CN115384151A - Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor - Google Patents

Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor Download PDF

Info

Publication number
CN115384151A
CN115384151A CN202211041119.4A CN202211041119A CN115384151A CN 115384151 A CN115384151 A CN 115384151A CN 202211041119 A CN202211041119 A CN 202211041119A CN 115384151 A CN115384151 A CN 115384151A
Authority
CN
China
Prior art keywords
parts
polyvinyl chloride
foaming
layer
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211041119.4A
Other languages
Chinese (zh)
Inventor
黄获君
吕爱龙
廖建训
唐训
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rifeng New Material Co ltd
Foshan Rifeng Enterprise Co Ltd
Rifeng Enterprise Group Co Ltd
Rifeng Technology Co Ltd
Original Assignee
Rifeng New Material Co ltd
Foshan Rifeng Enterprise Co Ltd
Rifeng Enterprise Group Co Ltd
Rifeng Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rifeng New Material Co ltd, Foshan Rifeng Enterprise Co Ltd, Rifeng Enterprise Group Co Ltd, Rifeng Technology Co Ltd filed Critical Rifeng New Material Co ltd
Priority to CN202211041119.4A priority Critical patent/CN115384151A/en
Publication of CN115384151A publication Critical patent/CN115384151A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • B32B27/065—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 of foam
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/046—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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

Abstract

The invention provides a polyvinyl chloride floor base material, a preparation method thereof and a polyvinyl chloride floor, and relates to the technical field of building material decoration production. The foaming material comprises solid layers and foaming layers, wherein the solid layers and the foaming layers are alternately arranged, and the number of the foaming layers is less than that of the solid layers. The solid layer comprises, by weight, 40-60 parts of polyvinyl chloride, 80-120 parts of filler, 20-30 parts of talcum powder and 1-10 parts of impact resistance agent. The foaming layer comprises, by weight, 40-60 parts of polyvinyl chloride, 20-30 parts of filler, 40-60 parts of modified reinforcing agent, 1-10 parts of impact resistance agent, 1-10 parts of foaming regulator and 1-5 parts of foaming agent. The foaming layer is arranged in the floor base material, so that the overall density of the floor base material is reduced, the weight of the floor is reduced, and meanwhile, the foaming layer can achieve better heat insulation and noise reduction effects.

Description

Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor
Technical Field
The invention relates to the technical field of building material decoration production, in particular to a polyvinyl chloride floor base material, a preparation method thereof and a polyvinyl chloride floor.
Background
At present, the floor commonly used in the room comprises a wooden floor, a ceramic floor, a bamboo floor, a polyvinyl chloride floor and the like, wherein the polyvinyl chloride is an environment-friendly nontoxic renewable resource, and has been widely used in daily life of people, such as non-food-grade packaging bags, garbage bags, building veneers and the like. However, the existing wood floor, ceramic floor, bamboo floor and polyvinyl chloride floor have the phenomena of large weight of the floor, poor sound insulation and heat insulation effects of the floor and the like, so that the difficulty of construction and production is increased, and the living experience of residents is also influenced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a polyvinyl chloride floor base material, a preparation method thereof and a polyvinyl chloride floor, which are light in weight and have the effects of heat insulation and noise reduction.
The embodiment of the invention is realized by the following steps:
in a first aspect, the invention provides a polyvinyl chloride floor base material, which comprises solid layers and foaming layers, wherein the solid layers and the foaming layers are alternately arranged, and the number of the foaming layers is less than that of the solid layers.
The solid layer comprises, by weight, 40-60 parts of polyvinyl chloride, 80-120 parts of filler, 20-30 parts of talcum powder and 1-10 parts of impact resistance agent.
The foaming layer comprises, by weight, 40-60 parts of polyvinyl chloride, 20-30 parts of filler, 40-60 parts of modified reinforcing agent, 1-10 parts of impact resistance agent, 1-10 parts of foaming regulator and 1-5 parts of foaming agent.
In the solid layer, polyvinyl chloride is used as a main raw material of the floor base material, is matched with filler, and is added with talcum powder as a reinforcing agent, so that the heat shrinkage performance of the material can be improved, and the heat shrinkage of the material can be reduced. And the use of an impact resistance agent is matched, so that the toughness and the impact property of the material can be improved, and the service life of the polyvinyl chloride floor is prolonged.
In the foaming layer, polyvinyl chloride is used as a main raw material of the floor base material and is matched with filler, and the foaming additive can change the strength of a solution and control the foaming process by adding the foaming agent and the foaming additive. And adding a modified reinforcing agent to adapt to a foaming structure with more holes in the foaming layer, so that the heat shrinkage performance of the material is improved, and the heat shrinkage of the material is reduced. And the use of an impact resistance agent is matched, so that the toughness and the impact property of the material can be improved, and the service life of the polyvinyl chloride floor is prolonged.
According to the invention, the foaming layer is arranged in the floor base material, so that the overall density of the floor base material is reduced, the weight of the floor is reduced, and meanwhile, the foaming layer can achieve better heat insulation and noise reduction effects. Meanwhile, according to the characteristics of the solid layer and the foaming layer, proper materials are selected for compounding, so that the strength of the plate is enhanced, the linear expansion coefficient of the floor base material is reduced, the influence of large contraction gap caused by overlarge difference of environmental temperature after floor splicing is avoided, the overall performance of the prepared polyvinyl chloride floor is improved, and the effects of light weight, noise reduction, heat insulation, material mechanical property enhancement and material linear expansion coefficient reduction are achieved.
In an alternative embodiment, the material of the solid layer further comprises a modifier and a thermal stabilizer.
Preferably, the modifier comprises, by weight, 1-5 parts of PA-20, 0.1-1 part of oxidized wax, 1-5 parts of PE wax, 1-5 parts of internal lubricant and 0.1-1 part of rutile titanium dioxide.
The rutile titanium dioxide can be used as a whitening agent and also has certain ultraviolet resistance.
Preferably, the heat stabilizer comprises 2-8 parts by weight of calcium zinc stabilizer, so that the processing heat stability of the solid layer material can be improved, and the polyvinyl chloride floor base material with higher mechanical property can be obtained.
Preferably, the material of the solid layer further comprises a colorant, and the colorant comprises 0.1-1 part by weight of carbon black and 0.01-0.5 part by weight of red pigment.
In an alternative embodiment, the material of the foamed layer further comprises a modifier and a thermal stabilizer.
Preferably, the modifier comprises 1 to 5 portions of PA-20, 0.1 to 1 portion of oxidized wax, 0.1 to 3 portions of PE wax, 0.1 to 3 portions of internal lubricant and 0.1 to 1 portion of rutile titanium dioxide.
In some embodiments of the present invention, the modifier, oxidized wax, PE wax, and internal slip agent used therein may be selected from the following materials.
PA-20 is an acrylate processing modifier, and can promote the plasticization of the solid layer material. The oxidized wax used in the invention is a high-viscosity high-density oxidized homopolymerized wax, the viscosity is 8000-8500 cps at 140 ℃, the fluidity of the solid layer material can be improved, and the plasticization of the solid layer material is promoted. In other embodiments, the oxidized wax may be selected from other commercially available materials as long as the properties match those of the oxidized wax.
The PE wax used in the invention is low-viscosity polyethylene wax, the viscosity of the PE wax is 50-100 cps at 140 ℃, and the PE wax can be used as an external lubricant to improve the fluidity of a solid layer material. In other embodiments, the PE wax may be selected from other commercially available materials, so long as the properties match those of the PE wax.
The PE wax serving as an external lubricant can reduce the interfacial friction between the polymer and the surface of a molding processing machine in the molding processing process, is an interfacial lubricant, has low compatibility with the polyvinyl chloride polymer, is easily transferred from the inside to the surface of the polyvinyl chloride polymer in the processing process, and forms a lubricant molecular layer at the interface.
The internal lubricant comprises any one of stearic acid or monoglyceride, and is added into polyvinyl chloride, so that the internal lubricant has good compatibility with the polyvinyl chloride, can improve the fluidity of a solid layer material and reduce the friction between melting materials.
The rutile titanium dioxide can be used as a whitening agent and also has certain ultraviolet resistance.
Preferably, the heat stabilizer comprises 2-8 parts by weight of calcium zinc stabilizer and 0.1-2 parts by weight of organic tin stabilizer, and can improve the processing heat stability of the solid layer material and obtain the polyvinyl chloride floor base material with higher mechanical property.
In an alternative embodiment, each solid layer has a thickness of 1 to 2mm and a density of 1.9 to 2.1g/cm 3 Each foaming layer has a thickness of 1-3 mm and a density of 0.8-1.0 g/cm 3 。
Preferably, the number of solid layers is 2 and a foamed layer is located between two solid layers.
After the polyvinyl chloride is foamed, the strength of the foaming layer is reduced, the foaming layer is directly filled with the reinforcing agent, the compatibility of the reinforcing agent and the foaming structure is poor, and the direct bonding strength of the reinforcing agent and the foaming structure is not high, so that the reinforcing agent cannot play a better supporting role, and the strength of the polyvinyl chloride plate is low.
Preferably, the addition amount of the aluminate coupling agent is 1-3% of the weight of the reinforcing agent, the activation temperature is 100-120 ℃, and the activation time is 8-10 min.
Preferably, the activation degree of the enhancer is greater than or equal to 98%.
Preferably, the reinforcing agent comprises wollastonite and/or talc.
In alternative embodiments, the impact modifier is an acrylate based impact modifier, and in some embodiments, the impact modifier may be at least one of commercially available materials such as KM-355, MBS B-564.
Preferably, the foam modifier is an acrylate-based foam modifier, and in some embodiments, the impact modifier can be a commercially available material such as at least one of ZB-530, ACR 530.
Preferably, the blowing agent is a chemical blowing agent comprising at least one of azodicarbonamide, trihydrazinotriazine.
Preferably, the filler comprises any one of calcium carbonate and talc.
In an optional embodiment, the material of the solid layer comprises 40-60 parts of polyvinyl chloride, 80-120 parts of filler, 20-30 parts of talcum powder, 1-10 parts of impact resistance agent, 1-5 parts of PA-20, 0.1-1 part of oxidized wax, 1-5 parts of PE wax, 1-5 parts of internal slipping agent, 0.1-1 part of rutile titanium dioxide, 2-8 parts of calcium-zinc stabilizer, 0.1-1 part of carbon black and 0.01-0.5 part of red pigment.
In an optional embodiment, the foaming layer comprises 40-60 parts of polyvinyl chloride, 20-30 parts of filler, 40-60 parts of modification reinforcing agent, 1-10 parts of impact resistance agent, 1-10 parts of foaming regulator, 1-5 parts of foaming agent, 1-5 parts of PA-20, 0.1-1 part of oxidized wax, 0.1-3 parts of PE wax, 0.1-3 parts of internal slipping agent, 0.1-1 part of rutile titanium dioxide, 2-8 parts of calcium-zinc stabilizer and 0.1-2 parts of organic tin stabilizer.
It should be noted that all the raw materials mentioned in the present invention may be commercially relevant materials as long as the relevant properties of the raw materials meet the properties required in the present application.
In a second aspect, the present invention provides a method for preparing a polyvinyl chloride flooring substrate as in any one of the above embodiments, comprising mixing the materials of the solid layer and the foamed layer in proportion respectively and then co-extruding.
In an alternative embodiment, the co-extrusion comprises conical twin-screw co-extrusion, wherein a first screw is filled with the mixed solid layer material, a second screw is filled with the mixed foamed layer material, the junction of the first screw and the second screw is a confluence core region, and the mixed solid layer material and the foamed layer material are co-extruded after passing through the confluence core region.
Preferably, the first screw or the second screw is provided with a feeding section, a compression section, a melting section and a metering section in sequence along the direction from the inlet section to the confluence core area, and the temperature is gradually reduced along the direction from the inlet section to the confluence core area.
Preferably, the temperature of the feeding section of the first screw is 200-240 ℃, the temperature of the compression section is 190-230 ℃, the temperature of the melting section is 170-210 ℃, and the temperature of the metering section is 160-200 ℃; the temperature of the feeding section of the second screw is 180-200 ℃, the temperature of the compression section is 170-190 ℃, the temperature of the melting section is 160-180 ℃, and the temperature of the metering section is 160-170 ℃; the temperature of the confluence core area is 150-170 ℃.
Preferably, the rotation speed of the first screw is 20-30 rpm, the feeding rotation speed of the raw materials entering the first screw in the mixing device is 30-40 rpm, and the host current is 115-120A.
Preferably, the rotation speed of the second screw is 15 to 25rpm, the feeding rotation speed of the raw materials into the second screw in the mixing device is 25 to 35rpm, and the main machine current is 100 to 105A. By controlling the screw rotation speed and temperature of the second screw within the above ranges, it is possible to ensure a sufficient foaming amount of the foaming layer material. When the rotating speed of the screw is too high, the phenomena of coke material, excessive foaming and the like can occur when the temperature in the screw is too high, and the product performance is influenced.
In an alternative embodiment, the material blending of the solid layers in proportions comprises: weighing the materials of the solid layer in proportion, and pouring the materials into a mixer for hot mixing and cold mixing respectively; preferably, the hot mixing temperature is 110-130 ℃, the time is 13-15 min, the cold mixing temperature is 50-70 ℃, and the time is 15-20 min;
preferably, the material of the foamed layer is mixed in proportions including: weighing the materials of the foaming layer in proportion, and pouring the materials into a mixer to respectively carry out hot mixing and cold mixing; preferably, the hot mixing temperature is 95-115 ℃ and the time is 10-12 min, and the cold mixing temperature is 50-70 ℃ and the time is 12-15 min.
In a third aspect, the present invention provides a polyvinyl chloride floor, comprising, in order, a wear-resistant layer, a color film layer, and a polyvinyl chloride floor substrate according to any one of 1 to 6 or a polyvinyl chloride floor substrate prepared by the preparation method according to any one of the foregoing embodiments;
preferably, the preparation of the polyvinyl chloride floor comprises the step of compacting and forming the wear-resistant layer, the color film layer and the polyvinyl chloride floor substrate by adopting a calendaring forming process.
Wherein, the wear-resistant layer and the color film layer are both of a structure which takes polyvinyl chloride as a main raw material, and the wear-resistant layer and the color film layer can be conventional materials sold in the market or materials prepared according to the prior art.
The embodiment of the invention has the beneficial effects that:
the invention provides the polyvinyl chloride floor base material and the preparation method and application thereof, and the foaming layer is arranged in the floor base material, so that the overall density of the floor base material is reduced, the weight of the floor is reduced, and meanwhile, the foaming layer can achieve better heat insulation and noise reduction effects. Meanwhile, according to the characteristics of the solid layer and the foaming layer, proper materials are selected for compounding, so that the strength of the plate is enhanced, the linear expansion coefficient of the floor base material is reduced, the influence of large contraction gap caused by overlarge difference of environmental temperature after floor splicing is avoided, the overall performance of the prepared polyvinyl chloride floor is improved, and the effects of light weight, noise reduction, heat insulation, material mechanical property enhancement and material linear expansion coefficient reduction are achieved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic structural view of a polyvinyl chloride flooring substrate provided in example 1 of the present invention;
FIG. 2 is a schematic view of a co-extrusion apparatus for a polyvinyl chloride floor substrate according to embodiment 1 of the present invention;
fig. 3 is a real object diagram of the polyvinyl chloride floor provided in embodiment 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined or explained in subsequent figures.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or the orientations or positional relationships that the products of the present invention are conventionally placed in use, and are only used for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Furthermore, the terms "horizontal", "vertical" and the like do not imply that the components are required to be absolutely horizontal or pendant, but rather may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
Referring to fig. 1, the present embodiment provides a polyvinyl chloride floor substrate 100 having a total thickness of 4mm and a width of 1m, and including solid layers 101 and foam layers 102, wherein the number of the solid layers 101 is 2, the foam layers 102 are located between two solid layers 101, each solid layer 101 has a thickness of 1.25mm and a density of 1.9-2.1 g/cm 3 Each foamed layer 102 has a thickness of 1.5mm and a density of 0.8 to 1.0g/cm 3 。
In this example, the material of each solid layer 101 includes, by weight, 50 parts of polyvinyl chloride, 100 parts of calcium carbonate, 25 parts of talc, 5 parts of impact modifier KM355, 2.5 parts of PA-20, 0.2 parts of oxidized wax, 2 parts of PE wax, 2 parts of internal lubricant, 0.8 parts of rutile titanium dioxide, 4.5 parts of calcium zinc stabilizer, 0.4 parts of carbon black, and 0.05 parts of red pigment.
The foaming layer 102 comprises, by weight, 50 parts of polyvinyl chloride, 25 parts of calcium carbonate, 50 parts of a modification reinforcing agent, 7 parts of an impact modifier KM355, 6 parts of a foaming regulator, 1.5 parts of azodicarbonamide, 2 parts of PA-20, 0.2 part of oxidized wax, 1.5 parts of PE wax, 1 part of an internal lubricant, 0.5 part of rutile titanium dioxide, 4 parts of calcium zinc stabilizer and 0.5 part of organic tin stabilizer.
The modification reinforcing agent is obtained by activating wollastonite and talcum powder by using an aluminate coupling agent, the activation temperature is 110 ℃, the activation time is 8-10 min, and the total activation degree of the wollastonite and the talcum powder is more than or equal to 98% after the activation is finished. In the modified reinforcing agent, the proportion of each raw material is that the aluminate coupling agent: wollastonite: talc =1.5:50:50.
the invention also provides a preparation method of the polyvinyl chloride floor base material 100, which comprises the following steps:
s1, preparing a modified reinforcing agent
Mixing aluminate coupling agent, wollastonite and talcum powder according to the weight ratio of 1.5:50: weighing 50 parts of the raw materials, mixing, firstly carrying out hot mixing at the heating temperature of 110 ℃, mixing for 8-10 min, then cooling the mixture, cooling to 50 ℃, and mixing for 15min to obtain the modified reinforcing agent.
S2, preparing a solid layer 101 material
Weighing the raw materials of the solid layer 101 in proportion, mixing, firstly carrying out hot mixing at a heating temperature of 120 ℃, mixing for 13min, then cooling the mixture, cooling to 60 ℃, and mixing for 15min to obtain the solid layer material.
S3, preparing a foaming layer 102 material
Weighing the raw materials of the foaming layer 102 in proportion, mixing, firstly carrying out hot mixing at a heating temperature of 105 ℃, mixing for 10min, then cooling the mixture, cooling to 60 ℃, and mixing for 12min to obtain the foaming layer material.
S4. Co-extrusion process
Referring to fig. 2, a 92-cone twin-screw extrusion device is adopted, wherein a solid layer 101 material is filled in a first screw, a foaming layer 102 material is filled in a second screw, a confluence core area is formed at the joint of the first screw and the second screw, and the mixed solid layer 101 material and the foaming layer 102 material are co-extruded after passing through the confluence core area.
In this example, the temperature of the feeding section of the first screw was 220 ℃, the temperature of the compression section was 210 ℃, the temperature of the melting section was 190 ℃, and the temperature of the metering section was 180 ℃; the temperature of the feeding section of the second screw is 190 ℃, the temperature of the compression section is 180 ℃, the temperature of the melting section is 170 ℃, and the temperature of the metering section is 165 ℃; the temperature of the confluent core region was 160 ℃.
The rotation speed of the metering section of the first screw is 25rpm, the rotation speed of the feeding section of the first screw is 35rpm, and the current of a main machine is 115-120A.
The rotation speed of the metering section of the second screw is 20rpm, the rotation speed of the feeding section of the second screw is 30rpm, and the current of a main machine is 100-105A.
Example 2
As shown in fig. 3, this embodiment provides a polyvinyl chloride floor, which comprises, from top to bottom, a polyvinyl chloride wear-resistant layer, a polyvinyl chloride color film layer, and the polyvinyl chloride floor substrate prepared in example 1. Wherein, the polyvinyl chloride wear-resistant layer is produced by Jiangsu Yingtai new materials, and the polyvinyl chloride color film layer is produced by Hangzhou good decoration materials.
The materials are subjected to four-roller calendering molding, wherein a No. 1 roller, a No. 2 roller and a No. 3 roller are mirror surface rollers with the diameter of D400mm and the length of 1.2m, and circulating oil is introduced into a roller for 180 ℃; the No. 4 roller is a patterned roller, the diameter D is 200mm, the length is 1.2m, and the circulating oil temperature in the roller is 180 ℃.
The No. 1 roller and the No. 2 roller are used for calendaring and shaping the polyvinyl chloride floor base material, the No. 3 roller is used for drawing the polyvinyl chloride floor base material, then the polyvinyl chloride color film layer and the polyvinyl chloride wear-resistant layer are sequentially hot-pasted, and finally, the No. 4 roller is used for rolling patterns.
Comparative example 1
This comparative example provides a polyvinyl chloride flooring, which was prepared in the same manner as in example 2 except that the polyvinyl chloride flooring base material had a structure of a foamed layer and a solid layer.
Comparative example 2
This comparative example provides a polyvinyl chloride flooring, which was prepared in the same manner as in example 2 except that the structure of the polyvinyl chloride flooring base was a solid layer.
Comparative example 3
The comparative example provides a polyvinyl chloride floor, the preparation method of which is the same as that of example 2, and the difference is only that the raw material proportion of the solid layer and the foaming layer is different, and the concrete steps are as follows:
the material of each solid layer comprises 50 parts of polyvinyl chloride, 125 parts of calcium carbonate, 25 parts of talcum powder, 5 parts of impact resistance KM355, 2.5 parts of PA-20, 0.2 part of oxidized wax, 2 parts of PE wax, 2 parts of internal lubricant, 0.8 part of rutile titanium dioxide, 4.5 parts of calcium-zinc stabilizer, 0.4 part of carbon black and 0.05 part of red pigment in parts by weight.
The foaming layer comprises, by weight, 50 parts of polyvinyl chloride, 50 parts of calcium carbonate, 50 parts of a modification reinforcing agent, 7 parts of an impact resistance KM355, 6 parts of a foaming regulator, 1.5 parts of azodicarbonamide, 2 parts of PA-20, 0.2 part of oxidized wax, 1.5 parts of PE wax, 1 part of an internal lubricant, 0.5 part of rutile titanium dioxide, 4 parts of calcium zinc stabilizer and 0.7 part of organic tin stabilizer.
Test example 1
The polyvinyl chloride flooring manufactured in example 2 and comparative examples 1 to 3 were examined and the results shown in table 1 were obtained.
TABLE 1 PVC flooring substrate Properties
Figure BDA0003820388790000101
Figure BDA0003820388790000111
From the data, the polyvinyl chloride floor provided by the embodiment of the invention has low density, but has good static bending strength, peeling strength, bending strength, elastic modulus and thermal shrinkage stability, so that the polyvinyl chloride floor provided by the invention has the advantages of light weight and excellent comprehensive mechanical property.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The polyvinyl chloride floor base material is characterized by comprising solid layers and foaming layers, wherein the solid layers and the foaming layers are alternately arranged, and the number of the foaming layers is smaller than that of the solid layers;
the solid layer comprises 40-60 parts by weight of polyvinyl chloride, 80-120 parts by weight of filler, 20-30 parts by weight of talcum powder and 1-10 parts by weight of impact resistance agent;
the foaming layer comprises, by weight, 40-60 parts of polyvinyl chloride, 20-30 parts of filler, 40-60 parts of modified reinforcing agent, 1-10 parts of impact resistance agent, 1-10 parts of foaming regulator and 1-5 parts of foaming agent.
2. The polyvinyl chloride flooring substrate of claim 1, wherein the material of the solid layer further comprises a modifier and a thermal stabilizer;
preferably, the modifier comprises, by weight, PA-201 to 5 parts, oxidized wax 0.1 to 1 part, PE wax 1 to 5 parts, internal lubricant 1 to 5 parts and rutile titanium dioxide 0.1 to 1 part;
preferably, the heat stabilizer comprises 2-8 parts by weight of calcium zinc stabilizer;
preferably, the material of the solid layer also comprises a colorant, and the colorant comprises 0.1-1 part of carbon black and 0.01-0.5 part of red pigment by weight.
3. The polyvinyl chloride floor substrate according to claim 2, wherein the material of the foamed layer further comprises a modifier and a heat stabilizer;
preferably, the modifier comprises, by weight, PA-201 to 5 parts, oxidized wax 0.1 to 1 part, PE wax 0.1 to 3 parts, internal lubricant 0.1 to 3 parts and rutile titanium dioxide 0.1 to 1 part;
preferably, the heat stabilizer comprises 2 to 8 parts by weight of calcium zinc stabilizer and 0.1 to 2 parts by weight of organic tin stabilizer.
4. Polyvinyl chloride floor according to claim 3The board substrate is characterized in that the thickness of each solid layer is 1-2 mm, and the density is 1.9-2.1 g/cm 3 Each foaming layer has a thickness of 1-3 mm and a density of 0.8-1.0 g/cm 3 ；
Preferably, the number of the solid layers is 2, and the foamed layer is located between two of the solid layers.
5. The polyvinyl chloride floor substrate according to claim 1, wherein the modification enhancing agent comprises activating the enhancing agent with an aluminate coupling agent;
preferably, the addition amount of the aluminate coupling agent is 1 to 3 percent of the weight of the reinforcing agent, the activation temperature is 100 to 120 ℃, and the activation time is 8 to 10min;
preferably, the activation degree of the reinforcing agent is more than or equal to 98 percent;
preferably, the reinforcing agent comprises wollastonite and/or talc.
6. The polyvinyl chloride flooring substrate of claim 1, wherein the impact modifier is an acrylate impact modifier comprising at least one of KM-355, MBS B-564;
preferably, the foaming regulator is an acrylate foaming regulator and comprises at least one of ZB-530 and ACR 530;
preferably, the blowing agent is a chemical blowing agent comprising at least one of azodicarbonamide, trihydrazinotriazine.
7. A method for preparing the polyvinyl chloride floor base material as claimed in any one of claims 1 to 6, which comprises mixing the materials of the solid layer and the foamed layer in proportion respectively and then co-extruding.
8. The method of claim 7, wherein the co-extrusion comprises a conical twin-screw co-extrusion, wherein a first screw is filled with the mixed solid layer material, a second screw is filled with the mixed foamed layer material, the junction of the first screw and the second screw is a confluence core region, and the mixed solid layer material and the foamed layer material are co-extruded after passing through the confluence core region;
preferably, the first screw or the second screw is provided with a compression section, a melting section and a metering section in sequence along the direction from the inlet section to the confluence core area, and the temperature is gradually reduced along the direction from the inlet section to the confluence core area;
preferably, the temperature of the feeding section of the first screw is 200-240 ℃, the temperature of the compression section is 190-230 ℃, the temperature of the melting section is 170-210 ℃, and the temperature of the metering section is 160-200 ℃; the temperature of the feeding section of the second screw is 180-200 ℃, the temperature of the compression section is 170-190 ℃, the temperature of the melting section is 160-180 ℃, and the temperature of the metering section is 160-170 ℃; the temperature of the confluence core area is 150-170 ℃;
preferably, the rotating speed of the first screw is 20-30 rpm, the feeding rotating speed of the solid layer material entering the first screw is 30-40 rpm, and the host machine current is 115-120A;
preferably, the rotation speed of the second screw is 15-25 rpm, the feeding rotation speed of the foaming layer material entering the second screw is 25-35 rpm, and the main machine current is 100-105A.
9. The method of claim 8, wherein the mixing the materials of the solid layer in proportions comprises: weighing the materials of the solid layer in proportion, and pouring the materials into a mixer for hot mixing and cold mixing respectively; preferably, the hot mixing temperature is 110-130 ℃, the time is 13-15 min, the cold mixing temperature is 50-70 ℃, and the time is 15-20 min;
preferably, the material proportion mixing of the foaming layer comprises: weighing the materials of the foaming layer in proportion, and pouring the materials into a mixer for hot mixing and cold mixing respectively; preferably, the hot mixing temperature is 95-115 ℃ and the time is 10-12 min, and the cold mixing temperature is 50-70 ℃ and the time is 12-15 min.
10. A polyvinyl chloride floor is characterized by comprising a wear-resistant layer, a color film layer and the polyvinyl chloride floor base material as defined in any one of 1 to 6 or the polyvinyl chloride floor base material prepared by the preparation method as defined in any one of claims 7 to 9 in sequence;
preferably, the preparation of the polyvinyl chloride floor comprises the step of compacting and molding the wear-resistant layer, the color film layer and the polyvinyl chloride floor substrate by adopting a calendering and molding process.
CN202211041119.4A 2022-08-29 2022-08-29 Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor Pending CN115384151A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211041119.4A CN115384151A (en) 2022-08-29 2022-08-29 Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211041119.4A CN115384151A (en) 2022-08-29 2022-08-29 Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor

Publications (1)

Publication Number Publication Date
CN115384151A true CN115384151A (en) 2022-11-25

Family

ID=84122564

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211041119.4A Pending CN115384151A (en) 2022-08-29 2022-08-29 Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor

Country Status (1)

Country Link
CN (1) CN115384151A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200967A (en) * 2017-07-17 2017-09-26 青岛三益塑料机械有限公司 Composition and sheet material and its production method comprising this composition for producing plate foaming layer
CN114044990A (en) * 2021-11-24 2022-02-15 河南君源塑业有限公司 High-strength polyvinyl chloride foam board and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200967A (en) * 2017-07-17 2017-09-26 青岛三益塑料机械有限公司 Composition and sheet material and its production method comprising this composition for producing plate foaming layer
CN114044990A (en) * 2021-11-24 2022-02-15 河南君源塑业有限公司 High-strength polyvinyl chloride foam board and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王文广: "《塑料配方设计》", pages: 406 - 152 *

Similar Documents

Publication Publication Date Title
WO2018098899A1 (en) Stone-like plastic flooring and preparation method thereof
KR101320265B1 (en) Composite board including polylacticacid cover
US7169460B1 (en) Thermoplastic planks and methods for making the same
EP2998353A1 (en) Pvc composite material, foaming board and production method, equipment and floor
WO2019000604A1 (en) Composite floor and preparation method therefor
CN106977833A (en) Polyvinyl chloride composite materials and its processing method
US20170240738A1 (en) Fiber-reinforced composite extrusion with enhanced properties
US11267963B2 (en) Composite extrusion with non-aligned fiber orientation
US6692683B2 (en) Method of making an extruded multilayer polymeric shell having textured and marbled surface
US20170044778A1 (en) Impact resistant wear layer
KR100909183B1 (en) Pvc pipe including carcon fiber and manufacturing method of the same
CN107200967A (en) Composition and sheet material and its production method comprising this composition for producing plate foaming layer
CN104403233A (en) Hollow board and composite board
CN111441555A (en) SPC stone plastic floor and preparation method thereof
CN102020814A (en) Recycled polypropylene modified polrvinyl chloride sectional material and preparation method thereof
CN113045245A (en) SPC floor and preparation method thereof
CN115384151A (en) Polyvinyl chloride floor base material, preparation method thereof and polyvinyl chloride floor
CN109591419B (en) PVC foaming folding plate and preparation method thereof
CN106905638A (en) A kind of flame-proof environmental protection PVC floors and preparation method thereof
CN110144092A (en) A kind of environmental protection hard PVC modified material and preparation method thereof
CN112746719A (en) Multilayer co-extrusion stone-plastic floor and manufacturing method thereof
CN107722492B (en) Straw plastic floor and preparation method thereof
EP3498774B1 (en) Resin composition obtained by mixing polyvinyl chloride resin and acrylic resin, and indoor interior material board produced using same
WO2020028633A1 (en) Calendered polyvinyl chlorsde/cellulose ester blend film
KR101977793B1 (en) Non-glossy two-layer sheet comprising embossed PMMA skin layer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination