CN113715450A - Assembled floor with double-layer structure and preparation method thereof - Google Patents

Assembled floor with double-layer structure and preparation method thereof Download PDF

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Publication number
CN113715450A
CN113715450A CN202110957712.2A CN202110957712A CN113715450A CN 113715450 A CN113715450 A CN 113715450A CN 202110957712 A CN202110957712 A CN 202110957712A CN 113715450 A CN113715450 A CN 113715450A
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polypropylene
layer
thermoplastic elastomer
injection molding
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CN113715450B (en
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方耀华
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Jiangmen Jiaxinda Mould Technology Co ltd
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Jiangmen Jiaxinda Mould Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/03—Injection moulding apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • 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
    • B32B27/08—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 synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • E04F15/105—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 of organic plastics with or without reinforcements or filling materials
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/22—Resiliently-mounted floors, e.g. sprung floors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Abstract

The invention discloses an assembled floor with a double-layer structure, which comprises a surface layer and a bottom layer, wherein the surface layer and the bottom layer are of an integral injection molding structure, and the surface layer is prepared from the following components in parts by weight: 100 parts of thermoplastic elastomer and 0.5-1 part of color master batch, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of hard rubber material and 1.5-2 parts of color master batch. The assembled floor has a double-layer structure, consists of a surface layer and a bottom layer which are integrally injection-molded, the surface layer is made of a thermoplastic elastomer with an improved formula, the bottom layer is made of a ebonite material with an improved formula, and the assembled floor has excellent shock absorption, stain resistance and aging resistance, can prolong the service life to more than 3 years, has good color retention and is not easy to fade.

Description

Assembled floor with double-layer structure and preparation method thereof
Technical Field
The invention relates to the technical field of rubber materials, in particular to a spliced floor with a double-layer structure and a preparation method thereof.
Background
The assembled floor is also called as a combined sports floor, and has the characteristics of simple assembly, convenient movement, rich colors, difficult water accumulation and the like. The anti-skid device adopts a suspended structural design and a firm reinforced supporting leg structure, has a vertical shock absorption effect, and can effectively prevent sports damage on an anti-skid surface, so that the anti-skid device is widely applied to indoor and outdoor sports fields in recent years.
However, most of the existing assembled floors are of single-layer structures, have poor damping effect, are poor in anti-fouling and anti-aging effects, have the defects of easy aging, brittleness and fouling when being used in outdoor places, and are short in service life and generally only capable of being maintained for about 1 year.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the assembled floor with the double-layer structure and the preparation method thereof. The assembled floor provided by the invention is composed of the surface layer and the bottom layer which are integrally formed by injection molding, and the surface layer is made of the thermoplastic elastomer, so that the assembled floor has excellent damping effect, dirt resistance and aging resistance, and the service life of the assembled floor is prolonged.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a bilayer structure's assemble floor, its includes surface course and bottom, the surface course with the bottom is integrative injection moulding structure, the surface course is made by the component of following part by weight: 100 parts of thermoplastic elastomer and 0.5-1 part of color master batch, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of hard rubber material and 1.5-2 parts of color master batch.
Preferably, the thermoplastic elastomer comprises the following components in parts by weight: 35-45 parts of SEBS, 8-12 parts of first polypropylene, 25-35 parts of 150N base oil, 6-10 parts of a toughening agent, 1-3 parts of a compatibilizer A, 1.5-2.5 parts of a lubricant, 8-12 parts of a filler A, 0.1-0.2 part of an anti-fouling assistant and 0.15-0.25 part of an anti-UV assistant; the first polypropylene comprises block copolymer polypropylene A and block copolymer polypropylene B; the melt index of the block copolymer polypropylene A under the test conditions of 190 ℃ and 2.16kg is 5-10 g/10min, and the melt index of the block copolymer polypropylene B under the test conditions of 190 ℃ and 2.16kg is 20-30 g/10 min. Experimental research shows that the combination of the block copolymer polypropylene A and the block copolymer polypropylene B can effectively improve the mechanical property and the high and low temperature resistance of the thermoplastic elastomer, and can also improve the fluidity of rubber materials, so that the product can be molded better.
Preferably, the thermoplastic elastomer comprises the following components in parts by weight: 40 parts of SEBS, 10 parts of first polypropylene, 30 parts of 150N base oil, 8 parts of toughening agent, 2 parts of compatibilizer A, 2 parts of lubricant, 10 parts of filler A, 0.15 part of anti-fouling assistant and 0.2 part of anti-UV assistant.
Preferably, the SEBS designation includes 7551. The SEBS of the brand has good aging resistance and mechanical property, can be processed and used without vulcanization, has good compatibility with 150N base oil, can adjust the hardness through the 150N base oil, and enables the thermoplastic elastomer to have the damping effect meeting the use requirement of assembled floors. In addition, the block copolymerization polypropylene A and the block copolymerization polypropylene B with the melt index have good compatibility with SEBS with the trade name of 7551, and the blending effect is good.
Preferably, in the thermoplastic elastomer, the mass ratio of the block copolymerization polypropylene A to the block copolymerization polypropylene B is 1: 2-1: 3. By regulating and controlling the proportion of the block copolymer polypropylene A and the block copolymer polypropylene B, the rubber material is ensured to have better fluidity, and the mechanical property and the high and low temperature resistance of the thermoplastic elastomer are better.
Preferably, in the thermoplastic elastomer, the mass ratio of the block copolymer polypropylene A to the block copolymer polypropylene B is 1: 2.5. When the block copolymer polypropylene A and the block copolymer polypropylene B are compounded and used according to the proportion, the mechanical property and the high and low temperature resistance of the thermoplastic elastomer are the best.
Preferably, the toughening agent comprises a POE3980 toughening agent. The addition of the POE3980 toughening agent can further improve the fluidity of the whole system, improve the toughness of the thermoplastic elastomer, ensure that the thermoplastic elastomer surface layer is not easy to delaminate from the PP bottom layer, and improve the firmness of the integrated injection molding structure of the assembled floor.
Preferably, the lubricant comprises silicone powder. In the formula of the invention, the addition of the silicone powder can play a role in lubrication, so that the product is easy to demould, and the surface wear resistance of the thermoplastic elastomer can be improved.
Preferably, the UV resistant auxiliary comprises at least one of EP-V701, KZ-1145. The UV resistant auxiliary agent with the above grade has good compatibility with the sizing material of the formula of the invention, and can improve the UV resistant performance of the sizing material.
Preferably, the anti-fouling aid comprises a fluorine-modified anti-fouling aid, and the trademark is diclok Lencolo 3007D. The prior art generally uses the auxiliary agent in the coating, however, the inventor of the invention finds that the auxiliary agent has better compatibility with the formula system of the invention, and a layer of anti-fouling protective film can be formed on the surface of the sizing material after blending, thereby improving the anti-fouling capability of the product.
Preferably, the hard rubber material comprises the following components in parts by weight: 70-90 parts of second polypropylene, 15-25 parts of filler B, 1-5 parts of compatibilizer B and 0.1-1 part of antioxidant, wherein the second polypropylene comprises polypropylene with the trademark of SP179 and polypropylene with the trademark of K9026. Researches show that the hardness and the impact strength of the ebonite material can be improved by combining the SP179 polypropylene and the K9026 polypropylene, so that the ebonite material can play a better supporting role when being applied to the bottom layer of an assembled floor.
Preferably, the hard rubber material comprises the following components in parts by weight: 80 parts of second polypropylene, 20 parts of filler B, 3 parts of compatibilizer B and 0.2 part of antioxidant.
Preferably, in the hard rubber material, the mass ratio of SP179 polypropylene to K9026 polypropylene is 0.8-1.2: 0.8-1.2. When the SP179 polypropylene and the K9026 polypropylene are used in combination according to the proportion, the effect of improving the hardness and the impact strength of the ebonite material is more remarkable.
Preferably, in the ebonite material, the mass ratio of the SP179 polypropylene to the K9026 polypropylene is 1: 1. When the P179 polypropylene and the K9026 polypropylene are used in combination according to the proportion, the effect of improving the hardness and the impact strength of the ebonite material is most remarkable.
Preferably, the filler A and the filler B are respectively composed of light calcium carbonate and heavy calcium carbonate, and the particle size of the heavy calcium carbonate is 600-800 meshes.
Preferably, in the filler A and the filler B, the mass ratio of the light calcium carbonate to the heavy calcium carbonate is 1: 0.3-1: 0.5.
Preferably, in the filler A and the filler B, the mass ratio of the light calcium carbonate to the heavy calcium carbonate is 1: 0.4.
The addition of the filler can improve the formability of the rubber material, increase the volume of the rubber material and achieve the aim of reducing the cost. Researches show that if only light calcium carbonate is added, the light calcium carbonate is easy to agglomerate and difficult to disperse uniformly; if only heavy calcium carbonate is added, the contact area with the rubber material is small, and the blending effect is poor. The light calcium carbonate and the heavy calcium carbonate are compounded, and the dispersion and blending effects can be simultaneously considered by regulating and controlling the proportion and the granularity of the light calcium carbonate and the heavy calcium carbonate, so that the filler which is not easy to agglomerate and disperse and has a good blending effect with the rubber is obtained, and the technical effects of improving the formability of the rubber and increasing the volume of the rubber are finally achieved.
Preferably, the compatibilizer a and the compatibilizer B respectively include at least one of styrene-butadiene-styrene block copolymer (SBS) and maleic anhydride grafted SBS (MAH-SBS).
Preferably, the antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, antioxidant 168.
The invention also provides a preparation method of the assembled floor with the double-layer structure, which comprises the following steps:
step one, preparing thermoplastic elastomer
Uniformly mixing SEBS and 150N base oil, adding other components of a thermoplastic elastomer formula, uniformly mixing, extruding by using a double-screw extruder, controlling the extrusion temperature to be 160-180 ℃, cooling, and granulating to obtain the thermoplastic elastomer;
step two, preparing the hard rubber material
Uniformly mixing the components in the formula of the hard rubber material, extruding the mixture by using a double-screw extruder, controlling the extrusion temperature to be 180-200 ℃, cooling and granulating to obtain the hard rubber material;
step three, preparing the assembled floor
Uniformly mixing the thermoplastic elastomer and color master according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material and color master according to a formula to obtain a second mixed material;
adding the second mixed material into an injection molding machine for one-time injection molding to obtain a bottom layer;
and putting the bottom layer into a mold, adding the first mixed material into an injection molding machine for secondary injection molding, and forming a surface layer on the bottom layer to obtain the assembled floor with the double-layer structure.
Preferably, the process conditions of the one-time injection molding are as follows: the molding temperature of the injection molding machine is 160-230 ℃, the injection pressure is 700-1400 bar, and the temperature of the mold is 20-50 ℃.
Preferably, the process conditions of the secondary injection molding are as follows: the molding temperature of the injection molding machine is 170-210 ℃, the injection pressure is 700-1400 bar, and the temperature of the mold is 40-50 ℃.
Compared with the prior art, the invention has the beneficial effects that: the assembled floor has a double-layer structure, consists of a surface layer and a bottom layer which are integrally injection-molded, the surface layer is made of a thermoplastic elastomer with an improved formula, the bottom layer is made of a ebonite material with an improved formula, and the assembled floor has excellent shock absorption, stain resistance and aging resistance, can prolong the service life to more than 3 years, has good color retention and is not easy to fade.
Drawings
Fig. 1 is a structural reference view of a two-layer structure assembled floor according to the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be understood that the examples are not intended to limit the scope of the present invention. The raw materials used in the present invention are all commercially available. Unless otherwise indicated, the methods used in the examples are all conventional in the art, and the equipment used is all conventional in the art.
The sources of the raw materials used in the examples are as follows:
Figure BDA0003219423580000051
Figure BDA0003219423580000061
examples 1 to 3
Examples 1-3 provide a thermoplastic elastomer having the formulation shown in Table 1. Comparative examples 1 to 3 also provide a thermoplastic elastomer whose formulation composition is shown in table 1.
In table 1, the polypropylene is composed of block copolymer polypropylene a and block copolymer polypropylene B, and the mass ratio of block copolymer polypropylene a to block copolymer polypropylene B is 1: 2.5. The filler is a mixture of light calcium carbonate and heavy calcium carbonate, and the mass ratio of the light calcium carbonate to the heavy calcium carbonate is 1: 0.4.
The preparation method of the thermoplastic elastomer of the embodiment 1 to 3 comprises the following steps: (1) mixing SEBS and 150N base oil uniformly, adding other components, and mixing uniformly to obtain a mixed material; (2) and (2) extruding the mixed material obtained in the step (1) by using a double-screw extruder, cooling and granulating to obtain the thermoplastic elastomer. Wherein the extrusion temperature of the double-screw extruder is controlled to be 160-180 ℃.
Comparative examples 1 to 3 the thermoplastic elastomer preparation method refers to examples 1 to 3.
TABLE 1
Figure BDA0003219423580000062
Figure BDA0003219423580000071
Note: in the table, "-" indicates that the component was not added.
Performance testing of thermoplastic elastomers
The thermoplastic elastomers of examples 1 to 3 and comparative examples 1 to 3 were molded into sheets, and cut into standard test specimens, and the test results are shown in Table 2.
Hardness: test method was according to ASTM D2240.
Tensile strength: test method is according to ASTM D412.
Elongation at break: test method is according to ASTM D412.
Compression set ratio: the temperature is 70 ℃ multiplied by 168h, the test method is in accordance with GB/T7759.1-2015, and the standard value is less than 50%.
And (3) aging performance test: 158 ℃ for 168 h.
And (3) testing the flame retardant property: and (4) vertical combustion, and testing according to GB/T2408-2008.
Measurement of embrittlement temperature: the sample is arranged in a clamp in a cantilever mode, is placed in a low-temperature medium for constant temperature, and is impacted at a certain speed by a punch after reaching a certain preset low temperature, and the temperature when the breakage rate of the sample reaches 50 percent is the embrittlement temperature.
Wear resistance: taber abrasion resistance test, abrasion conditions: h-18 grinding wheel, weight 2000g, revolution 1000r, revolution 72rpm, calculate the mass loss rate.
Stain resistance: smearing the surface of the sample with an oiliness pen, drying in a 60 ℃ oven (3min), taking out, wiping with a wet tissue, and counting the wiping times required for wiping each sample.
TABLE 2
Figure BDA0003219423580000081
Table 2 analysis of results: the thermoplastic elastomers of examples 1-3 have good toughness, elasticity and mechanical strength, and are good in aging resistance, high and low temperature resistance, abrasion resistance, flame retardancy and stain resistance, and the performance of example 1 is particularly the best. Comparative analysis of comparative examples 1-2 shows that the type of SEBS can significantly affect the performance of the thermoplastic elastomer, and comparative examples 1 and 2 using other grades of SEBS are inferior to example 1 in aging resistance, high and low temperature resistance, wear resistance, flame retardancy and stain resistance. Comparative example 3 shows that the fluorine modified anti-fouling additive of the invention can effectively improve the anti-fouling capability of the thermoplastic elastomer.
Secondly, 7 groups of test groups are set for researching the influence of the component composition and the component distribution ratio of the polypropylene on the performance of the thermoplastic elastomer, and the component composition and the component distribution ratio of each group of polypropylene are shown in table 3.
TABLE 3
Group of Polypropylene
Test group 1 Block copolymerized polypropylene A + block copolymerized polypropylene B, and A: B ═ 1:1
Test group 2 Block copolymerized polypropylene A + block copolymerized polypropylene B, and A: B ═ 1:2
Test group 3 Block copolymerized polypropylene A + block copolymerized polypropylene B, and A: B ═ 1:2.5
Test group 4 Block copolymerized polypropylene A + block copolymerized polypropylene B, and A: B ═ 1:3
Test group 5 Block copolymerized polypropylene A + block copolymerized polypropylene B, and A: B ═ 1:4
Test group 6 Block copolymerized polypropylene A
Test group 7 Block copolymerized polypropylene B
The test groups 1 to 7 were used to prepare thermoplastic elastomers (10 parts of polypropylene were used in total) according to the formulation and preparation method of example 1, and the performance of the thermoplastic elastomers was tested, and the test results are shown in table 4.
TABLE 4
Figure BDA0003219423580000091
Figure BDA0003219423580000101
Table 4 analysis of results: from test groups 1-5, the proportion of the block copolymer polypropylene A and the block copolymer polypropylene B can influence the mechanical property and the high and low temperature resistance of the thermoplastic elastomer, and when the mass ratio of the block copolymer polypropylene A to the block copolymer polypropylene B is 1 (2-3), the mechanical property and the high and low temperature resistance of the thermoplastic elastomer are better. When only the block copolymerization polypropylene A is used, the thermoplastic elastomer is too soft and has poor toughness, the application requirement of the assembled floor cannot be met, and the high and low temperature resistance and the wear resistance of the assembled floor are also obviously reduced. When only the block copolymerization polypropylene B is used, the thermoplastic elastomer is too hard and has poor toughness, the application requirement of the assembled floor cannot be met, and the high and low temperature resistance and the wear resistance of the assembled floor are also obviously reduced.
Examples 4 to 6
Examples 4-6 provide a ebonite material having a formulation as shown in Table 5. Comparative examples 4 to 7 also provide a ebonite material having the formulation shown in table 5.
In table 5, the filler is a mixture of light calcium carbonate and heavy calcium carbonate, and the mass ratio of light calcium carbonate to heavy calcium carbonate is 1: 0.4.
The preparation method of the ebonite material of the embodiment 4-6 comprises the following steps: and uniformly mixing all the raw materials, extruding by using a double-screw extruder, cooling and granulating to obtain the hard rubber material. Wherein the extrusion temperature of the double-screw extruder is controlled to be 180-200 ℃.
Comparative examples 4 to 7 are the methods of preparing the ebonite material according to examples 4 to 6.
TABLE 5
Figure BDA0003219423580000102
Figure BDA0003219423580000111
Note: in the table, "-" indicates that the component was not added.
Third, performance test of ebonite material
The ebonite materials of examples 4-6 and comparative examples 4-7 were compression molded into sheets and cut into standard test specimens with the test results shown in table 6.
Hardness: test method was according to ASTM D2240.
Impact strength: the test method is based on GB/T18943-
TABLE 6
Figure BDA0003219423580000112
Table 6 analysis of results: the ebonite materials of examples 4-6 have higher hardness and stronger impact strength, especially the best performance of example 1. Comparing and analyzing the example 4 and the comparative examples 4 to 5, it can be seen that the ratio of the SP179 to the K9026 has an influence on the performance of the ebonite material. When the mass ratio of SP179 to K9026 is 0.8-1.2: 0.8-1.2, the mechanical property of the ebonite material is good. When the mass ratio of SP179 to K9026 is 1:1, the mechanical property of the ebonite material is the best. Comparative analysis of comparative examples 6-7 shows that compared with the single use of SP179 or K9026, when the SP179 and the K9026 are used in combination, the hardness and the impact strength of the ebonite material are both remarkably improved.
Example 7
The utility model provides a bilayer structure's assemble floor, it comprises surface course and bottom, and surface course and bottom be integrative injection moulding structure, and the surface course is made by the component of following part by weight: 100 parts of thermoplastic elastomer and 0.8 part of red mother rubber in example 1, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of the ebonite material of example 4 and 1.5 parts of black master batch. The structure of the assembled floor can refer to fig. 1, and in actual production, the assembled floor can be formed by relating a mold according to a required shape.
The preparation method of the spliced floor comprises the following steps:
uniformly mixing a thermoplastic elastomer and a red master according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material and the black master batch according to the formula to obtain a second mixed material;
adding the second mixed material into an injection molding machine for one-time injection molding, wherein the molding temperature of the injection molding machine is 190 ℃, the injection pressure is 1000bar, and the temperature of a mold is 40 ℃ to obtain a bottom layer;
and (3) putting the bottom layer into a mold, adding the first mixed material into an injection molding machine for secondary injection molding, and forming a surface layer on the bottom layer, wherein the molding temperature of the injection molding machine is 210 ℃, the injection pressure is 1400bar, and the temperature of the mold is 50 ℃, so that the assembled floor with the double-layer structure is obtained.
Example 8
The utility model provides a bilayer structure's assemble floor, it comprises surface course and bottom, and surface course and bottom be integrative injection moulding structure, and the surface course is made by the component of following part by weight: the thermoplastic elastomer of the embodiment 2 comprises 100 parts of thermoplastic elastomer and 1 part of red masterbatch, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of the ebonite material of example 5 and 2 parts of black master batch.
The preparation method of the spliced floor comprises the following steps:
uniformly mixing a thermoplastic elastomer and a red master according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material and the black master batch according to the formula to obtain a second mixed material;
adding the second mixed material into an injection molding machine for one-time injection molding, wherein the molding temperature of the injection molding machine is 230 ℃, the injection pressure is 700bar, and the temperature of a mold is 30 ℃ to obtain a bottom layer;
and (3) putting the bottom layer into a mold, adding the first mixed material into an injection molding machine for secondary injection molding, and forming a surface layer on the bottom layer, wherein the molding temperature of the injection molding machine is 180 ℃, the injection pressure is 700bar, and the temperature of the mold is 40 ℃, so that the assembled floor with the double-layer structure is obtained.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The utility model provides a bilayer structure's assembles floor, its characterized in that includes surface course and bottom, the surface course with the bottom is integrative injection moulding structure, the surface course is made by the component of following parts by weight: 100 parts of thermoplastic elastomer and 0.5-1 part of color master batch, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of a hard rubber material and 1.5-2 parts of color master batch;
the thermoplastic elastomer comprises the following components in parts by weight: 35-45 parts of SEBS, 8-12 parts of first polypropylene, 25-35 parts of 150N base oil, 6-10 parts of a toughening agent, 1-3 parts of a compatibilizer, 1.5-2.5 parts of a lubricant, 8-12 parts of a filler A, 0.1-0.2 part of an anti-fouling aid and 0.15-0.25 part of an anti-UV aid; the first polypropylene comprises a block copolymerization polypropylene A and a block copolymerization polypropylene B, the melt index of the block copolymerization polypropylene A under the test condition of 190 ℃ and 2.16kg is 5-10 g/10min, and the melt index of the block copolymerization polypropylene B under the test condition of 190 ℃ and 2.16kg is 20-30 g/10 min;
the hard rubber material comprises the following components in parts by weight: 70-90 parts of second polypropylene, 15-25 parts of filler B, 1-5 parts of compatibilizer B and 0.1-1 part of antioxidant, wherein the second polypropylene comprises polypropylene with the trademark of SP179 and polypropylene with the trademark of K9026.
2. The two-layer construction panel floor of claim 1, wherein the thermoplastic elastomer comprises the following components in parts by weight: 40 parts of SEBS, 10 parts of first polypropylene, 30 parts of 150N base oil, 8 parts of toughening agent, 2 parts of compatibilizer A, 2 parts of lubricant, 10 parts of filler A, 0.15 part of anti-fouling assistant and 0.2 part of anti-UV assistant; preferably, the SEBS designation includes 7551.
3. The assembled floor of a two-layer structure of claim 1, wherein the thermoplastic elastomer comprises a block copolymer polypropylene A and a block copolymer polypropylene B in a mass ratio of 1:2 to 1: 3.
4. The assembled floor of a double-layer structure of claim 1, wherein the hard glue material comprises the following components in parts by weight: 80 parts of second polypropylene, 20 parts of filler B, 3 parts of compatibilizer B and 0.2 part of antioxidant.
5. The assembled floor of the double-layer structure as claimed in claim 1, wherein the mass ratio of SP179 polypropylene to K9026 polypropylene in the hard rubber material is 0.8-1.2: 0.8-1.2.
6. The assembled floor of a double-layer structure as claimed in claim 1, wherein the filler a and the filler B are composed of light calcium carbonate and heavy calcium carbonate, respectively, and the particle size of the heavy calcium carbonate is 600-800 meshes; in the filler A and the filler B, the mass ratio of the light calcium carbonate to the heavy calcium carbonate is 1: 0.3-1: 0.5.
7. The two-layer structured parquet floor as claimed in claim 1, wherein said compatibilizer a and said compatibilizer B each comprise at least one of styrene-butadiene-styrene block copolymer and maleic anhydride grafted SBS.
8. The two-layer construction panel flooring of claim 1, wherein the flexibilizer comprises POE3980 flexibilizer, the lubricant comprises silicone powder, the UV resistant adjuvant comprises at least one of EP-V701, KZ-1145, and the soil resistant adjuvant comprises a fluorine modified soil resistant adjuvant.
9. The bi-layer construction parquet floor as claimed in claim 1, wherein said antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, antioxidant 168.
10. A method for manufacturing the assembled floor of the double-layer structure as claimed in any one of claims 1 to 9, comprising the steps of:
step one, preparing thermoplastic elastomer
Uniformly mixing SEBS and 150N base oil, adding other components of a thermoplastic elastomer formula, uniformly mixing, extruding by using a double-screw extruder, controlling the extrusion temperature to be 160-180 ℃, cooling, and granulating to obtain the thermoplastic elastomer;
step two, preparing the hard rubber material
Uniformly mixing the components in the formula of the hard rubber material, extruding the mixture by using a double-screw extruder, controlling the extrusion temperature to be 180-200 ℃, cooling and granulating to obtain the hard rubber material;
step three, preparing the assembled floor
Uniformly mixing the thermoplastic elastomer and color master according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material and color master according to a formula to obtain a second mixed material;
adding the second mixed material into an injection molding machine for one-time injection molding to obtain a bottom layer;
putting the bottom layer into a mold, adding the first mixed material into an injection molding machine for secondary injection molding, forming a surface layer on the bottom layer, and integrally injection molding the surface layer and the bottom layer to obtain the assembled floor with a double-layer structure;
the process conditions of the one-time injection molding are as follows: the molding temperature of the injection molding machine is 160-230 ℃, the injection pressure is 700-1400 bar, and the temperature of the mold is 20-50 ℃;
the process conditions of the secondary injection molding are as follows: the molding temperature of the injection molding machine is 170-210 ℃, the injection pressure is 700-1400 bar, and the temperature of the mold is 40-50 ℃.
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