤表面材料选用环保高分子材料，不引入增塑剂，不含卤素，在焚烧处理时不会产生有害物质。装饰层采用特殊工艺印刷TPU薄膜，克服了TPU印刷时因弹性变形而导致的图案走样的缺陷。

Description

一种非卤表面材料及其制造方法
优先权声明
本发明主张同一申请人于2016年5月25日于中国大陆地区申请的申请号为201610353389.7、名称为“一种非卤表面材料及其制造方法”的专利申请的优先权。
技术领域
本发明涉及一种室内外装潢领域使用的表面材料及其制造方法，特别是关于一种环保型非卤表面材料及其制造方法。
背景技术
在室内外装潢领域，人们会选择不同的表面铺装材料来铺设地面。表面铺装材料通常分为原木、石材、橡胶、亚麻及复合材料等。PVC(聚氯乙烯)因其出色的防水、阻燃和耐磨性能，以及花色多样、美观耐用、铺装简单及更换成本低廉的优点，在复合材料市场上占有率最大。
然而，由于高分子聚氯乙烯即PVC材料在自然界中无法自然降解，所以采用焚烧的方法进行处理。由于PVC是一种高卤聚合物，自身含有卤素，在燃烧时会产生HCl气体及二噁英等有害物质，所以有必要开发一款环保的非卤表面材料。
CN102733581A号揭露了一种非PVC材质的地砖，其采用PETG(聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯)作为原料，制作出符合环保要求的地砖。然而，PETG不能添加无机填料，成本高昂，且PETG虽具有易于印刷的特性，但其本身的热收缩性能非常大，尺寸稳定性较差。PETG透明耐磨层，抗刮性能交叉。实验还发现，用PETG作为印刷膜制备的非PVC地砖，经过回火处理后，产品仍不能克服翘曲变形的缺陷。
因此，有必要开发一种尺寸稳定性好，且成本能够被市场所接受的用于铺装的环保非卤表面材料。
发明内容
有鉴于此，本发明提供一种环保型的非卤表面材料及其制造方法。
本发明提供的非卤表面材料，包括基体层、装饰层及耐磨层，该耐磨层为TPU透明片材，该装饰层为TPU印刷膜，该基体层为非卤高分子片材，该耐磨层的材料包括TPU和添加剂，该基体层的材料包括非卤高分子材料和填料，该非卤高分子材料为TPU或TPU、NBR、ABS、PETG中至少两种的混合物。
根据本发明的一个实施例，该耐磨层的材料包括TPU颗粒100份以及添加剂1-15份，该添加剂为稳定剂或稳定剂与抗氧剂和消烟剂中至少一种的混合物。
根据本发明的一个实施例，该基体层的材料包括非卤高分子材料颗粒100份、填料100-300份以及添加剂1-15份，该添加剂为稳定剂或稳定剂与阻燃剂和消烟剂中至少一种的混合物，该填料为石粉、方解石和高岭土中至少一种。
根据本发明的一个实施例，100份的该混合物包括：75-95份的TPU颗粒和5-25份的NBR颗粒，或者80-95份的TPU颗粒和5-20份的PETG颗粒，或者55-90份的TPU颗粒、5-25份的NBR颗粒和5-20份的PETG颗粒，或者70-90份的TPU颗粒和10-30份的ABS颗粒，或者85-95份的ABS颗粒和5-15份的NBR颗粒，或者80-95份的PETG颗粒和5-20份的NBR颗粒，或者20-40份的TPU颗粒、10-30份的ABS颗粒、10-20份的NBR颗粒以及15-30份的PETG颗粒。
本发明提供的非卤表面材料的制造方法，包括：制备非卤高分子材料和填料的混合料，以挤出成型法或压延成型法制备基体层；制备装饰层，包括：准备TPU薄膜；准备支撑膜；将TPU薄膜和支撑膜假性贴合并开始印刷，在TPU薄膜的背向支撑膜一侧表面印刷图案；印刷完毕后将两层膜分离，得到TPU印刷膜；制备TPU和添加剂的混合料，采用合适的工艺制备耐磨层；将基体层、装饰层和耐磨层通过热压贴合或在线贴合法贴合在一起，制得非卤表面材料。
根据本发明的一个实施例，制备基体层时，压延成型温度为120-170℃， 挤出成型温度为150-190℃。
根据本发明的一个实施例，热压贴合的步骤包括：将制得的基体层、装饰层和耐磨层按顺序叠放；将叠放好的膜层通过热压机，在100-170℃温度和25-180MPa压力下进行热压贴合，形成非卤表面材料。
根据本发明的一个实施例，在线贴合的步骤包括：将基体层、装饰层和耐磨层按顺序置于挂料辊中；将基体层、装饰层和耐磨层同时送入在线贴合装置进行贴合，形成非卤表面材料，该在线贴合装置包括沿水平线方向设置的若干组压辊，各组压辊包括上下对称的压辊。
根据本发明的一个实施例，制备装饰层时采用的支撑膜为植物纤维纸、PP膜、PET膜、PA膜、PC膜、PS膜、PETG膜和POM膜中的一种。
根据本发明的一个实施例，该非卤高分子材料为TPU或TPU、NBR、ABS、PETG中至少两种的混合物，100份的该混合物包括：75-95份的TPU颗粒和5-25份的NBR颗粒，或者80-95份的TPU颗粒和5-20份的PETG颗粒，或者55-90份的TPU颗粒、5-25份的NBR颗粒和5-20份的PETG颗粒，或者70-90份的TPU颗粒和10-30份的ABS颗粒，或者85-95份的ABS颗粒和5-15份的NBR颗粒，或者80-95份的PETG颗粒和5-20份的NBR颗粒，或者20-40份的TPU颗粒、10-30份的ABS颗粒、10-20份的NBR颗粒以及15-30份的PETG颗粒。
综上所述，本发明的非卤表面材料通过采用TPU作为装饰层和耐磨层的材料，并采用环保型的非卤高分子材料作为基体层的材料，使制得的表面材料不含卤素，因而在焚烧处理过程中不会产生有害物质，达到环保的要求；并且，由于基体层材料中不含PVC，所以本发明的非卤表面材料无需添加增塑剂(邻苯二甲酸酯类)，从而可以避免因引入邻苯二甲酸酯类而引起的人体危害。另外，本发明制备装饰层时采用假性贴合印刷法，将TPU薄膜和其支撑膜固定在一起印刷，可以缩小装饰层基层(即TPU薄膜)的弹性变形，避免印刷图案走样。再者，使用TPU印刷膜代替PETG印刷膜，能有效降低产品成本及因印刷膜本身的收缩导致的产品变形问题。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，而可依照说明书的内容予以实施，并且为了让本发明的上述和其它 目的、特征和优点能够更明显易懂，以下特举实施例，并配合附图，详细说明如下。
附图概述
图1是本发明非卤表面材料的结构示意图。
图2是本发明非卤表面材料的一种制造方法的流程示意图。
图3是图2中步骤S13的示意图。
图4是本发明非卤表面材料的另一种制造方法的流程示意图。
图5是图4中步骤J14的示意图。
本发明的较佳实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效，以下结合附图及较佳实施例，对依据本发明提出的非卤表面材料及其制造方法的具体实施方式、结构、特征及其功效，详细说明如下：
有关本发明的前述及其它技术内容、特点及功效，在以下配合参考图式的较佳实施例的详细说明中将可清楚呈现。通过具体实施方式的说明，当可对本发明为达成预定目的所采取的技术手段及功效得以更加深入且具体的了解，然而所附图式仅是提供参考与说明之用，并非用来对本发明加以限制。
第一实施例：
本发明的非卤表面材料为复合材料，其不仅可用于铺设地面，还可用于铺设天花板、墙壁、衣柜等。在本发明中，该非卤表面材料优选为复合地板。请参见图1，该非卤表面材料100由下而上依次包括基体层10、装饰层20和耐磨层30。
基体层10为TPU片材，其包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10可以不包括中间层12。
底料层11的材料包括TPU颗粒、填料及添加剂。在本实施例中，底料层11的材料由TPU颗粒、填料和添加剂组成。底料层11的材料中各组分的 配比如下：TPU(热塑性聚氨酯)颗粒100份，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12包括TPU颗粒、填料及添加剂。在本实施例中，中间层12的材料由TPU颗粒、填料和添加剂组成。中间层12的材料中各组分的配比如下：TPU颗粒100份，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
在底料层11和中间层12中，填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
在本实施例中，基体层10的基材为TPU，在本发明的其它实施例中，基体层10的基材也可以为其它非卤高分子材料，例如TPU、NBR(丁腈橡胶)、ABS(丙烯腈-丁二烯-苯乙烯共聚物)、PETG(聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯)中至少两种的混合物。
装饰层20为TPU印刷膜，该印刷膜通过假性贴合印刷法制备而成。由于TPU弹性大且柔韧性好，使得TPU印刷膜在印刷时容易“走版(对版不准)”，无法实现印刷。为解决TPU薄膜印刷时的“走版”问题，本发明提出假性贴合印刷法。假性贴合印刷法是在TPU薄膜的一侧表面假性贴合支撑膜，印刷时，在TPU薄膜的背向支撑膜的一侧表面上印刷图案，印刷完毕后将两层膜分离，即制得TPU印刷膜。在假性贴合印刷法中，采用的支撑膜可以为植物纤维纸、PP(聚丙烯)膜、PET(聚对苯二甲酸乙二醇酯)膜、PA(聚酰胺)膜、PC(聚碳酸酯)膜、PS(聚苯乙烯)膜、PETG(聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯)膜和POM(聚甲醛)膜中的一种。
耐磨层30为TPU透明片材，耐磨层30的材料包括TPU颗粒和添加剂。在本实施例中，耐磨层30的材料由TPU颗粒和添加剂组成。耐磨层30的材料中各组分的配比如下：TPU颗粒100份，添加剂1-15份(其中包括稳定剂1-10份，抗氧剂0-10份，消烟剂0-1份)。
在本发明的另一个实施例中，耐磨层30中的添加剂或添加剂中的某些 组成可酌情省略。
耐磨层30的稳定剂可以为聚碳化二亚胺(型号：UN-03)，抗氧剂可以是抗氧剂1010(四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)，消烟剂为透明料专用消烟剂，例如二茂铁、钼系消烟剂。
下面介绍上述非卤表面材料的一种制造方法，该方法称为热压贴合法，请参见图2，该方法包括以下步骤：
步骤S11：制备底料层11。具体方法包括：按照底料层11的材料组成及配比称取各物质，将它们高速搅拌后，投放到混练机中混炼3-15min成混合料；将制得的混合料通过压延机压延成型而制得底料层11。压延成型温度为135-150℃。
步骤S12：制备中间层12。具体方法包括：按照中间层12的材料组成及配比称取各物质，将它们高速搅拌后，投放到混练机中混炼3-15min成混合料；将制得的混合料通过压延机压延成型而制得中间层12。压延成型温度为135-150℃。
步骤S13：制备装饰层20，具体方法包括：以TPU薄膜作为表层膜；准备支撑膜，支撑膜可以为植物纤维纸、PP膜、PET膜、PA膜、PC膜、PS膜、PETG膜和POM膜中的一种；将TPU薄膜和支撑膜假性贴合后开始印刷，印刷面为TPU薄膜的背向支撑膜一侧的表面；印刷完毕后将两层膜分离，得到TPU印刷膜。假性贴合时，TPU薄膜和支撑膜借助于两层薄膜之间的表面张力假性贴合在一起。如图3所示，印刷时，将TPU薄膜21和支撑膜22固定在一位于传送滚轮23或传送带上的固定治具24上，令固定治具24依次通过若干个印刷滚轮25，每个印刷滚轮25上涂覆有一种颜料，当固定治具24经过所有的印刷滚轮25后即在TPU薄膜21的表面印刷好完整的图案。
步骤S14：制备耐磨层30。具体方法包括：按照耐磨层30的材料组成及配比准备各物质；采用压延法、流延法、吹塑法等合适的工艺制得耐磨层30。
步骤S15：将步骤S11-S14制得的底料层11、中间层12、装饰层20和耐磨层30按顺序叠放，在100-170℃的温度和25-180MPa的压力下热压贴合 10-20min，形成非卤表面材料100。
下面介绍非卤表面材料的另一种制造方法，该方法称为在线贴合法，请参见图4，该方法包括以下步骤：
步骤J11：制备底料层11。具体方法包括：按照底料层11的材料组成及配比称取各物质，将它们高速搅拌后，投放到混练机中混炼3-15min成混合料；将制得的混合料通过挤出机挤出成型制得底料层11。挤出成型温度为160-180℃。
步骤J12：制备装饰层20，具体方法同步骤S13。
步骤J13：制备耐磨层30。具体方法包括：按照耐磨层30的材料组成及配比准备各物质；采用压延法、流延法、吹塑法等合适工艺制得耐磨层30。
步骤J14：如图5所示，将步骤J11-J13制得的底料层11、装饰层20、耐磨层30按顺序置于挂料辊40中，经过在线贴合装置进行贴合，形成非卤表面材料100。该在线贴合装置包括沿水平线设置的若干组上下对称的压辊50，底料层11、装饰层20、耐磨层30共同经过上下对称的压辊50之间时，在压辊50的作用下贴合在一起。为了使底料层11、装饰层20和耐磨层30沿特定的方向进入上下对称的压辊50之间，在线贴合装置还设有导向辊60。当利用压辊50进行贴合时，需根据需要对压辊50加热，并且各组压辊50的温度沿物料的进行方向依次递增，以使经过的物料可以更为容易地压合在一起。但为了便于将贴合好的产品从在线贴合装置上引离下来，最后两组压辊50的温度应比较接近。在贴合时，为了便于经过的物料更好地贴合，各组压辊50的线速度也应该沿物料的进行方向逐渐增大。
在上述两种制备方法中，由于挤出成型和压延成型加工出的片材的厚度和性能的不同，采用挤出成型的方式制备基体层10时，一般仅制作单层结构，而采用压延成型的方式制备基体层10时，可以制作多层结构。
第二实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的 中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括TPU/NBR混合物、填料和添加剂。在本实施例中，底料层11的材料由TPU/NBR混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：TPU/NBR混合物100份(其中包括TPU颗粒75-95份，NBR颗粒5-25份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括TPU/NBR混合物、填料和添加剂。在本实施例中，中间层12的材料由TPU/NBR混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：TPU/NBR混合物100份(其中包括TPU颗粒75-95份，NBR颗粒5-25份)，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。加工温度的改变是由于基体层材料中NBR的加入，NBR与TPU的相容性非常好，且NBR的加入能提高TPU的柔韧性，有效拓宽基体层的成型加工温度，但加入太多容易使TPU变软，因此，控制NBR的含量为5-25％。
第三实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括TPU/PETG混合物、填料和添加剂。在本实施例中，底料层11的材料由TPU/PETG混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：TPU/PETG混合物100份(其中包括TPU颗粒80-95份，PETG颗粒5-20份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括TPU/PETG混合物、填料和添加剂。在本实施例中，中间层12的材料由TPU/PETG混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：TPU/PETG混合物100份(其中包括TPU颗粒80-95份，PETG颗粒5-20份)，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。PETG与TPU的相容性非常好，且PETG的加入也可以影响基体层的成型加工温度。另外，PETG的加入还可以显著提高基体层材料的硬度，但加入太多PETG的话基体层材料易脆，因此，控制PETG的含量为5-20％。
第四实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括TPU/NBR/PETG混合物、填料和添加剂。在本实 施例中，底料层11的材料由TPU/NBR/PETG混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：TPU/NBR/PETG混合物100份(其中包括TPU颗粒55-90份，NBR颗粒5-25份，PETG颗粒5-20份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括TPU/NBR/PETG混合物、填料和添加剂。在本实施例中，中间层12的材料由TPU/NBR/PETG混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：TPU/NBR/PETG混合物100份(其中包括TPU颗粒55-90份，NBR颗粒5-25份，PETG颗粒5-20份)，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。
第五实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括TPU/ABS混合物、填料和添加剂。在本实施例中，底料层11的材料由TPU/ABS混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：TPU/ABS混合物100份(其中包括TPU颗粒70-90 份，ABS颗粒10-30份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括TPU/ABS混合物、填料和添加剂。在本实施例中，中间层12的材料由TPU/ABS混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：TPU/ABS混合物100份(其中包括TPU颗粒70-90份，ABS颗粒10-30份)，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。通过调整基体层材料中ABS的含量，也可以将加工温度控制在上述范围内。
第六实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括ABS/NBR混合物、填料和添加剂。在本实施例中，底料层11的材料由ABS/NBR混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：ABS/NBR混合物100份(其中包括ABS颗粒85-95份，NBR颗粒5-15份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括ABS/NBR混合物、填料和添加剂。在本实施例中， 中间层12的材料由ABS/NBR混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：ABS/NBR混合物100份(其中包括ABS颗粒85-95份，NBR颗粒5-15份)，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。通过基体层材料中ABS和NBR的配比，也可以将加工温度控制在上述范围内。
第七实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括PETG/NBR混合物、填料和添加剂。在本实施例中，底料层11的材料由PETG/NBR混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：PETG/NBR混合物100份(其中包括PETG颗粒80-95份，NBR颗粒5-20份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括PETG/NBR混合物、填料和添加剂。在本实施例中，中间层12的材料由PETG/NBR混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：PETG/NBR混合物100份(其中包括PETG颗粒80-95份，NBR颗粒5-20份)，填料200-300份，添加剂1-15份(其中 包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。通过基体层材料中PETG和NBR的配比，也可以将加工温度控制在上述范围内。
第八实施例：
本实施例的非卤表面材料的装饰层20和耐磨层30与第一实施例的非卤表面材料完全相同，本实施例与第一实施例的不同之处在于基体层10。
在本实施例中，基体层10同样包括底料层11与位于底料层11之上的中间层12。在本发明的另一个实施例中，基体层10也可以不包括中间层12。
底料层11的材料包括TPU/ABS/NBR/PETG混合物、填料和添加剂。在本实施例中，底料层11的材料由TPU/ABS/NBR/PETG混合物、填料和添加剂组成。底料层11的材料中各组分的配比如下：TPU/ABS/NBR/PETG混合物100份(其中包括TPU颗粒20-40份，ABS颗粒10-30份，NBR颗粒10-20份，PETG颗粒15-30份)，填料100-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
中间层12的材料包括TPU/ABS/NBR/PETG混合物、填料和添加剂。在本实施例中，中间层12的材料由TPU/ABS/NBR/PETG混合物、填料和添加剂组成。中间层12的材料中各组分的配比如下：TPU/ABS/NBR/PETG混合物100份(其中包括TPU颗粒20-40份，ABS颗粒10-30份，NBR颗粒10-20份，PETG颗粒15-30份)，填料200-300份，添加剂1-15份(其中包括稳定剂1-10份，阻燃剂0-5份，消烟剂0-1份)。
在本发明的另一个实施例中，基体层10中的添加剂或添加剂中的某些组成可酌情省略。
底料层11和中间层12的填料可以为石粉、方解石或高岭土，稳定剂可以为聚碳化二亚胺(型号：UN-03)，阻燃剂可以为氢氧化镁、氢氧化铝、水合硼酸锌和水滑石，消烟剂可以为二茂铁或钼系消烟剂。
本实施例的非卤表面材料的制造方法同第一实施例基本相同，不同之处在于加工温度。当利用热压贴合法制备非卤表面材料时，步骤S11和S12中的压延成型温度为120-170℃。当利用在线贴合法制备非卤表面材料时，步骤J11中的挤出成型温度在150-190℃。
综上所述，本发明具有下述至少其中之一个优点：
(1)本发明的非卤表面材料通过采用TPU作为装饰层和耐磨层的材料，并采用环保型的非卤高分子材料作为基体层的材料，使制得的表面材料不含卤素，因而在焚烧处理过程中不会产生有害物质，达到环保的要求。
(2)采用假性贴合印刷法，将TPU薄膜和其支撑膜固定在一起印刷，可以缩小装饰层基层(即TPU薄膜)的弹性变形，避免印刷图案走样；再者，使用TPU印刷膜代替PETG印刷膜，能有效降低产品成本及因印刷膜本身的收缩导致的产品变形问题。
(3)由于基体层材料中不含PVC，所以本发明的非卤表面材料无需添加增塑剂(邻苯二甲酸酯类)，从而可以避免因引入邻苯二甲酸酯类而引起的人体危害。
(4)基体层和耐磨层均能直接混炼后压延成型，成型快，尺寸准，可批量生产。
(5)在本发明中，优选基体层的基材为TPU/NBR混合物，TPU/PETG混合物和TPU/NBR/PETG混合物中的一种。首先，由于NBR、PETG与TPU三者之间的相容性非常好，保证了混合后材料的性质良好；再者，PETG的加入能显著提高混合料的硬度，但加入太多PETG导致混合料易脆，因此控制PETG的含量为5-20％；NBR的加入能提高混合料的柔韧性，有效拓宽基体层的成型加工温度，但加入太多NBR容易使混合料变软，因此控制NBR 的含量为5-25％，与单纯采用TPU相比，采用压延成型法制备时加工温度可以拓宽到120-170℃，采用挤出成型制备时加工温度可以拓宽到150-190℃。
以上所述，仅是本发明的实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
工业实用性
本发明的非卤表面材料通过采用TPU作为装饰层和耐磨层的材料，并采用环保型的非卤高分子材料作为基体层的材料，使制得的表面材料不含卤素，因而在焚烧处理过程中不会产生有害物质，达到环保的要求；并且，由于基体层材料中不含PVC，所以本发明的非卤表面材料无需添加增塑剂(邻苯二甲酸酯类)，从而可以避免因引入邻苯二甲酸酯类而引起的人体危害。另外，本发明制备装饰层时采用假性贴合印刷法，将TPU薄膜和其支撑膜固定在一起印刷，可以缩小装饰层基层(即TPU薄膜)的弹性变形，避免印刷图案走样。再者，使用TPU印刷膜代替PETG印刷膜，能有效降低产品成本及因印刷膜本身的收缩导致的产品变形问题。

Claims (10)

  1. 一种非卤表面材料，包括基体层、装饰层及耐磨层，其特征在于，该耐磨层为TPU透明片材，该装饰层为TPU印刷膜，该基体层为非卤高分子片材，该耐磨层的材料包括TPU和添加剂，该基体层的材料包括非卤高分子材料和填料，该非卤高分子材料为TPU或TPU、NBR、ABS、PETG中至少两种的混合物。
  2. 如权利要求1所述的非卤表面材料，其特征在于，该耐磨层的材料包括TPU颗粒100份以及添加剂1-15份，该添加剂为稳定剂或稳定剂与抗氧剂和消烟剂中至少一种的混合物。
  3. 如权利要求1所述的非卤表面材料，其特征在于，该基体层的材料包括非卤高分子材料颗粒100份、填料100-300份以及添加剂1-15份，该添加剂为稳定剂或稳定剂与阻燃剂和消烟剂中至少一种的混合物，该填料为石粉、方解石和高岭土中至少一种。
  4. 如权利要求1所述的非卤表面材料，其特征在于，100份的该混合物包括：75-95份的TPU颗粒和5-25份的NBR颗粒，或者80-95份的TPU颗粒和5-20份的PETG颗粒，或者55-90份的TPU颗粒、5-25份的NBR颗粒和5-20份的PETG颗粒，或者70-90份的TPU颗粒和10-30份的ABS颗粒，或者85-95份的ABS颗粒和5-15份的NBR颗粒，或者80-95份的PETG颗粒和5-20份的NBR颗粒，或者20-40份的TPU颗粒、10-30份的ABS颗粒、10-20份的NBR颗粒以及15-30份的PETG颗粒。
  5. 一种非卤表面材料的制造方法，其特征在于，其包括如下步骤：
    制备非卤高分子材料和填料的混合料，以挤出成型法或压延成型法制备基体层；
    制备装饰层，包括：准备TPU薄膜；准备支撑膜；将TPU薄膜和支撑膜假性贴合并开始印刷，在TPU薄膜的背向支撑膜一侧的表面印刷图案；印刷完毕后将两层膜分离，得到TPU印刷膜；
    制备TPU和添加剂的混合料，采用合适的工艺制备耐磨层；
    将基体层、装饰层和耐磨层通过热压贴合或在线贴合法贴合在一起，制 得非卤表面材料。
  6. 如权利要求5所述的非卤表面材料的制造方法，其特征在于，制备基体层时，压延成型温度为120-170℃，挤出成型温度为150-190℃。
  7. 如权利要求5所述的非卤表面材料的制造方法，其特征在于，热压贴合的步骤包括：
    将制得的基体层、装饰层和耐磨层按顺序叠放；
    将叠放好的膜层通过热压机，在100-170℃温度和25-180MPa压力下热压贴合，形成非卤表面材料。
  8. 如权利要求5所述的非卤表面材料的制造方法，其特征在于，在线贴合的步骤包括：
    将基体层、装饰层和耐磨层按顺序置于挂料辊中；
    将基体层、装饰层和耐磨层同时送入在线贴合装置进行贴合，形成非卤表面材料，该在线贴合装置包括沿水平线方向设置的若干组压辊，各组压辊包括上下对称的压辊。
  9. 如权利要求5所述的非卤表面材料的制造方法，其特征在于，制备装饰层时采用的支撑膜为植物纤维纸、PP膜、PET膜、PA膜、PC膜、PS膜、PETG膜和POM膜中的一种。
  10. 如权利要求5所述的非卤表面材料的制造方法，其特征在于，该非卤高分子材料为TPU或TPU、NBR、ABS、PETG中至少两种的混合物，100份的该混合物包括：75-95份的TPU颗粒和5-25份的NBR颗粒，或者80-95份的TPU颗粒和5-20份的PETG颗粒，或者55-90份的TPU颗粒、5-25份的NBR颗粒和5-20份的PETG颗粒，或者70-90份的TPU颗粒和10-30份的ABS颗粒，或者85-95份的ABS颗粒和5-15份的NBR颗粒，或者80-95份的PETG颗粒和5-20份的NBR颗粒，或者20-40份的TPU颗粒、10-30份的ABS颗粒、10-20份的NBR颗粒以及15-30份的PETG颗粒。
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