CN113715450B - 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
CN113715450B
CN113715450B CN202110957712.2A CN202110957712A CN113715450B CN 113715450 B CN113715450 B CN 113715450B CN 202110957712 A CN202110957712 A CN 202110957712A CN 113715450 B CN113715450 B CN 113715450B
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parts
polypropylene
double
injection molding
assembled floor
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CN113715450A (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 integrated 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 masterbatch, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of hard gum material and 1.5 to 2 parts of color masterbatch. The assembled floor has a double-layer structure, is formed by an integrally injection molded surface layer and a bottom layer, wherein the surface layer is made of thermoplastic elastomer with improved formula, and the bottom layer is made of hard rubber material with improved formula, so that the assembled floor has excellent shock absorption, pollution resistance and ageing 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 double-layer structure assembled floor and a preparation method thereof.
Background
The assembled floor is also called a combined sports floor, and has the characteristics of simple assembly, convenient movement, rich colors, difficult water accumulation and the like. The anti-skid support adopts a suspension type structural design and a firm reinforced support foot structure, has a vertical damping effect, and can effectively prevent sports injury on the anti-skid surface, so that the anti-skid support is widely applied to indoor and outdoor sports fields in recent years.
However, most of the existing assembled floors are of a single-layer structure, the shock absorption effect is poor, the anti-fouling and anti-aging effects are not ideal, and especially when the assembled floors are used in outdoor places, the assembled floors have the defects of easy aging and embrittlement and easy fouling, the service life is short, and the assembled floors can be maintained for about 1 year generally.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an assembled floor with a double-layer structure and a preparation method thereof. The assembled floor is composed of the surface layer and the bottom layer which are integrally injection molded, and the surface layer is made of the thermoplastic elastomer, so that the assembled floor has excellent damping effect, pollution resistance and aging resistance, and the service life of the assembled floor is prolonged.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the assembled floor with the double-layer structure comprises a surface layer and a bottom layer, wherein the surface layer and the bottom layer are of an integrated 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 masterbatch, wherein the bottom layer is prepared from the following components in parts by weight: 100 parts of hard gum material and 1.5 to 2 parts of color masterbatch.
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 flexibilizer, 1-3 parts of compatibilizer A, 1.5-2.5 parts of lubricant, 8-12 parts of filler A, 0.1-0.2 part of anti-fouling additive and 0.15-0.25 part of anti-UV additive; the first polypropylene comprises block copolymerized polypropylene A and block copolymerized polypropylene B; the melt index of the block copolymerized polypropylene A under the test condition of 190 ℃ and 2.16kg is 5-10 g/10min, and the melt index of the block copolymerized polypropylene B under the test condition of 190 ℃ and 2.16kg is 20-30 g/10min. Experimental study shows that the combination of the block copolymerized polypropylene A and the block copolymerized polypropylene B can effectively improve the mechanical property and the high-low temperature resistance of the thermoplastic elastomer, and can also improve the flowability of the sizing material, so that the product is better molded.
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 additive and 0.2 part of anti-UV additive.
Preferably, the SEBS brand comprises 7515. The brand SEBS has good ageing resistance and mechanical properties, can be processed and used without vulcanization, has good compatibility with 150N base oil, and can adjust the hardness through 150N base oil, so that the thermoplastic elastomer has a damping effect meeting the use requirement of an assembled floor. In addition, the segmented polypropylene A and the segmented polypropylene B with the melt index have better compatibility with SEBS with the brand 7511, and the blending effect is good.
Preferably, in the thermoplastic elastomer, the mass ratio of the block copolymerized polypropylene A to the block copolymerized polypropylene B is 1:2-1:3. By regulating the proportion of the block copolymerized polypropylene A and the block copolymerized 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 also better.
Preferably, in the thermoplastic elastomer, the mass ratio of the block copolymerized polypropylene A to the block copolymerized polypropylene B is 1:2.5. When the block copolymerized polypropylene A and the block copolymerized polypropylene B are compounded and used in the proportion, the thermoplastic elastomer has the best mechanical property and high and low temperature resistance.
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 be layered with the PP bottom layer, and improve the firmness of the integral 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 not only can play a role in lubrication, so that the product is easy to demould, but also can improve the surface wear resistance of the thermoplastic elastomer.
Preferably, the UV resistant auxiliary comprises at least one of EP-V701, KZ-1145. The UV-resistant auxiliary agent of the brand has good compatibility with the sizing material of the formula, and can improve the UV-resistant performance of the sizing material.
Preferably, the anti-soil additive comprises a fluorine modified anti-soil additive, under the trade designation blue Ke Lu lencoo 3007D. In the prior art, the auxiliary agent is generally used in the coating, however, the inventor has found unexpectedly 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, so that the anti-fouling capability of the product is improved.
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 SP179 and polypropylene with the trademark K9026. The study shows that the combination of SP179 polypropylene and K9026 polypropylene can improve the hardness and impact strength of hard rubber material, and can exert better supporting effect when applied to the bottom layer of 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 the SP179 polypropylene to the 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 hardness and the impact strength of the hard rubber material are improved remarkably.
Preferably, in the hard rubber 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 hard rubber material is most obvious.
Preferably, the filler A and the filler B are respectively composed of light calcium carbonate and heavy calcium carbonate, and the granularity 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 sizing material, can also increase the volume of the sizing material, and achieves the aim of reducing the cost. According to the research, 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 problem of small contact area with sizing material and poor blending effect can occur. The light calcium carbonate and the heavy calcium carbonate are compounded, and the dispersing 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 difficult to agglomerate, easy to disperse and good in blending effect with the sizing material is obtained, and finally the technical effects of improving the formability of the sizing material and increasing the volume of the sizing material are achieved.
Preferably, the compatibilizer a and the compatibilizer B each include at least one of styrene-butadiene-styrene block copolymer (SBS), 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 a thermoplastic elastomer
Mixing SEBS and 150N base oil uniformly, adding other components of a thermoplastic elastomer formula, mixing uniformly, extruding by a double-screw extruder, controlling the extrusion temperature to be 160-180 ℃, cooling, and granulating to obtain the thermoplastic elastomer;
step two, preparing hard rubber material
Uniformly mixing the components in the hard gum material formula, extruding by a double-screw extruder, controlling the extrusion temperature to be 180-200 ℃, cooling and granulating to obtain the hard gum material;
step three, preparing assembled floor
Uniformly mixing the thermoplastic elastomer and the color master batch according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material with a color masterbatch 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 placing the bottom layer into a mould, 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 primary 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, is formed by an integrally injection molded surface layer and a bottom layer, wherein the surface layer is made of thermoplastic elastomer with improved formula, and the bottom layer is made of hard rubber material with improved formula, so that the assembled floor has excellent shock absorption, pollution resistance and ageing 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 diagram of a double-layer structured assembled floor according to the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following 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 invention can be purchased commercially. Unless otherwise indicated, the methods used in the examples were all conventional in the art, and the equipment used was all conventional in the art.
The sources of the raw materials used in the examples are as follows:
examples 1 to 3
Examples 1 to 3 provide thermoplastic elastomers whose formulation compositions are shown in Table 1. Comparative examples 1 to 3 also provide thermoplastic elastomers whose formulation compositions are shown in Table 1.
In Table 1, polypropylene consisted of block copolymerized polypropylene A and block copolymerized polypropylene B, and the mass ratio of block copolymerized polypropylene A to block copolymerized polypropylene B was 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 thermoplastic elastomers of examples 1 to 3 were prepared by: (1) Uniformly mixing SEBS and 150N base oil, then adding other components, and uniformly mixing to obtain a mixed material; (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 twin-screw extruder is controlled between 160 and 180 ℃.
The method for producing the thermoplastic elastomer of comparative examples 1 to 3 is described in examples 1 to 3.
TABLE 1
Note that: in the table "-" indicates that the component was not added.
1. Performance testing of thermoplastic elastomers
The thermoplastic elastomers of examples 1 to 3 and comparative examples 1 to 3 were molded into sheets, cut into standard test pieces, and the test results are shown in Table 2.
Hardness: test methods are in accordance with ASTM D2240.
Tensile strength: test methods are in accordance with ASTM D412.
Elongation at break: test methods are in accordance with ASTM D412.
Compression set rate: the test method is carried out at 70 ℃ for 168 hours according to GB/T7759.1-2015, and the standard value is less than 50%.
Aging performance test: 158 ℃ x 168h.
Flame retardant performance test: vertical burn, tested according to GB/T2408-2008.
Embrittlement temperature measurement: the sample is arranged in a fixture in a cantilever mode, is placed in a low-temperature medium for constant temperature, and is impacted by a punch at a certain speed after reaching a certain preset low temperature, and the temperature when the destruction rate of the sample reaches 50% is the embrittlement temperature.
Abrasion resistance: taber abrasion resistance test, abrasion conditions: the H-18 grinding wheel, weight 2000g, revolution 1000r, revolution 72rpm, calculate the mass loss rate.
Stain resistance: the surface of the sample is smeared by an oil pen, the sample is put into a baking oven at 60 ℃ for drying (3 min), the sample is taken out and is wiped clean by wet paper towels, and the wiping times required by wiping each sample are counted.
TABLE 2
Table 2 analysis of results: the thermoplastic elastomers of examples 1 to 3 have good toughness, elasticity and mechanical strength, and are excellent in aging resistance, high and low temperature resistance, abrasion resistance, flame retardancy and stain resistance, and are particularly excellent in the performance of example 1. As can be seen from comparative analysis of comparative examples 1 to 2, the types of SEBS significantly affect the properties of thermoplastic elastomers, and comparative examples 1 and 2 using other grades of SEBS were inferior to example 1 in terms of aging resistance, high and low temperature resistance, abrasion resistance, flame retardancy, and stain resistance. Comparative analysis comparative example 3 shows that the fluorine modified anti-fouling additive of the brand adopted by the invention can effectively improve the anti-fouling capability of the thermoplastic elastomer.
2. To investigate the influence of the component composition and the component ratio of polypropylene on the performance of the thermoplastic elastomer, 7 groups of test groups were set, and the component composition and the component ratio of each group of polypropylene are shown in Table 3.
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 Polypropylene A
Test group 7 Block Polypropylene B
Thermoplastic elastomers (10 parts of polypropylene total) were prepared according to the formulation and preparation method of example 1 from test groups 1 to 7, and the properties of the thermoplastic elastomers were tested, and the test results are shown in Table 4.
TABLE 4 Table 4
Table 4 analysis of results: from test groups 1 to 5, it can be seen that the ratio of the block copolymerized polypropylene A to the block copolymerized polypropylene B can affect the mechanical property and the high and low temperature resistance of the thermoplastic elastomer, and when the mass ratio of the block copolymerized polypropylene A to the block copolymerized polypropylene B is 1 (2 to 3), the mechanical property and the high and low temperature resistance of the thermoplastic elastomer are better. When only the block copolymerized 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 meanwhile, the high and low temperature resistance and the wear resistance of the block copolymerized polypropylene A are also obviously reduced. When only the block copolymerized 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 meanwhile, the high-low temperature resistance and the wear resistance of the block copolymerized polypropylene B are also obviously reduced.
Examples 4 to 6
Examples 4-6 provide a hard gelatin material having a formulation shown in Table 5. Comparative examples 4 to 7 also provide a hard gelatin material having a formulation composition 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 the light calcium carbonate to the heavy calcium carbonate is 1:0.4.
The preparation method of the hard gum materials of examples 4 to 6 comprises the following steps: and (3) 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 twin-screw extruder is controlled to be 180-200 ℃.
The preparation methods of the hard rubber materials of comparative examples 4 to 7 are described with reference to examples 4 to 6.
TABLE 5
Note that: in the table "-" indicates that the component was not added.
3. Performance test of hard gum material
The hard rubber materials of examples 4 to 6 and comparative examples 4 to 7 were molded into sheets, cut into standard test pieces, and the test results are shown in Table 6.
Hardness: test methods are in accordance with ASTM D2240.
Impact strength: test method according to GB/T18943-2008
TABLE 6
Table 6 analysis of results: the hard rubber materials of examples 4 to 6 have a high hardness and a high impact strength, and are particularly excellent in the performance of example 1. As can be seen from a comparison of analytical example 4 and comparative examples 4 to 5, the ratio of SP179 to K9026 has an effect on the properties of the hard gelatin material. When the mass ratio of SP179 to K9026 is 0.8-1.2:0.8-1.2, the mechanical property of the hard rubber material is better. When the mass ratio of SP179 to K9026 is 1:1, the mechanical property of the hard rubber material is the best. Comparative analysis of comparative examples 6 to 7 shows that the hardness and impact strength of the hard gum material are significantly improved compared to the SP179 or K9026 alone or in combination with K9026.
Example 7
The assembled floor with the double-layer structure consists of a surface layer and a bottom layer, wherein the surface layer and the bottom layer are of an integrated injection molding structure, and the surface layer is prepared from the following components in parts by weight: 100 parts of the thermoplastic elastomer of example 1 and 0.8 part of a red masterbatch, the bottom layer being made of the following components in parts by weight: 100 parts of hard rubber material of example 4 and 1.5 parts of black matrix. The structure of the assembled floor can refer to fig. 1, and in actual production, a mold is involved according to the required shape.
The preparation method of the assembled floor comprises the following steps:
uniformly mixing a thermoplastic elastomer and a red masterbatch according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material and the black matrix 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, 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 mould, adding the first mixed material into an injection molding machine for secondary injection molding, 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 mould is 50 ℃, so that the assembled floor with the double-layer structure is obtained.
Example 8
The assembled floor with the double-layer structure consists of a surface layer and a bottom layer, wherein the surface layer and the bottom layer are of an integrated injection molding structure, and the surface layer is prepared from the following components in parts by weight: 100 parts of the thermoplastic elastomer of example 2 and 1 part of the red masterbatch, the bottom layer being made of the following components in parts by weight: 100 parts of the hard rubber material of example 5 and 2 parts of black matrix.
The preparation method of the assembled floor comprises the following steps:
uniformly mixing a thermoplastic elastomer and a red masterbatch according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material and the black matrix 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, 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 mould, adding the first mixed material into an injection molding machine for secondary injection molding, 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 mould 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 for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (8)

1. The assembled floor with the double-layer structure is characterized by comprising a surface layer and a bottom layer, wherein the surface layer and the bottom layer are of an integrated 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 masterbatch, 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 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 flexibilizer, 1-3 parts of compatibilizer A, 1.5-2.5 parts of lubricant, 8-12 parts of filler A, 0.1-0.2 part of anti-fouling additive and 0.15-0.25 part of anti-UV additive; the first polypropylene comprises block copolymerized polypropylene A and block copolymerized polypropylene B, wherein the melt index of the block copolymerized polypropylene A is 5-10 g/10min under the test condition of 2.16kg at 190 ℃, and the melt index of the block copolymerized polypropylene B is 20-30 g/10min under the test condition of 2.16kg at 190 ℃; the model of the SEBS is 7551; the mass ratio of the block copolymerized polypropylene A to the block copolymerized polypropylene B is 1:2-1:3;
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 SP179 and polypropylene with the trademark K9026, and the mass ratio of the SP179 polypropylene to the K9026 polypropylene is 0.8-1.2:0.8-1.2; the filler A and the filler B are respectively composed of light calcium carbonate and heavy calcium carbonate, and the mass ratio of the light calcium carbonate to the heavy calcium carbonate in the filler A and the filler B is 1:0.3-1:0.5.
2. The assembled floor of a double-layer structure as claimed in 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 additive and 0.2 part of anti-UV additive.
3. The assembled floor of a double-layer structure as claimed in 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.
4. The assembled floor of a double-layer structure according to claim 1, wherein the granularity of the heavy calcium carbonate is 600-800 meshes.
5. The assembled floor of double-layered structure according to claim 1, wherein the compatibilizer a and the compatibilizer B each comprise at least one of styrene-butadiene-styrene block copolymer, and maleic anhydride grafted SBS.
6. The engineered flooring of claim 1, wherein the toughening agent comprises POE3980 toughening agent, the lubricant comprises silicone powder, the UV resistant aid comprises at least one of EP-V701, KZ-1145, and the stain resistant aid comprises a fluorine modified stain resistant aid.
7. The double-layered assembled floor of claim 1, wherein the antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, and antioxidant 168.
8. A method for producing the double-layer structured assembled floor as claimed in any one of claims 1 to 7, comprising the steps of:
step one, preparing a thermoplastic elastomer
Uniformly mixing SEBS and 150N base oil, then adding other components of a thermoplastic elastomer formula, uniformly mixing, extruding by a double-screw extruder, controlling the extrusion temperature to be 160-180 ℃, cooling, and granulating to obtain the thermoplastic elastomer;
step two, preparing hard rubber material
Uniformly mixing the components in the hard gum material formula, extruding by a double-screw extruder, controlling the extrusion temperature to be 180-200 ℃, cooling and granulating to obtain the hard gum material;
step three, preparing assembled floor
Uniformly mixing the thermoplastic elastomer and the color master batch according to a formula to obtain a first mixed material;
uniformly mixing the hard rubber material with a color masterbatch 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;
placing the bottom layer into a mould, 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 an assembled floor with a double-layer structure;
the technological conditions of the primary 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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