WO2017016206A1 - 复合地板及其制备方法 - Google Patents

复合地板及其制备方法 Download PDF

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Publication number
WO2017016206A1
WO2017016206A1 PCT/CN2016/072020 CN2016072020W WO2017016206A1 WO 2017016206 A1 WO2017016206 A1 WO 2017016206A1 CN 2016072020 W CN2016072020 W CN 2016072020W WO 2017016206 A1 WO2017016206 A1 WO 2017016206A1
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Prior art keywords
layer
weight
composite floor
resin
group
Prior art date
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PCT/CN2016/072020
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English (en)
French (fr)
Inventor
张明奇
Original Assignee
明和（芦台）科技有限公司
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Publication of WO2017016206A1 publication Critical patent/WO2017016206A1/zh

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    • 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
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • E04F15/107—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials composed of several layers, e.g. sandwich panels
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    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/12—Compression moulding
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    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/04—Conditioning or physical treatment of the material to be shaped by cooling
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    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B32B2419/04—Tiles for floors or walls
    • 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
    • B32B2471/00—Floor coverings
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention relates to a composite floor and a preparation method thereof, in particular to an environment-friendly composite floor which can be repeatedly used repeatedly and a preparation method thereof.
  • the floor is an indispensable decorative material in the home decoration.
  • floors such as wooden floors, laminate flooring, ceramic tiles and plastic flooring.
  • the wooden floor and the reinforced floor are all bonded by 3-4 layers, and most of the layers are bonded by a binder, and the adhesive contains not only harmful substances such as melamine, phenol, formaldehyde, but also Not waterproof, and the price, installation and maintenance costs are high; tiles are prone to cracks, difficult to replace and difficult to clean and so on; plastic flooring has the advantages of cheap, waterproof, moisture-proof, wear-resistant and scratch-resistant, and has been favored by people.
  • the current plastic flooring also has many problems.
  • the plastic flooring on the market is generally polyvinyl chloride (PVC) flooring, and the dimensional stability of the PVC flooring is not good, especially when the household is equipped with floor heating, the floor size is obviously changed due to the large temperature difference; and the PVC floor Plasticizers are usually added, usually accompanied by precipitation of plasticizers, which are reproductively harmful and harmful to humans; in addition, PVC flooring does not achieve environmental protection in the true sense because PVC cracking It will produce substances such as HCl and CO, and will produce toxic gases such as dioxane after combustion.
  • PVC polyvinyl chloride
  • plastic flooring Different types are installed in different ways.
  • the types of plastic flooring currently on the market include dry bottom flooring, adhesive flooring, and lock flooring.
  • dry bottom flooring When the dry bottom floor is under construction, the floor must be kept level and clean. First apply a layer of thick and uniform adhesive on the floor, then lay the floor on the floor. After the adhesive is fully cured, the floor can be paved. If the floor is replaced, it takes time and effort, and the adhesive will remain on the ground and even damage the floor.
  • the adhesive floor is coated with a layer of hot melt adhesive on the back of the floor. The floor is directly laid on the floor when paving. It is faster and easier to construct than the dry bottom floor. However, the adhesive floor is not suitable for future replacement, such as tearing the floor. After that, the hot melt adhesive will lose its viscosity, and the ground will have residual hot melt adhesive, which is difficult to clean. When the floor is applied, there is no residual glue in comparison with the former two, but the mute effect of the floor is not ideal.
  • the present invention provides a composite floor comprising a protective layer, a decorative layer and a support layer, wherein the protective layer comprises a UV coating and an abrasion resistant layer, the decorative layer comprising an ink and a printing substrate, the support layer comprising An inorganic mineral powder of calcium carbonate, diatomaceous earth, titanium white powder, talc powder and mica powder, a polyolefin selected from the group consisting of polypropylene and polyethylene, and a thermoplastic polyolefin elastomer, a coupling agent and a flame retardant.
  • the protective layer comprises a UV coating and an abrasion resistant layer
  • the decorative layer comprising an ink and a printing substrate
  • the support layer comprising An inorganic mineral powder of calcium carbonate, diatomaceous earth, titanium white powder, talc powder and mica powder, a polyolefin selected from the group consisting of polypropylene and polyethylene, and a thermoplastic polyolefin elastomer, a coupling agent
  • a balance layer is further disposed on a side of the support layer facing the ground, the balance layer comprising polypropylene or polyethylene filled with calcium carbonate, diatomaceous earth, An inorganic mineral powder of titanium dioxide, talc and mica powder, and optionally one or more processing aids selected from the group consisting of dispersants, lubricants, coupling agents, antistatic agents, antioxidants and flame retardants, And the balance layer does not contain a plasticizer.
  • a backing layer is further disposed on the side of the balance layer facing the ground,
  • the adhesive layer is a pressure sensitive hot melt adhesive.
  • a layer of cork is further disposed between the support layer and the balance layer, the cork layer being passed through a binder resin selected from the group consisting of acrylic resins, polyurethane resins, epoxy resins, and phenolic resins. Bonded to the support layer and the balance layer.
  • the composite floor of the invention can meet environmental protection requirements, meets the European Union standards such as VOC (0-VOC), CE, FDA, REACH, etc., and can realize quick and convenient construction, and no residual glue is left on the ground when replacing, and can be repeatedly used, and The floor is dimensionally stable and does not warp.
  • FIG. 1 is a schematic view showing the layer structure of an embodiment of a composite flooring of the present invention.
  • Figure 2 is a schematic view showing the layer structure of another embodiment of the composite flooring of the present invention.
  • Figure 3 is a schematic view showing the layer structure of still another embodiment of the composite flooring of the present invention.
  • thermoplastic Elastomer refers to a material that can be plasticized at high temperatures and exhibits the elasticity of vulcanized rubber at room temperature. These materials combine the processing formability of thermoplastics with vulcanized rubber. Highly elastic properties.
  • Thermoplastic elastomers generally include the following categories: 1) thermoplastic polyurethane elastomers (TPU); 2) styrenic block thermoplastics, typically of the thermoplastic styrene-butadiene-styrene (SBS) block copolymer.
  • thermoplastic styrene-isoprene-styrene block copolymer thermoplastic styrene-isoprene-styrene block copolymer, and styrene-butadiene star block copolymer, etc.
  • thermoplastic polyester elastomer which is usually composed of dicarboxylic acid a turtle block copolymer obtained by melt transesterification of a mixture of an acid and a derivative thereof (such as dimethyl terephthalate), a polyether diol (molecular weight 600-6000), and a low molecular diol
  • Thermoplastic polyolefin elastomer thermoplastic styrene-isoprene-styrene block copolymer, and styrene-butadiene star block copolymer, etc.
  • thermoplastic polyester elastomer which is usually composed of dicarboxylic acid a turtle block copolymer obtained by melt trans
  • thermoplastic Polyolefin is one of the thermoplastic elastomers which are usually prepared by blending, for example using ethylene propylene rubber with thermoplastic polyethylene or poly Propylene blending, or blending, while the dynamic vulcanization method is used to crosslink the rubber part, even grafting polyethylene or polypropylene on the rubber chain, and also including the thermoplastic polyolefin elasticity obtained by grafting polyethylene with butyl rubber. body.
  • polyolefin Elastomer refers to a thermoplastic having a narrow relative molecular weight distribution and a uniform short-chain distribution prepared by using a metallocene as a catalyst.
  • sexual elastomer For example, an ethylene-octene copolymer prepared by a solution polymerization method in which a crystalline region of a polyethylene chain functions as a physical crosslinking point, and the introduction of a certain amount of octene weakens the crystallization region of the polyethylene chain, forming a rubber elasticity. Amorphous zone.
  • OPE Oxidized Polyethylene
  • a polyethylene wax or a low molecular weight ethylene-vinyl acetate copolymer The oxidized polyethylene wax has a certain functional group on the molecular chain, so its compatibility with the polar resin is significantly improved, which is superior to polyethylene wax.
  • UV coating refers to a coating layer that is curable by ultraviolet light, which has the function of preventing ultraviolet light and functions such as abrasion resistance, scratch resistance, slip resistance, and antibacterial properties.
  • the present invention provides a composite floor comprising a protective layer, a decorative layer and a support layer, and optionally a balance layer, a softwood layer and a backing layer.
  • a composite floor comprising a protective layer, a decorative layer and a support layer, and optionally a balance layer, a softwood layer and a backing layer.
  • the protective layer is made of:
  • the protective layer in the composite flooring of the present invention comprises a UV coating, and a wear resistant layer.
  • the coating for forming the UV coating comprises 30-80% by weight, preferably 30-50% by weight, of one or more selected from the group consisting of polyfunctional polyurethane resins, polyacrylic resins, and epoxy resins, 20- 50% by weight of acrylic monomer, 4-15% by weight, preferably 4-8% by weight of photoinitiator and 0.08-0.2% by weight, preferably 0.08-0.12% by weight of oxidized polyethylene wax (OPE), said oxidation
  • the polyethylene wax is preferably a fine powder high density polyethylene wax having a density of, for example, about 0.98 g/cc and a melting point of, for example, 140 °C.
  • a fine powder of high density oxidized polyethylene wax referred to as OPE
  • OPE high density oxidized polyethylene wax
  • Oxidized polyethylene wax is an excellent new type of polar wax. Since the molecular chain of oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl groups, it has significant improvement in compatibility with fillers, pigments and polar resins, and also has excellent wear resistance. And toughness and other effects. OPE can distribute evenly in the UV coating and improve the wear and scratch resistance of the floor.
  • the wear layer in the protective layer comprises a resin selected from the group consisting of polyethylene and polypropylene, a polyolefin elastomer (POE), and a transparent nucleating agent, an antioxidant, One or more processing aids for UV absorbers, light stabilizers, modifiers, and flame retardants.
  • the modifier is, for example, a polypropylene grafted maleic anhydride copolymer.
  • the wear layer comprises 75 to 90% by weight of a polyethylene resin or a polypropylene resin, and 8 to 15% by weight of a polyolefin elastomer.
  • the processing aid is preferably used in the abrasion resistant layer in an amount of from 2 to 10% by weight.
  • the wear layer is the main force protecting the entire floor. Due to the problem of poor anti-aging of polyolefin, large shrinkage of molding, etc., it is preferred to add an antioxidant, an ultraviolet absorber, a light stabilizer, etc. to the wear-resistant layer to improve the aging resistance of the wear-resistant layer, reduce the shrinkage rate, and ensure the floor. It is exposed to the sun for a long time without problems such as floor deformation and aging.
  • a polyolefin elastomer is preferably added to the wear layer to increase the softness of the wear layer, and it is preferred that the polyolefin elastomer is contained in the wear layer in an amount of 8 to 15% by weight.
  • the transparency of the conventional polyolefin is not good.
  • a nucleating agent such as a transparent nucleating agent such as Millad 3988, NX4000 and ADK STAB NA-21 produced by Milliken is added, and it is rapidly made in production. Cooling produces a highly transparent wear layer that enhances overall transparency and enhances the visual impact of the floor.
  • the thickness of the wear resistant layer is preferably from 0.1 to 0.7 mm.
  • the surface of the wear layer is preferably treated with a "bridge agent" prior to applying the UV coating to the wear layer.
  • the bridging agent comprises 20-40% by weight of polyfunctional urethane acrylate or polyester acrylate, 2-6% by weight of photoinitiator, 2-8% by weight of surfactant, such as high activity phosphate LYCO-PO8, And 50-70% by weight of an organic solvent such as ethyl acetate, toluene and xylene.
  • LYCO-PO8 is a mixture of medium carbon chain phosphate monoester and diester specially prepared by Nortel Biotechnology (Hefei) Co., Ltd.
  • LYCO-PO8 can also be used in the processing of fiber oils and the like.
  • the decorative layer in the composite flooring of the present invention comprises an ink and a printed substrate.
  • the pattern of the decorative layer is liable to cause discoloration, and it is preferable to use an ink having a high temperature resistance of 170 ° C or more and strong adhesion.
  • CPP chlorinated polypropylene
  • CEVA chlorinated ethylene-vinyl acetate copolymer ink
  • a polyurethane ink is used as the ink for the decorative layer, the polyurethane ink comprising 8-25% by weight of a polyurethane resin, for example, having a molecular weight of 80-90 and a density of about 1 g/cm 3 .
  • Polyurethane resin 50-80% by weight, preferably 60-75% by weight, of one or more organic solvents such as ethyl acetate, n-propyl acetate, ethanol, isopropanol, etc., pigments and viscosity modifiers.
  • a bonding agent is preferably applied on the polyurethane ink layer, the bonding agent comprising a copolymer selected from the group consisting of polypropylene and ethylene-vinyl acetate.
  • the bonding agent comprising a copolymer selected from the group consisting of polypropylene and ethylene-vinyl acetate.
  • the chlorinated polypropylene ink (CPP)
  • the color development effect of the pigment and the printing effect of the ink are inferior, and the effect of using the ethylene chloride-vinyl acetate copolymer ink (CEVA) alone is improved, but it is ideal.
  • the use of the two is to improve the matching and coordination of the ink.
  • the chlorinated polypropylene ink used comprises: 5-30% by weight of chlorinated polypropylene having a chlorine content of 25-40 mol%, and a chlorine content of 7-11 wt% It is 28-38 mol% of a vinyl chloride-vinyl acetate copolymer, 60-70 wt% of one or more organic solvents, such as ethyl acetate, n-propyl acetate, ethanol, isopropanol, etc., pigments and Viscosity modifier.
  • the ink needs to cure quickly to prevent the web from sticking together.
  • the speed of curing depends on the type of solvent in the ink.
  • one or more solvents selected from the group consisting of ethyl acetate, n-propyl acetate, ethanol, and isopropanol are used as the ink solvent.
  • connection of the ink to the wear layer is important.
  • the ink and the components of the wear layer are chemically cross-linked by means of polar molecules in the ink.
  • the wear layer and the decorative layer are closely adhered.
  • the fine pigment particles of the ink in the decorative layer will migrate out through the wear layer, thereby affecting the visual effect of the decorative layer and affecting the wear resistance and scratch resistance of the wear layer. Contaminated equipment materials, etc.
  • the pigment in the ink used in the composite floor of the present invention is resistant to high temperatures, and the pigment particles are relatively large, and in addition, the polymer in the ink can adsorb the pigment molecules, so that the ink of the present invention avoids the bleeding and migration of the pigment particles.
  • the printed substrate of the decorative layer comprises a color selected from One or more inorganic mineral powders of calcium carbonate, diatomaceous earth, titanium dioxide, talc and mica powder, polyolefins selected from the group consisting of PE and PP, and optionally processing aids.
  • the processing aid includes one or more selected from the group consisting of a dispersant, a lubricant, a coupling agent, an antistatic agent, an antioxidant, and a flame retardant.
  • the printed substrate of the decorative layer comprises from 20 to 80% by weight, preferably from 40 to 70% by weight of polypropylene, from 18 to 70% by weight, preferably from 28 to 55% by weight of inorganic Mineral powder and 2 to 10% by weight, preferably 2 to 5% by weight, of a polypropylene printing substrate selected from one or more processing aids of dispersants, lubricants, coupling agents, antistatic agents.
  • the printed substrate of the decorative layer comprises from 10 to 50% by weight, preferably from 10 to 25% by weight, of polyethylene, from 40 to 80% by weight, preferably from 70 to 80% by weight.
  • An inorganic mineral powder selected from one or more of calcium carbonate, diatomaceous earth, titanium white powder, talc powder and mica powder, and 3 to 10% by weight selected from the group consisting of a dispersant, a lubricant, a coupling agent, an antioxidant, and A polyethylene printed substrate of one or more processing aids in a flame retardant.
  • the inorganic ore powder filling is used in the printing substrate of the composite floor of the invention, in particular, the content of the inorganic ore powder in the polyethylene printing substrate is relatively large, and in order to improve the printing effect of the ink thereon, it is preferable to print the substrate.
  • the printing surface is treated with a coating liquid, which may be a rubber emulsion, a polyacrylate emulsion, or a polyvinyl alcohol emulsion.
  • a coating liquid is used which comprises 60 to 85% by weight of isopropanol and/or water, 2 to 5% by weight of a film former, for example PVA, 0.5 to 1 by weight.
  • % antistatic agent 0.5-1% by weight of antioxidant, 15-33% by weight of one or more emulsions selected from rubber, polyacrylate or polyvinyl acetate.
  • the surface of the printing substrate is smooth, and no inorganic mineral powder molecules such as calcium carbonate are exposed, which can ensure a good printing effect.
  • the one side (bonding surface) of the printing substrate facing the supporting layer needs to be bonded to the supporting layer, and the bonding surface does not need to be coated in order to ensure the bonding fastness.
  • the substrate and the ink are darkened as a whole, and it is necessary to add a flame retardant and an antioxidant to increase the thermal oxidation temperature and inhibit the thermal oxidation thereof.
  • a flame retardant and an antioxidant may not be added, but in the production process, an antistatic agent is required to prevent the electrostatic connection after the production.
  • the composite flooring of the present invention when a PP printing substrate is used, in order to obtain an excellent bonding effect between the printing substrate and the support layer, it is preferred to treat the bonding surface of the PP printing substrate and the support layer.
  • the water is treated, and the treated water contains a mixed solvent of water and an alcohol solvent, and A crosslinking agent (such as Dow Corning 6040), an antioxidant (such as pentaerythritol ester), a film former (such as PVA), a surfactant (such as stearic acid), and a crosslinking agent (such as maleimide).
  • a crosslinking agent such as Dow Corning 6040
  • an antioxidant such as pentaerythritol ester
  • a film former such as PVA
  • a surfactant such as stearic acid
  • a crosslinking agent such as maleimide
  • the treated water comprises water and isopropanol as a solvent, 0.5% to 1% by weight of a coupling agent Dow Corning 6040, and 1-2% by weight of an antioxidant pentaerythritol ester, 0.3% to 2% by weight of the film former PVA, 0.3 to 0.8% by weight of the surfactant stearic acid, and 0.5% to 1% by weight of the crosslinking agent maleimide.
  • the bonding surface (back surface) of the printed substrate coated with the treated water forms a very thin treatment layer which chemically crosslinks with the components of the support layer during high temperature heat bonding.
  • the composite floor of the present invention includes a support layer as a host material.
  • the support layer comprises an inorganic ore powder selected from the group consisting of calcium carbonate, diatomaceous earth, titanium dioxide, talc, and mica powder, and a polyolefin selected from the group consisting of polypropylene and polyethylene.
  • the support layer comprises 65 to 85% by weight, preferably 75 to 85% by weight, of an inorganic ore selected from the group consisting of calcium carbonate, diatomaceous earth, titanium dioxide, talc and mica powder. Powder, 8 to 35% by weight, preferably 8 to 25% by weight, of one or more polyolefins selected from the group consisting of polypropylene and polyethylene, 1-2% by weight of thermoplastic polyolefin elastomer (TPO), 0.5-1 weight % coupling agent, 1-2% by weight of flame retardant.
  • TPO thermoplastic polyolefin elastomer
  • a coupling agent and a dispersing agent are added to the inorganic mineral powder-filled polymer material of the support layer, and the inorganic ore fine particles such as calcium carbonate can be uniformly dispersed on the plastic spherulites such as polyolefin. Make the two compatible. After the coupling agent and the dispersing agent are added, the exposed particles of the inorganic ore powder such as calcium carbonate are not present on the surface of the support layer.
  • the addition of a coupling agent enhances the fusion between the molecules, softens the overall material, improves the toughness, and the entire floor becomes soft and does not break due to external forces.
  • the addition of a dispersing agent makes the intermolecular mixing more uniform and acts as a lubricating agent, reduces the viscosity of the material after mixing, reduces the shrinkage rate, and avoids the problem of overall arching and warping of the floor.
  • the thickness of the support layer is preferably from 0.08 to 0.16 mm, more preferably from 0.08 mm to 0.12 mm.
  • a layer of polyester fiber mesh or glass mat may also be added inside the support layer, and the polyester fiber may be composed of an organic dibasic acid and a glycol.
  • Polycondensed such as polyethylene terephthalate, polybutylene terephthalate, and the like.
  • the fiber mesh may have a density of, for example, about 1.37 g/cm 3 and a diameter of the fiber of, for example, about 23 nm.
  • the fiberglass mat preferably has a basis weight of from 950 to 1000 grams per square meter and a thickness of preferably from 0.2 to 1.0 mm, more preferably from 0.2 to 0.5 mm.
  • the polyester fiber mesh cloth or the glass fiber felt can increase the shrinkage resistance and strength of the support layer, increase the overall stability of the floor, and avoid the problem of arching of the floor.
  • a balancing layer is also provided on the side of the support layer facing the ground.
  • the balancing layer comprises 70 to 95% by weight of at least one resin selected from the group consisting of polyethylene and polypropylene, 2 to 20% by weight of a polyolefin elastomer (POE), And 0 to 10% by weight of one or more processing aids selected from the group consisting of dispersants, lubricants, coupling agents, antistatic agents, antioxidants, and flame retardants, and not in the equilibrium layer Contains plasticizer.
  • the balance layer acts as a balance on the entire floor to avoid the problem of floor arching.
  • the balance weight of the polyolefin elastomer (POE) is present in an amount of from 8 to 15% by weight based on the total weight of the balance layer.
  • the composite floor of the present invention may be a "dry bottom" floor, i.e., the floor does not have a backing layer; it may also be a floor with a backing layer as described below.
  • the main component of the balance layer is a polyolefin
  • the ground-facing side of the balancing layer is treated with a bonding agent comprising a material selected from the group consisting of polypropylene, ethylene-vinyl acetate copolymer (EVA), epoxy resin, phenolic resin, rosin resin, and maleic anhydride.
  • EVA ethylene-vinyl acetate copolymer
  • the glue layer is a pressure sensitive hot melt adhesive.
  • the pressure sensitive hot melt adhesive forming the backing layer comprises 15-45% by weight of thermoplastic elastomer selected from the group consisting of thermoplastic polyurethane elastomer, styrene block thermoplastic rubber, and thermoplastic polyester.
  • Body thermoplastic elastomer 30-60% by weight selected from rosin resin, hydrogen A rosin glyceride, a C5 petroleum resin, a tackifying resin of a C9 petroleum resin and an alicyclic hydrogenated petroleum resin, an O-2% by weight antioxidant, and 0-25% by weight of a paraffin oil or a naphthenic oil. Soften the oil.
  • the content of the tackifying resin is high, so that the cohesive force of the adhesive layer is large, and the bonding force inside the colloid is strong, which is favorable for not leaving on the ground when peeling off from the ground. gum.
  • the amount of pressure sensitive hot melt adhesive of the backing layer is from 10 to 50 g/m 2 , more preferably from 15 to 25 g/m 2 .
  • a backing layer is provided on the side of the balancing layer facing the ground so that the adhesive layer adheres better to the floor body. Since the plasticizer is not used in the balance layer used in the present invention, the hot melt adhesive does not fall off due to precipitation of the plasticizer in the balance layer.
  • the side of the support layer or the balance layer facing the ground is selected before applying the adhesive layer to the ground facing side of the support layer or balance layer of the floor.
  • Surface treatment from corona treatment, flame treatment, chemical treatment and high energy treatment. The surface treatment enables the surface of the bottom surface of the adhesive layer to be applied to reach a suitable range of factors, for example, a surface tension of 42 dyne or more, thereby making the hot melt adhesive applied thereto and the bottom surface of the floor very A strong bond that is higher than the bond between the hot melt and the ground.
  • the floor can be easily bonded to the ground, and the shearing force of the hot melt adhesive is utilized, so that it is not easily misplaced on the ground, and is not caused by people walking or external forces.
  • the hot melt adhesive of the adhesive layer in the composite floor of the invention has high cohesion, and the cohesive force is greater than the adhesion of the hot melt adhesive to the ground, thereby easily separating the adhesive layer as a whole from the ground without being on the ground. Residual glue on the top makes it easy to construct and replace simple functions.
  • a cork layer is further disposed between the support layer and the balance layer or inside the support layer, and the softwood layer is selected from the group consisting of acrylic resin, polyurethane resin, and ring.
  • the binder resin of the oxyresin and the phenol resin is bonded to the support layer and the balance layer.
  • the resulting cork flooring not only enhances the woody feel, but also makes the overall floor elastic. Improve the user experience during use.
  • the softwood layer can achieve the effect of mute, and the mute of the softwood composite floor of the present invention can reach the detection standard of 55 decibels according to the ASTM test method for measuring the impact sound wave through the floor.
  • FIG. 1 shows an embodiment of a composite floor of the present invention comprising: a protective layer 1, a decorative layer 2, a support layer 3 and a balancing layer 4.
  • the protective layer 1 comprises a wear layer and a UV coating.
  • the decorative layer 2 comprises an ink and a printed substrate.
  • the main component of the support layer 3 is an inorganic mineral powder such as calcium carbonate and a polypropylene filled with a processing aid.
  • the main component of the balance layer 4 is an inorganic ore-filled polypropylene such as calcium carbonate, and the balance layer 4 does not contain a plasticizer.
  • FIG. 2 shows another embodiment of the composite floor of the present invention, which comprises: a protective layer 1, a decorative layer 2, a support layer 3, a balance layer 5, and a joint between the support layer 3 and the balance layer 5.
  • Cork layer 4. Adding a cork layer can achieve a silent effect.
  • ASTM ASTM, the fighter's laboratory measures the propagation of impact sound waves through the floor, and the floor mute can reach the detection standard of 55 decibels.
  • Figure 3 shows still another embodiment of the composite floor of the present invention, comprising a floor body 1 and a backing layer 2 composed of a protective layer, a decorative layer and a support layer, the backing layer 2 being passed through a pressure sensitive hot melt adhesive It is uniformly applied to the bottom surface of the floor body 1, and the amount of the glue is between 10 and 25 g/m 2 , and then the release paper is coated thereon.
  • the pressure sensitive hot melt adhesive comprises 15-40% by weight of a thermoplastic elastomer, 15-60% by weight of a tackifying resin, 0-2% by weight of an antioxidant, and 0-25% by weight of a softening oil.
  • the invention also provides a preparation method of the above composite floor, comprising the following steps:
  • the wear layer, the decorative layer and the support layer are heat-pressed together at a temperature of 140-170 ° C under a pressure of 40-80 kg to form a whole, and then
  • a UV coating is applied over the wear layer to form a protective layer comprising a UV coating and an abrasion resistant layer.
  • the wear resistant layer is prepared by using polyolefin (PP or PE) particles, a nucleating agent, a light stabilizer, an antioxidant, a flame retardant, and an ultraviolet absorber. After being uniformly mixed by a high-speed mixer, and then extruded through a planetary extruder, it enters the filter to remove impurities in the material, and is cooled by calendering or casting into a cooling wheel to form a high transparent thickness of 0.1-0.7 mm. membrane.
  • the wear layer increases the wear resistance of the floor and protects the appearance of the decorative layer, so that the floor maintains a beautiful appearance during long-term use.
  • the printing substrate is prepared by passing inorganic mineral powder such as calcium carbonate or diatomaceous earth, PP or PE particles, a coupling agent, a dispersing agent, a lubricant, and the like.
  • inorganic mineral powder such as calcium carbonate or diatomaceous earth, PP or PE particles, a coupling agent, a dispersing agent, a lubricant, and the like.
  • the machine is densely packed and then extrusion blow molded or calendered to form a film having a thickness of 0.08 to 0.16 mm.
  • the printing surface of the printing substrate is coated with a coating liquid, and the coating liquid is selected from the group consisting of Rubber emulsion, acrylic emulsion, and polyvinyl alcohol emulsion.
  • the coating liquid may, for example, comprise from 60 to 80% by weight of a mixture of isopropanol and water, from 2 to 5% by weight of a film former, such as PVA, from 0.5 to 1% by weight of an antistatic agent, from 0.5 to 1% by weight.
  • An antioxidant and 15 to 33% by weight of rubber, acrylic or polyvinyl alcohol.
  • the support layer is prepared by using inorganic mineral powder such as calcium carbonate or diatomaceous earth, PP or PE particles, a coupling agent, a dispersing agent, a lubricant, and a flame retardant.
  • the antistatic agent or the like is kneaded by an internal mixer and then extrusion-rolled to form a layer having a thickness of 0.6 to 1.2 mm.
  • the coupling agent may be selected, for example, from Dow Corning 6030 or 6040, the dispersing agent may be selected from Lubrizol 32500 or Mitsubishi P533J, the lubricant may be, for example, calcium stearate, or may be replaced by a dispersing agent, for example, a flame retardant may be used. It is selected from halogen-free flame retardants such as magnesium hydroxide.
  • the method further comprises providing a layer of polyester fiber mesh or glass fiber felt inside the support layer.
  • the polyester fiber may be obtained by polycondensation of an organic dibasic acid and a glycol, such as polyethylene terephthalate, polybutylene terephthalate or the like.
  • the fiber mesh may have a density of, for example, about 1.37 g/cm 3 and a diameter of the fiber of, for example, about 23 nm.
  • the UV coating is applied Prior to application to the wear layer, the wear layer is surface treated with a bridging agent comprising 20-40% by weight of polyfunctional urethane acrylate, 2-6 wt% of light priming
  • the agent is 2-8 wt% phosphate and 50-70 wt% organic solvent such as ethyl acetate, toluene and xylene.
  • a PP printing substrate is used, and preferably, the bonding surface to which the PP printing substrate and the supporting layer are bonded is surface-treated with treated water,
  • the treated water comprises solvent water and isopropanol, a coupling agent (such as Dow Corning 6030 or 6040) pentaerythritol ester, a film forming agent (such as PVA) surfactant (such as stearic acid), a crosslinking agent (such as maleimide).
  • the treated water comprises solvent water and isopropanol, 0.5-1% by weight of a coupling agent (for example, Dow Corning 6030 or 6040), and 1-2% by weight of pentaerythritol. Ester, 0.3-2% by weight of a film former (for example PVA), 0.3-0.8% by weight of a surfactant (for example stearic acid) and 0.5-1% by weight of a crosslinking agent (for example maleimide).
  • a coupling agent for example, Dow Corning 6030 or 6040
  • pentaerythritol Ester, 0.3-2% by weight of a film former (for example PVA), 0.3-0.8% by weight of a surfactant (for example stearic acid) and 0.5-1% by weight of a crosslinking agent (for example maleimide).
  • the treated water is prepared by incorporating PVA into water and continuously injecting hot steam to a temperature between 80 and 90 °C. After the PVA is completely dissolved in water, the coupling agent is added to stir and mix, and then an auxiliary agent such as PETM, stearic acid or maleimide is added, and then the solvent isopropanol is added, and the mixture is stirred at a high speed until a slightly white liquid is formed.
  • an auxiliary agent such as PETM, stearic acid or maleimide is added, and then the solvent isopropanol is added, and the mixture is stirred at a high speed until a slightly white liquid is formed.
  • the method further comprises preparing a polypropylene or polyethylene, selected from the group consisting of calcium carbonate, diatomaceous earth, titanium white powder, by a method of compact calendering, before the thermocompression bonding.
  • a polypropylene or polyethylene selected from the group consisting of calcium carbonate, diatomaceous earth, titanium white powder, by a method of compact calendering, before the thermocompression bonding.
  • An equilibrium layer of inorganic mineral powder and processing aid of talc and mica powder, and the protective layer, the decorative layer, the support layer and the balancing layer are subjected to the thermocompression bonding described above.
  • the method further comprises applying a pressure sensitive hot melt adhesive to form a backing layer on the side of the floor facing the ground after the hot pressing is applied to obtain the integral floor.
  • the method further comprises: performing a surface selected from the group consisting of corona treatment, flame treatment, chemical treatment, and high energy treatment on the side of the floor facing the ground before applying the adhesive. After treatment, the surface after treatment was tested by Dyne pen and the surface tension reached above 42 dynes.
  • the method further comprises: providing a cork layer between the support layer and the balance layer before the thermocompression bonding, the softwood layer passing through the propylene selected from the group consisting of propylene
  • the binder resin of the acid resin, the urethane resin, the epoxy resin, and the phenol resin is bonded to the support layer and the balance layer.
  • the thermocompression bonding process is performed as follows: the wear layer, the decorative layer, the support layer, and optionally the cork layer and the balance layer are placed in order It is laminated by a multi-layer hydraulic press to form a whole.
  • the temperature of the hot press bonding is set between 140 and 170 ° C, and then the temperature is increased in three stages: (a) the water intake is 3-5 min, (b) ) The temperature is raised for 20-30 minutes, and (c) the exhaust gas is fed for 30-40 minutes.
  • the last three stages of pressure are set at (a) 40-50 kg / 30 min (b) 60-70 kg / 30 min (c) 80-90 kg / 30min.
  • the temperature range of the machine is controlled within 5 °C.
  • the heat bonding forms a floor body, wherein the adhesion between the wear layer and the support layer, the support layer and the balance layer is tested by the test method of EN431 to show that the degree of conformity is up to standard.
  • Support layer formula (weight percent based on total weight of the formula):
  • the support layer is prepared by mixing, kneading, melting, calendering, and cooling the various materials in the above support layer formulation.
  • the specific process parameters of each step are shown in Table 1 below:
  • Polyethylene printing substrate formulation (weight percent based on total weight of the formula):
  • Coating solution formulation (weight percent based on total weight of the formula):
  • Ink formulation (weight percent based on total weight of the formula):
  • the bottom connecting layer substrate is obtained by mixing, extruding, calendering and cooling the raw materials in the above balancing layer formulation.
  • the specific process parameters are shown in Table 3 below:
  • the hydraulic hot press laminating machine is composed of a plurality of laminates and a multi-column hydraulic press, and each layer of the laminate can be heated, pressurized and cooled by hot oil or steam.
  • Table 4 The specific process parameters are shown in Table 4 below. :
  • the upper surface of the wear-resistant layer of the laminate obtained by the above-mentioned hot-press lamination is surface-treated with a bridging agent, and the formulation of the bridging agent is as follows:
  • Bridging agent formulation (weight percent based on total weight of the formula) :
  • a polyurethane-based UV coating is applied to the surface of the treated wear layer to form a UV layer, the UV coating being formulated as follows:
  • UV coating formulation (weight percent based on total weight of the formula) :
  • the surface corona treatment is performed on the side of the balance layer after the hot press lamination.
  • the hot melt adhesive for the adhesive layer is then applied to the ground facing side of the balancing layer to form a backing layer.
  • the peeling force of the adhesive floor of the present invention prepared above and the ground is 0.08 N/mm, the adhesion between the adhesive layer and the ground is small, and the floor can be easily peeled off from the ground. Underneath, and no glue remains on the ground, which has the effect of convenient construction.

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Abstract

一种复合地板，包括保护层（1）、装饰层（2）和支撑层（3），其中保护层（1）包括UV涂层和耐磨层，装饰层（2）包括油墨和印刷基材。还提供在支撑层（3）下方设置有平衡层（4）的复合地板、在地板最下面设置有背胶层（5）的背胶地板、以及在支撑层（3）和平衡层（4）之间或支撑层内部设置有软木层的复合地板。该复合地板方便施工，具有良好静音效果，可随意局部更换。

Description

复合地板及其制备方法 技术领域
本发明涉及复合地板及其制备方法，特别是涉及能够被多次反复使用的环保型复合地板及其制备方法。
背景技术
随着生活水平的提高，人们越来越重视家中的装潢。地板是家装中一个不可缺少的装饰材料。地板的种类、样式繁多，如木质地板、强化地板、瓷砖和塑胶地板等。其中木质地板和强化地板都是3-4层粘合而成，并且其层与层之间大多通过粘合剂粘合，所述粘合剂中不仅含有三聚氰胺、苯酚、甲醛等有害物质，而且不防水，并且价格、安装及保养费用不菲；瓷砖容易出现裂痕、更换困难以及不易清理等问题；塑胶地板具有价格便宜、防水防潮、耐磨耐刮等方面的优势，受到了人们的青睐，但是目前的塑胶地板也存在诸多问题。
目前市场上的塑胶地板普遍都是聚氯乙烯(PVC)地板，PVC地板的尺寸稳定性不佳，尤其在家庭装有地暖时，地板尺寸由于温差较大的原因有明显的改变；并且PVC地板中通常添加有增塑剂，使用时通常会伴有增塑剂的析出，所述的增塑剂具有生殖毒性，对人体有害；此外，PVC地板达不到真正意义上的环保，因为PVC裂解会产生HCl、CO等物质，燃烧后会产生二噁烷等有毒气体。
不同种类的塑胶地板的安装方式也不一样，市场上目前分布的塑胶地板种类有干底地板、背胶地板、和锁扣地板。干底地板在施工时，地面必须保持平整清洁，先在地面涂上一层厚薄均匀的粘合剂，然后将地板铺装于地面，待粘合剂完全固化才能完成地板的铺装。若更换地板，费时费力，且粘合剂会残留于地面，甚至破坏地板。背胶地板在地板背面涂覆有一层热熔胶，铺装时直接将地板铺装于地面，相对于干底地板施工更加快捷、简便；但是背胶地板不利于日后的更换，如将地板撕下后，热熔胶会失去粘性，地面也会有残留的热熔胶，很难清理。扣地板施工时，相对于前两者来说无残留胶的困扰，但是其地板的静音效果不够理想。
于是，理想的是，找到更好的地板来代替目前的塑胶地板，既符合环 保无毒的要求，又可以方便施工，并具有良好的静音效果，并且地板可随意局部更换。
发明内容
本发明提供一种复合地板，其包括保护层、装饰层和支撑层，其中所述保护层包括UV涂层和耐磨层，所述装饰层包括油墨和印刷基材，所述支撑层包含选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉，选自聚丙烯和聚乙烯的聚烯烃、以及热塑性聚烯烃弹性体，偶联剂和阻燃剂。
在本发明的复合地板的一些实施方式中，在支撑层的朝向地面的一侧还设置有一平衡层，所述平衡层包含聚丙烯或聚乙烯，其中填充有选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉，以及任选存在的选自分散剂、润滑剂、偶联剂、抗静电剂、抗氧化剂和阻燃剂中的一种或多种加工助剂，并且所述平衡层中不含有增塑剂。
在本发明的复合地板的一些实施方式中，在支撑层的朝向地面的一侧，或当复合地板具有平衡层时，在平衡层的朝向地面的一侧，还设置有背胶层，所述背胶层是压敏热熔胶。
在本发明的复合地板的一些实施方式中，在支撑层和平衡层之间还设置有一层软木，所述软木层通过选自丙烯酸树脂、聚氨酯树脂、环氧树脂和酚醛树脂的粘合剂树脂与支撑层和平衡层粘合。
本发明的复合地板能够达到环保要求，符合VOC(0-VOC)、CE、FDA、REACH等欧盟标准，并且能够实现快速便捷的施工，且更换时地面上不留残胶，可以反复使用，而且该地板尺寸稳定性优良，不会产生翘曲。
附图说明
图1是本发明的复合地板的一个实施例的层结构示意图。
图2是本发明的复合地板的另一个实施例的层结构示意图。
图3是本发明的复合地板的再一个实施例的层结构示意图。
具体实施方式
除非另外定义，本文所使用的所有技术和科学术语具有本发明所属领 域普通技术人员通常所理解的相同含义。在相抵触的情况下，以本说明书中的定义为准。
除非另外说明，所有的百分数、份数、比例等都以重量计。
当给出数值或数值范围、优选范围或一系列下限优选值和上限优选值时，应理解其具体公开了由任何较小的范围限值或优选值和任何较大的范围限值或优选值的任何一对数值所形成的所有范围，而无论范围是否分别被公开。除非另有说明，在本文描述数值范围之处，所述范围意图包括范围端值和范围内的所有整数和分数。
当术语“约”用于描述数值或范围的端值时，所公开的内容应理解为包括该具体数值或所涉及的端值。
采用“一”和“一个/种”的用法描述本发明的要素和组分。这只是出于便利和为了给出本发明的一般情况。除非另有明显表示，应将该说明理解为包括一个/种或至少一个/种。
术语“热塑性弹性体”(Thermoplastic Elastomer)，简写为TPE，是指在高温下能塑化成型，而在常温下能显示硫化橡胶弹性的材料，这类材料兼有热塑性塑料的加工成型性和硫化橡胶的高弹性性能。热塑性弹性体通常包括下面几类：1)热塑性聚氨酯弹性体(TPU)；2)苯乙烯嵌段类热塑性橡胶，典型的品种为热塑性苯乙烯-丁二烯-苯乙烯(SBS)嵌段共聚物、热塑性苯乙烯-异戊二烯-苯乙烯嵌段共聚物，和苯乙烯-丁二烯星形嵌段共聚物等；3)热塑性聚酯弹性体，该类弹性体通常是由二元羧酸及其衍生物(如对苯二甲酸二甲酯)、聚醚二醇(分子量600-6000)及低分子二醇的混合物通过熔融酯交换反应而得到的乌龟嵌段共聚物；以及4)热塑性聚烯烃弹性体。
术语“热塑性聚烯烃弹性体”(Thermoplastic Polyolefin)，简写为TPO，是热塑性弹性体中的一种，该类弹性体通常是通过共混法来制备，例如应用乙丙橡胶与热塑性聚乙烯或聚丙烯共混，或在共混的同时采用动态硫化法使橡胶部分得到交联，甚至在橡胶链上接枝聚乙烯或聚丙烯，还包括丁基橡胶接枝聚乙烯而得到的热塑性聚烯烃弹性体。
术语“聚烯烃弹性体”(Polyolefin Elastomer)，简写为POE，是指以茂金属为催化剂制备的具有窄的相对分子量分布和均匀的短支链分布的热塑 性弹性体。例如，通过溶液聚合方法制备的乙烯-辛烯共聚物，其中聚乙烯链结晶区起物理交联点的作用，一定量的辛烯的引入削弱了聚乙烯链的结晶区，形成了呈现橡胶弹性的无定型区。
术语“氧化聚乙烯蜡”(Oxidized Polyethylene)，简写为OPE，是由聚乙烯蜡经氧化制备，也可以是低分子量的乙烯-乙酸乙烯共聚物。氧化聚乙烯蜡分子链上带有一定的功能基团，所以它与极性树脂的相容性能得到显著改善，优于聚乙烯蜡。
术语“UV涂层”是指可经紫外线光固化的涂料层，其具有防紫外线光的功能和耐磨、耐刮、防滑、抗菌等功能。
本发明提供复合地板，其包括保护层、装饰层和支撑层，以及任选存在的平衡层、软木层和背胶层。下面对本发明的复合地板的各层分别予以说明。
保护层
本发明复合地板中的保护层包括UV涂层，和耐磨层。形成所述UV涂层的涂料包含30-80重量％，优选30-50重量％的选自多官能团聚氨酯类树脂、聚丙烯酸类树脂、和环氧类树脂中的一种或多种，20-50重量％的丙烯酸类单体，4-15重量％，优选4-8重量％的光引发剂和0.08-0.2重量％，优选0.08-0.12重量％的氧化聚乙烯蜡(OPE)，所述氧化聚乙烯蜡优选为微粉高密度聚乙烯蜡，其密度例如在0.98g/cc左右，熔点例如为140℃。
为了提高地板表面耐刮耐磨作用，在本发明的优选实施方式中，在UV涂层中加入了微粉高密度氧化聚乙烯蜡，简称OPE。氧化聚乙烯蜡为优良的新型极性蜡，由于氧化聚乙烯蜡分子链带有一定量的羰基和羟基，所以与填料、颜料、极性树脂的相溶性有显著改善，还具有优越的耐磨性及韧性等作用。OPE能够在UV涂层中分布均匀，提高地板的耐磨耐刮等性能。
在本发明的复合地板的一些实施方式中，所述保护层中的耐磨层包含选自聚乙烯和聚丙烯的树脂、聚烯烃弹性体(POE)和选自透明成核剂、抗氧化剂、紫外线吸收剂、光稳定剂、改性剂和阻燃剂的一种或多种加工助剂。所述改性剂例如聚丙烯接枝马来酸酐共聚物。优选所述耐磨层包含75-90重量％的聚乙烯树脂或聚丙烯树脂，8-15重量％的聚烯烃弹性体，所 述加工助剂在耐磨层中的用量优选为2-10重量％。
在本发明的复合地板中，耐磨层是保护整个地板的主力。由于聚烯烃的抗老化差，成型收缩率大等问题，优选在耐磨层中加入抗氧化剂、紫外线吸收剂、光稳定剂等，提高耐磨层的抗老化性，降低收缩率，可以保证地板长时间在太阳下照射而不发生地板变形和老化等问题。为了保证地板的柔软度，在耐磨层中优选加入聚烯烃弹性体(POE)以增加耐磨层的柔软度，优选聚烯烃弹性体在耐磨层中的含量为8-15重量％。此外，传统聚烯烃的透明度不佳，为提高耐磨层的透明度，加入成核剂，例如Milliken公司生产的Millad3988、NX4000和ADK STAB NA-21等透明成核剂，并在生产中使其急速冷却，制得高透明的耐磨层，可提高整体透明性，增强地板的视觉效果。耐磨层的厚度优选为0.1-0.7mm。
在本发明复合地板的优选实施方式中，在将所述的UV涂层施加于所述耐磨层之前，优选使用一种“架桥剂”对所述耐磨层的表面进行处理，所述架桥剂包含20-40重量％的多官能团聚氨酯丙烯酸酯或聚酯丙烯酸酯，2-6重量％的光引发剂，2-8重量％的表面活性剂，例如高活性磷酸酯LYCO-PO8，和50-70重量％的有机溶剂，例如乙酸乙酯、甲苯和二甲苯。其中，LYCO-PO8是诺泰生物科技(合肥)有限公司生产的，为改善磷酸三酯的溶解性、增加极压与抗磨性而特别制备的中碳链磷酸单酯与双酯的混合物，其含磷量高，分散溶解性增加，尤其在亲水性流体中，例如切削液，磨削液、冷轧液等中，应用广泛，其钾盐或有机胺盐更具有抗静电性能，使得LYCO-PO8还可应用于纤维油剂等加工中。采用架桥剂处理耐磨层表面后，再施加UV涂层，可以提高UV涂层与耐磨层之间的结合牢固度。
装饰层
本发明复合地板中的装饰层包括油墨和印刷基材。
在本发明的复合地板的一些实施方式中，考虑到地板需要长时间的暴露于外界，装饰层的图案容易出现变色的问题，优选使用耐高温170℃以上、附着力强的油墨。同时考虑到装饰层的油墨能更好地与耐磨层高温贴合，优选使用聚氨酯油墨、氯化聚丙烯(CPP)油墨或氯化乙烯-乙酸乙烯酯共聚物油墨(CEVA)。
在本发明的复合地板的一些实施方式中，使用聚氨酯油墨作为装饰层的油墨，所述聚氨酯油墨包含8-25重量％的聚氨酯树脂，例如分子量为80-90、密度在1g/cm3左右的聚氨酯树脂，50-80重量％、优选60-75重量％的一种或多种有机溶剂，例如乙酸乙酯、乙酸正丙酯、乙醇、异丙醇等，颜料和粘度调节剂。
在本发明的复合地板的优选实施方式中，在采用聚氨酯油墨用于装饰层时，在聚氨酯油墨层上面优选施加有连接剂，所述连接剂包含选自聚丙烯、乙烯-乙酸乙烯酯共聚物(EVA)、环氧树脂、酚醛树脂、松香树脂以及经马来酸酐接枝改性或氯化改性的上述树脂中的至少一种，和选自乙酸乙酯和乙酸正丙酯的有机溶剂。
单独使用氯化聚丙烯油墨(CPP)时，颜料的显色效果和油墨的印刷效果较差，单独使用氯化乙烯-乙酸乙烯酯共聚物油墨(CEVA)的效果虽然有所改善，但最理想的是两者配合使用，全面提高油墨的匹配与协调作用。在本发明的复合地板的优选实施方式中，所使用的氯化聚丙烯油墨包含：5-30重量％的氯含量为25-40摩尔％的氯化聚丙烯，7-11重量％的氯含量为28-38摩尔％的氯化乙烯-乙酸乙烯酯共聚物，60-70重量％的一种或多种有机溶剂，例如乙酸乙酯、乙酸正丙酯、乙醇、异丙醇等，颜料和粘度调节剂。
在复合地板中，油墨需要快速固化，以防卷材面料粘到一起。固化时间的快慢，取决于油墨中溶剂的类型。在本发明的复合地板的优选实施方式中，使用选自乙酸乙酯、乙酸正丙酯、乙醇、异丙醇中的一种或多种溶剂作为油墨溶剂。
油墨与耐磨层的连接很重要。在本发明的复合地板的一些实施方式中，在将装饰层和耐磨层高温热贴合的过程中，借助于油墨中的极性分子，油墨与耐磨层的成分发生化学交联反应，使耐磨层和装饰层紧密贴合。
此外，在已有复合地板的高温热贴合的过程中，装饰层中油墨细小颜料粒子会透过耐磨层渗出迁移，从而影响装饰层视觉效果，影响耐磨层的耐磨耐刮，污染设备材料等。本发明复合地板中所用的油墨中的颜料耐高温，并且颜料粒子比较大，此外油墨中的聚合物可以吸附颜料分子，因此本发明的油墨避免了颜料粒子的渗出和迁移。
在本发明的复合地板的一些实施方式中，装饰层的印刷基材包含选自 碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉中的一种或多种无机矿粉，选自PE和PP的聚烯烃，以及任选存在的加工助剂。所述的加工助剂包括选自分散剂、润滑剂、偶联剂、抗静电剂、抗氧化剂和阻燃剂中的一种或多种。
在本发明的复合地板的一些实施方式中，装饰层的印刷基材是包含20-80重量％、优选40-70重量％的聚丙烯，18-70重量％、优选28-55重量％的无机矿粉和2-10重量％、优选2-5重量％的选自分散剂、润滑剂、偶联剂、抗静电剂中的一种或多种加工助剂的聚丙烯印刷基材。
在本发明的复合地板的另一些实施方式中，装饰层的印刷基材是包含10-50重量％、优选10-25重量％的聚乙烯，40-80重量％、优选70-80重量％的选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉中的一种或多种的无机矿粉，和3-10重量％的选自分散剂、润滑剂、偶联剂、抗氧化剂和阻燃剂中的一种或多种加工助剂的聚乙烯印刷基材。
由于本发明的复合地板的印刷基材中使用了无机矿粉填充，特别是聚乙烯印刷基材中无机矿粉的含量比较大，为改善油墨在其上的印刷效果，优选对印刷基材的印刷面用涂布液处理，所述涂布液可以是橡胶乳液、聚丙烯酸酯乳液、或聚乙烯醇乳液。在本发明的一个优选实施方式中，采用一种含有下列物质的涂布液：60-85重量％的异丙醇和/或水、2-5重量％成膜剂，例如PVA，0.5-1重量％的抗静电剂，0.5-1重量％的抗氧剂，15-33重量％的选自橡胶、聚丙烯酸酯或聚乙酸乙烯酯的一种或多种乳液。经涂布液涂布后，使得印刷基材表面光滑，没有碳酸钙等无机矿粉分子裸露，能够保证好的印刷效果。印刷基材的朝向支撑层的一面(贴合面)需要和支撑层贴合，为了保证贴合牢度，贴合面不需要涂布处理。
对于PE印刷基材，考虑其热氧化产生碳，会导致基材和油墨整体变暗，需要加入阻燃剂和抗氧化剂提高其热氧化温度和抑制其热氧化。对于PP印刷基材，由于PP热氧化温度较高，可以不加入抗氧化剂和阻燃剂，但其在生产过程中需要加入抗静电剂防止生产之后的静电连接。
在本发明的复合地板的一些实施方式中，当使用PP印刷基材时，为了获得印刷基材与支撑层的优异的贴合效果，优选对PP印刷基材与支撑层的贴合面用处理水进行处理，所述处理水包含水和醇类溶剂的混合溶剂、偶 联剂(例如道康宁6040)、抗氧剂(例如季戊四醇酯)、成膜剂(例如PVA)、表面活性剂(例如硬脂酸)，和交联剂(例如马来酰亚胺)。在本发明的复合地板的优选实施方式中，所述处理水包含水和异丙醇作为溶剂、0.5％-1重量％的偶联剂道康宁6040、1-2重量％的抗氧剂季戊四醇酯、0.3％-2重量％的成膜剂PVA、0.3-0.8重量％的表面活性剂硬脂酸、0.5％-1重量％的交联剂马来酰亚胺。经所述处理水涂覆的印刷基材的贴合面(背面)，形成一层很薄的处理层，在高温热贴合过程中与支撑层的成分产生化学交联作用。
支撑层
本发明的复合地板包括作为主体材料的支撑层。
在本发明的复合地板的一些实施方式中，所述支撑层包含选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉，选自聚丙烯和聚乙烯的聚烯烃、热塑性聚烯烃弹性体，以及选自偶联剂、分散剂和阻燃剂的助剂。
在本发明的复合地板的优选实施方式中，所述支撑层包含65-85重量％，优选75-85重量％的选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉，8-35重量％，优选8-25重量％的选自聚丙烯和聚乙烯的一种或多种聚烯烃、1-2重量％的热塑性聚烯烃弹性体(TPO)，0.5-1重量％的偶联剂、1-2重量％的阻燃剂。
在本发明的复合地板中，在支撑层的填充有无机矿粉的聚合物材料中加入偶联剂和分散剂，能将碳酸钙等无机矿粉粒子均匀分散于聚烯烃等塑料球晶上，使两者相容。加入偶联剂和分散剂后，支撑层的表面上无碳酸钙等无机矿粉的裸露粒子。除此之外，加入偶联剂提升分子间的融合，使整体物料变软，提高韧性，地板整体也随之变柔软，不会因为外力断裂。加入分散剂使分子间混合更均匀，并起到润滑的作用，减低物料混合后的粘度，同时减少收缩率，避免地板的整体拱、翘问题。支撑层的厚度优选为0.08-0.16mm，更优选为0.08mm-0.12mm。
在本发明的复合地板的优选实施方案中，还可以在支撑层的内部加入一层聚酯纤维网格布或玻纤毡，所述的聚酯纤维可以是由有机二元酸与二元醇缩聚而成的，例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等。所述的纤维网格布的密度例如可以是1.37g/cm3左右，纤维的直径例如可以 是23纳米左右。所述玻纤毡的克重优选为950-1000克每平米，厚度优选为0.2-1.0mm，更优选0.2-0.5mm。所述聚酯纤维网格布或玻纤毡可以增加支撑层的抗收缩性和强度，增加地板的整体稳定性，避免地板的拱翘问题。
平衡层
在本发明的复合地板的优选实施方式中，在所述支撑层的朝向地面的一侧还设置有一平衡层。
在本发明的复合地板的一些实施方式中，所述平衡层包含70-95重量％的选自聚乙烯和聚丙烯的至少一种树脂、2-20重量％的聚烯烃弹性体(POE)、以及0-10重量％的任选存在的选自分散剂、润滑剂、偶联剂、抗静电剂、抗氧化剂和阻燃剂中的一种或多种加工助剂，并且所述平衡层中不含有增塑剂。该平衡层对地板整体起到平衡的作用，可以避免地板拱翘的问题。
在本发明的复合地板的优选实施方式中，平衡重的聚烯烃弹性体(POE)的含量占平衡层总重量的8-15％。
本发明的复合地板可以是“干底”地板，即地板不带有背胶层；也可以是如下文所述的带有背胶层的地板。在干底地板的情况下，由于平衡层的主要成分是聚烯烃，为增加平衡层底面的极性，以利于其与施加到地面的干底胶(例如丙烯酸类粘合剂)的粘合，优选对平衡层的朝向地面的一侧用连接剂处理，所述连接剂包含选自聚丙烯、乙烯-乙酸乙烯酯共聚物(EVA)、环氧树脂、酚醛树脂、松香树脂以及经马来酸酐接枝改性或氯化改性的上述树脂中的至少一种，和选自乙酸乙酯和乙酸正丙酯的有机溶剂。
背胶层
在本发明的复合地板的优选实施方式中，在支撑层的朝向地面的一侧，或当设置有平衡层时，在平衡层的朝向地面的一侧，还设置有背胶层，所述背胶层是压敏热熔胶。
在本发明的复合地板的优选实施方式中，形成所述背胶层的压敏热熔胶包含15-45重量％的选自热塑性聚氨酯弹性体、苯乙烯嵌段类热塑性橡胶、热塑性聚酯弹性体的热塑性弹性体、30-60重量％的选自松香树脂、氢 化松香甘油酯、C5系石油树脂、C9系石油树脂和脂环系氢化石油树脂的增粘树脂、O-2重量％的抗氧化剂和0-25重量％的选自石蜡油或环烷油的软化油。
在本发明的复合地板所用的压敏热熔胶中，增粘树脂的含量高，使得背胶层的内聚力大，胶体内部的结合力强，有利于在与地面剥离的时候，不在地面上残留胶。
在本发明的复合地板的优选实施方案中，所述背胶层的压敏热熔胶的量是10-50g/m2，更优选是15-25g/m2。
在本发明的复合地板的优选实施方式中，优选在地板具有平衡层的情况下，在平衡层的朝向地面的一侧设置背胶层，以使得背胶层更好地粘附于地板本体。由于本发明所采用的平衡层中不使用增塑剂，不会因为平衡层中增塑剂的析出而导致热熔胶脱落。
在本发明的复合地板的优选实施方式中，在向地板的支撑层或平衡层的朝向地面的一侧涂覆背胶层之前，对所述支撑层或平衡层的朝向地面的一侧进行选自电晕处理、火焰处理、化学处理和高能处理的表面处理。所述的表面处理使得待涂覆背胶层的底面的表面能到达合适范围的达因数，例如表面张力为42达因以上，由此使得涂覆于其上的热熔胶与地板底面具有非常牢固的粘结，该粘结力高于所述热熔胶与地面之间的粘结力。同时利用热熔胶与地面之间的粘结力，能轻松地将地板粘结于地面，并利用热熔胶的剪切力，使其在地面不易错位，不会因为人的走动或者是外力的情况，导致地板随其移动。本发明复合地板中的背胶层的热熔胶具有高的内聚力，该内聚力大于该热熔胶与地面的粘结力，由此可以容易地使背胶层整体轻松与地面分开，而不在地面上残留胶，从而实现方便施工、更换简单的功能。
软木层
在本发明的复合地板的优选实施方式中，在所述的支撑层和平衡层之间或者所述支撑层的内部还设置有软木层，所述软木层通过选自丙烯酸树脂、聚氨酯树脂、环氧树脂和酚醛树脂的粘合剂树脂与支撑层和平衡层粘合。由此形成的软木地板不仅能提升木质感，还能使地板整体富有弹性， 提高用户使用过程中的体验感。此外，加软木层能达到静音的效果，根据ASTM用夯击机实验室测量冲击声波通过地板的传播方法测得，本发明的加有软木的复合地板的静音能达到55分贝的检测标准。
下面结合附图，对本发明的非PVC复合地板的层结构进行示例性的说明。
图1所示为本发明的复合地板的一个实施例，该复合地板包括：保护层1、装饰层2、支撑层3和平衡层4。
其中，保护层1包括耐磨层和UV涂层。装饰层2包括油墨和印刷基材。支撑层3的主要成分是碳酸钙等无机矿粉以及加工助剂填充的聚丙烯。平衡层4的主要成分是碳酸钙等无机矿粉填充的聚丙烯，并且平衡层4中不含有增塑剂。
图2所示为本发明的复合地板的另一个实施例，该复合地板包括：保护层1、装饰层2、支撑层3、平衡层5，以及在支撑层3和平衡层5之间加入的软木层4。加入软木层能达到静音的效果。根据ASTM用夯击机实验室测量冲击声波通过地板的传播方法，该地板的静音能达到55分贝的检测标准。
图3所示为本发明的复合地板的又一个实施例，其包括由保护层、装饰层和支撑层构成的地板本体1和背胶层2，背胶层2是通过将压敏热熔胶均匀涂覆于地板本体1的底面而形成，涂胶量在10-25g/m2之间，随后将离型纸覆于其上。所述压敏热熔胶包含15-40重量％的热塑性弹性体、15-60重量％的增粘树脂、0-2重量％的抗氧化剂和0-25重量％的软化油。
本发明还提供上述复合地板的制备方法，包括如下步骤：
通过混炼然后压延或流延的方法制备耐磨层；
通过混炼然后吹塑或压延的方法制备印刷基材，并将油墨印刷到印刷基材上，形成装饰层；
通过混炼然后压延的方法制备支撑层；
在140-170℃的温度、40-80kg的压力下将上述耐磨层、装饰层和支撑层热压贴合形成一个整体，随后
在耐磨层上涂覆UV涂料，形成包括UV涂层和耐磨层的保护层。
在本发明的复合地板的制备方法的一些实施方式中，耐磨层的制备是将聚烯烃(PP或PE)粒子、成核剂、光稳定剂、抗氧剂、阻燃剂、紫外线吸收剂等通过高速混合机均匀混合，然后通过行星式挤出机挤出后进入过滤机，去除物料中的杂质，通过压延或流延成型后进入冷却轮冷却，形成厚度在0.1-0.7mm的高透明膜。该耐磨层增加地板的耐磨性，保护装饰层的呈现效果，使地板在长期使用过程中保持漂亮的外观。
在本发明的复合地板的制备方法的一些实施方式中，印刷基材的制备是将碳酸钙、硅藻土等无机矿粉、PP或PE粒子、偶联剂、分散剂、润滑剂等通过密炼机密炼，然后挤出吹塑或压延形成厚度为0.08-0.16mm的薄膜。
在本发明的复合地板的制备方法的优选实施方式中，在向印刷基材施加油墨之前，对所述的印刷基材的印刷表面用涂布液进行涂覆处理，所述涂布液选自橡胶乳液、丙烯酸树脂乳液、和聚乙烯醇乳液。所述的涂布液例如可以包含60-80重量％的异丙醇和水的混合物、2-5重量％的成膜剂，例如PVA，0.5-1重量％的抗静电剂，0.5-1重量％的抗氧剂，以及15-33重量％的橡胶、丙烯酸树脂或聚乙烯醇。
在本发明的复合地板的制备方法的一些实施方式中，支撑层的制备是将碳酸钙、硅藻土等无机矿粉、PP或PE粒子、偶联剂、分散剂、润滑剂、阻燃剂、抗静电剂等通过密炼机密炼，然后挤出压延形成厚度为0.6-1.2mm的层。其中所述的偶联剂例如可以选自道康宁6030或6040，分散剂可选自路博润32500或三菱P533J，润滑剂例如为硬脂酸钙，也可以用分散剂代替，阻燃剂例如可选自氢氧化镁等无卤素阻燃剂。
在本发明的复合地板的制备方法的优选实施方式中，还包括在支撑层内部设置一层聚酯纤维网格布或玻纤毡。所述聚酯纤维可以是由有机二元酸与二元醇缩聚而成的，例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等。所述的纤维网格布的密度例如可以是1.37g/cm3左右，纤维的直径例如可以是23纳米左右。
在本发明的复合地板的制备方法的优选实施方式中，在将所述UV涂层 涂覆到耐磨层上之前，采用一种架桥剂对所述耐磨层进行表面处理，所述架桥剂包含20-40重量％的多官能团聚氨酯丙烯酸，2-6重量％的光引发剂，2-8重量％的磷酸酯和50-70重量％的有机溶剂，例如乙酸乙酯、甲苯和二甲苯。
在本发明的复合地板的制备方法的优选实施方式中，采用PP印刷基材，并优选对所述PP印刷基材与所述支撑层贴合的贴合面用处理水进行表面处理，所述处理水包含溶剂水和异丙醇、偶联剂(例如道康宁6030或6040)季戊四醇酯、成膜剂(例如PVA)表面活性剂(例如硬脂酸)、交联剂(例如马来酰亚胺)。
在本发明复合地板的制备方法的优选实施方式中，所述处理水包含溶剂水和异丙醇、0.5-1重量％的偶联剂(例如道康宁6030或6040)、1-2重量％的季戊四醇酯、0.3-2重量％的成膜剂(例如PVA)、0.3-0.8重量％的表面活性剂(例如硬脂酸)和0.5-1重量％的交联剂(例如马来酰亚胺)。
在本发明复合地板的制备方法的优选实施方式中，所述处理水的制备如下：将PVA融入水中并连续注入热蒸汽，使温度在80-90℃之间。PVA完全溶于水中后，加入偶联剂搅拌混合，随后添加PETM、硬脂酸、马来酰亚胺等助剂，再添加溶剂异丙醇，高速搅拌直至形成微白色的液体。
在本发明的复合地板的制备方法的一些实施方式中，还包括在热压贴合之前，通过密炼压延的方法制备包含聚丙烯或聚乙烯、选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉和加工助剂的平衡层，并将所述保护层、装饰层、支撑层和平衡层一起进行所述的热压贴合。
在本发明的复合地板的制备方法的一些实施方式中，还包括在热压贴合获得整体地板后，在地板整体的朝向地面的一侧涂覆压敏热熔胶形成背胶层。
在本发明的复合地板的制备方法的优选实施方式中，还包括在涂覆背胶之前，对地板整体的朝向地面的一侧进行选自电晕处理、火焰处理、化学处理和高能处理的表面处理，处理之后的表面经达因笔检测，表面张力达到42达因以上。
在本发明的复合地板的制备方法的一些实施方式中，还包括在热压贴合之前，在支撑层和平衡层之间设置一软木层，所述软木层通过选自丙烯 酸树脂、聚氨酯树脂、环氧树脂和酚醛树脂的粘合剂树脂与支撑层和平衡层粘合。
在本发明的复合地板的制备方法的一些实施方式中，所述的热压贴合过程如下进行：将耐磨层、装饰层、支撑层，以及任选存在的软木层和平衡层按顺序放置，采用多层油压机进行层合，使其形成一个整体。在本发明的复合地板的制备方法的优选实施方式中，所述热压贴合的温度设定在140-170℃之间，然后三段升温：(a)排水进气3-5min，(b)升温20-30min，(c)排气进水30-40min。最后三段压力设定在(a)40-50kg/30min(b)60-70kg/30min(c)80-90kg/30min。机台温度范围控制在5℃以内。热贴合形成地板本体，其中耐磨层和支撑层、支撑层和平衡层之间的贴合通过EN431的测试方法显示贴合度达标。
实施例
聚丙烯背胶地板的制备
1)支撑层的制备
支撑层配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000001
将上述支撑层配方中的各种物质分别通过混合、密炼、开炼、压延和冷却等步骤制备出支撑层。各步骤的具体工艺参数见下表1：
表1
Figure PCTCN2016072020-appb-000002
2)耐磨层的制备
耐磨层的配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000003
将上述耐磨层配方中的原料进料到行星式挤出机中，经挤出压延和快速冷却的步骤，制得耐磨层。具体工艺参数见下表2：
表2
Figure PCTCN2016072020-appb-000004
3)装饰层的制备
3.1)聚乙烯印刷基材的制备
聚乙烯印刷基材配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000005
3.2)用涂布液对聚乙烯印刷基材的表面处理
涂布液配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000006
3.3)在聚乙烯印刷基材上施加油墨形成装饰层
油墨配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000007
Figure PCTCN2016072020-appb-000008
4)平衡层的制备
平衡层的配方(基于配方总重量的重量百分数)：
聚丙烯(燕化公司2401，分子量约250,000)     93％
聚烯烃弹性体(POE，美国陶氏8540)           7％
将上述平衡层配方中的原料经混合、挤出、压延和冷却的步骤，制得底连接层基材。具体工艺参数见下表3：
表3
Figure PCTCN2016072020-appb-000009
5)热压层合步骤
将上述制得的各层按照耐磨层、装饰层、支撑层、和平衡层的顺序热压层合在一起，形成层合体。具体采用油压热压贴合机，其由多个层压板和多柱液压机组成，每层层压板都可通过热油或蒸汽方式控温加热、加压和冷却，具体工艺参数见下表4：
表4
Figure PCTCN2016072020-appb-000010
6)UV涂层的制备
首先对上述热压层合获得的层合体的耐磨层的上表面用架桥剂进行表面处理，架桥剂的配方如下：
架桥剂配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000011
将基于聚氨酯的UV涂料施加于经上述处理的耐磨层的表面上，形成UV层，所述UV涂料的配方如下：
UV涂料配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000012
Figure PCTCN2016072020-appb-000013
7)背胶层的制备
对热压层合后的平衡层的朝向地面一侧进行表面电晕处理。
然后将用于背胶层的热熔胶涂覆到平衡层的朝向地面的一侧，形成背胶层。
热熔胶的配方(基于配方总重量的重量百分数)：
Figure PCTCN2016072020-appb-000014
通过NF T76-126测试方法测得，如上制备的本发明的背胶地板与地面的剥离力为0.08N/mm，背胶层与地面的粘结力很小，地板能轻易地从地面上撕下，且不在地面残留任何胶，达到了施工便利的效果。
上面通过一些实施方式和实施例对本发明进行了具体的描述，但是这些实施方式和实施例不是对本发明的范围的限制，本领域技术人员应该明白的是，在本申请公开内容的基础上可以对复合地板做出很多改变，这些改变都包括在本发明的精神范围内。

Claims (33)

  1. 复合地板，包括保护层、装饰层和支撑层，其中所述保护层包括UV涂层和耐磨层，所述装饰层包括油墨和印刷基材，所述支撑层包含选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉，选自聚丙烯和聚乙烯的至少一种聚烯烃树脂、热塑性聚烯烃弹性体(TPO)，以及选自偶联剂、分散剂、润滑剂、抗静电剂、抗氧化剂和阻燃剂中的一种或多种助剂。
  2. 如权利要求1所述的复合地板，其中在所述支撑层的朝向地面的一侧还设置有一平衡层，所述平衡层包含70-95重量％的选自聚丙烯和聚乙烯的至少一种聚烯烃树脂、2-20重量％的聚烯烃弹性体(POE)、以及0-10重量％的任选存在的选自分散剂、润滑剂、偶联剂、抗静电剂、抗氧化剂和阻燃剂中的一种或多种加工助剂，并且所述平衡层中不含有增塑剂。
  3. 如权利要求1或2所述的复合地板，其中在所述的支撑层的朝向地面的一侧，或所述平衡层的朝向地面的一侧，还设置有背胶层，所述背胶层由压敏热熔胶形成。
  4. 如权利要求2所述的复合地板，其中在所述的支撑层和平衡层之间或所述支撑层的内部还设置有软木层，所述软木层通过选自丙烯酸树脂、聚氨酯树脂、环氧树脂和酚醛树脂的粘合剂与所述支撑层和平衡层粘合。
  5. 如权利要求1-4任一项所述的复合地板，其中所述支撑层包含65-85重量％的选自碳酸钙、硅藻土、钛白粉、滑石粉和云母石粉的无机矿粉，8-35重量％的选自聚丙烯和聚乙烯的一种或多种聚烯烃、1-2重量％的热塑性聚烯烃弹性体(TPO)，0.5-1重量％的偶联剂、和1-2重量％的阻燃剂。
  6. 如权利要求1-4任一项所述的复合地板，其中所述保护层中的UV涂层包含30-80重量％的选自多官能团聚氨酯类树脂、聚丙烯酸类树脂、和环氧类树脂中的一种或多种树脂，20-50重量％的丙烯酸类单体，4-15重量％的光引发剂和0.08-0.2％重量的氧化聚乙烯蜡(OPE)。
  7. 如权利要求1-4任一项所述的复合地板，其中所述耐磨层包含选自聚乙烯和聚丙烯的树脂、聚烯烃弹性体(POE)和选自透明成核剂、抗氧化剂、紫外线吸收剂、光稳定剂、改性剂和阻燃剂的一种或多种加工助剂。
  8. 如权利要求7所述的复合地板，其中所述耐磨层中的聚烯烃弹性体(POE)的含量占耐磨层总重量的8-15重量％。
  9. 如权利要求1-4任一项所述的复合地板，其中在将所述UV涂层施加到所述耐磨层上之前，所述耐磨层经架桥剂处理，所述架桥剂包含20-40重量％的多官能团聚氨酯丙烯酸酯或聚酯丙烯酸酯，2-6重量％的光引发剂，2-8重量％的表面活性剂，和50-70重量％的选自乙酸乙酯、乙酸丙酯、甲苯和二甲苯的有机溶剂。
  10. 如权利要求1-4任一项所述的复合地板，其中所述装饰层中的印刷基材包含选自碳酸钙、硅藻土、钛自粉、滑石粉和云母石粉中的一种或多种无机矿粉，选自PE和PP的聚烯烃，以及选自分散剂、润滑剂、偶联剂、抗静电剂、抗氧化剂和阻燃剂中的一种或多种的加工助剂。
  11. 如权利要求10所述的复合地板，其中所述印刷基材是包含20-80重量％的聚丙烯，18-70重量％的无机矿粉和2-10重量％的选自分散剂、润滑剂、偶联剂、抗静电剂中的一种或多种加工助剂的聚丙烯印刷基材。
  12. 如权利要求10所述的复合地板，其中所述印刷基材是包含10-50重量％的聚乙烯，40-80重量％的无机矿粉，和3-10重量％的选自分散剂、 润滑剂、偶联剂、抗氧化剂和阻燃剂中的一种或多种加工助剂的聚乙烯印刷基材。
  13. 如权利要求1-4任一项所述的复合地板，其中所述装饰层中的油墨层由聚氨酯油墨或氯化聚丙烯油墨形成。
  14. 如权利要求13所述的复合地板，其中所述聚氨酯油墨包含8-25重量％的聚氨酯树脂，60-75重量％的选自乙酸乙酯、乙酸正丙酯、乙醇和异丙醇的一种或多种溶剂，颜料和粘度调节剂。
  15. 如权利要求14所述的复合地板，其中在所述装饰层的聚氨酯油墨上面施加有连接剂，所述连接剂包含选自聚丙烯、乙烯-乙酸乙烯酯共聚物(EVA)、环氧树脂、酚醛树脂、松香树脂以及经马来酸酐接枝改性或氯化改性的上述树脂中的至少一种，和选自乙酸乙酯和乙酸正丙酯的有机溶剂。
  16. 如权利要求13所述的复合地板，其中所述氯化聚丙烯油墨包含：5-30重量％的氯含量为25-40摩尔％的氯化聚丙烯，7-11重量％的氯含量为28-38摩尔％的氯化乙烯-乙酸乙烯酯共聚物，60-70重量％的选自乙酸乙酯、乙酸正丙酯、乙醇和异丙醇的一种或多种溶剂，颜料和粘度调节剂。
  17. 如权利要求12所述的复合地板，其中采用聚乙烯印刷基材，并且在施加油墨之前，所述的聚乙烯印刷基材的表面经涂布液处理，所述涂布液选自橡胶乳液、丙烯酸树脂乳液、或聚乙烯醇乳液。
  18. 如权利要求12所述的复合地板，其中所述PP印刷基材与所述支撑层贴合的贴合面经处理水表面处理，所述处理水包含水和醇类溶剂的混合溶剂、0.5-1重量％的偶联剂、1-2重量％的抗氧剂、0.3-2重量％的成膜剂、0.3-0.8重量％的表面活性剂和0.5-1重量％的交联剂。
  19. 如权利要求3所述的复合地板，其中所述背胶层的压敏热熔胶包含15-45重量％的选自热塑性聚氨酯弹性体、苯乙烯嵌段类热塑性橡胶、热塑性聚酯弹性体的一种或多种热塑性弹性体、30-60重量％的选自松香树脂、C5系石油树脂、C9系石油树脂和脂环系氢化石油树脂的一种或多种增粘树脂、0-2重量％的抗氧化剂和0-25重量％的软化油。
  20. 如权利要求3所述的复合地板，其中所述背胶层的压敏热熔胶的量是10-26g/m2。
  21. 如权利要求3所述的复合地板，其中在向地板的平衡层的朝向地面的一侧涂覆背胶层之前，所述平衡层的朝向地面的一侧经过选自电晕处理、火焰处理、化学处理和高能处理的表面处理。
  22. 如权利要求2所述的复合地板，其中所述平衡层的朝向地面的一侧经连接剂处理，所述连接剂包含选自聚丙烯、乙烯-乙酸乙烯酯共聚物(EVA)、环氧树脂、酚醛树脂、松香树脂以及经马来酸酐接枝改性或氯化改性的上述树脂中的至少一种，和选自乙酸乙酯和乙酸正丙酯的有机溶剂。
  23. 如权利要求1所述的复合地板，其中所述支撑层的内部还加入有一层聚酯纤维网格布或玻纤毡。
  24. 如权利要求1所述的复合地板的制备方法，包括：
    通过混炼然后压延或流延的方法制备耐磨层；
    通过混炼然后吹塑或压延的方法制备印刷基材，并将油墨印刷到印刷基材上，形成装饰层；
    通过混炼然后压延的方法制备支撑层；
    在140-170℃的温度、40-80kg的压力下将上述耐磨层、装饰层和支撑层热压贴合形成一个整体，随后
    在耐磨层上涂覆UV涂料，形成包括UV涂层和耐磨层的保护层。
  25. 如权利要求24所述的复合地板的制备方法，其中还包括在热压贴合之前，制备平衡层，并将所述保护层、装饰层、支撑层和平衡层一起进行所述的热压贴合。
  26. 如权利要求25所述的复合地板的制备方法，其中还包括在热压贴合后，对所述平衡层的朝向地面的一侧用连接剂处理，所述连接剂包含选自聚丙烯、乙烯-乙酸乙烯酯共聚物(EVA)、环氧树脂、酚醛树脂、松香树脂以及经马来酸酐接枝改性或氯化改性的上述树脂中的至少一种，和选自乙酸乙酯和乙酸正丙酯的有机溶剂。
  27. 如权利要求25所述的复合地板的制备方法，其中还包括在热压贴合后，对所述支撑层或所述平衡层的朝向地面的一侧涂覆压敏热熔胶形成背胶层，其中在涂覆压敏热熔胶之前，所述平衡层的朝向地面的一侧任选经过选自电晕处理、火焰处理、化学处理和高能处理的表面处理。
  28. 如权利要求24-27任一项所述的复合地板的制备方法，其中还包括在热压贴合之前，在所述的支撑层和平衡层之间或在支撑层内部设置一软木层，所述软木层通过选自丙烯酸树脂、聚氨酯树脂、环氧树脂和酚醛树脂的粘合剂树脂与支撑层和平衡层粘合。
  29. 如权利要求24-28任一项所述的复合地板的制备方法，其中还包括在支撑层内部设置一层聚酯纤维网格布或玻纤毡。
  30. 如权利要求24-29任一项所述的复合地板的制备方法，其中在将所述UV涂层涂覆到所述耐磨层上之前，采用架桥剂对所述耐磨层进行表面处理，所述架桥剂包含20-40重量％的多功能团聚氨酯丙烯酸酯或聚酯丙烯酸酯，2-6重量％的光引发剂，2-8重量％的磷酸酯盐和50-70重量％的选自乙酸乙酯、乙酸丙酯、甲苯和二甲苯的有机溶剂。
  31. 如权利要求24-30任一项所述的方法，其中在制备装饰层的步骤中，包括在施加油墨之前，对所述的印刷基材的表面用涂布液进行涂覆处理，所述涂布液选自橡胶乳液、丙烯酸树脂乳液、或聚乙烯醇乳液。
  32. 如权利要求24-31任一项所述的方法，其中装饰层中使用聚氨酯油墨，并且在所述聚氨酯油墨上面施加连接剂，所述连接剂包含选自聚丙烯、乙烯-乙酸乙烯酯共聚物(EVA)、环氧树脂、酚醛树脂、松香树脂以及经马来酸酐接枝改性或氯化改性的上述树脂中的至少一种，和选自乙酸乙酯和乙酸正丙酯的有机溶剂。
  33. 如权利要求24-32任一项所述的方法，其中所述印刷基材是PP印刷基材，并且对所述PP印刷基材与所述支撑层贴合的贴合面用处理水进行表面处理，所述处理水包含水、异丙醇、偶联剂、抗氧剂、成膜剂、表面活性剂和交联剂。
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