CN111792876B - SPC stone plastic floor material and floor thereof - Google Patents
SPC stone plastic floor material and floor thereof Download PDFInfo
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- CN111792876B CN111792876B CN202010725836.3A CN202010725836A CN111792876B CN 111792876 B CN111792876 B CN 111792876B CN 202010725836 A CN202010725836 A CN 202010725836A CN 111792876 B CN111792876 B CN 111792876B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing halogen
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
- E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
- E04F15/105—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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/54—Pigments; Dyes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/60—Flooring materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/80—Optical properties, e.g. transparency or reflexibility
- C04B2111/82—Coloured materials
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed is an SPC stone plastic flooring material comprising: 100 parts by weight of PVC resin; 220-260 parts of heavy calcium carbonate; 40-80 parts of nano calcium carbonate; 2-4 parts of stearic acid; 8-12 parts of impact modifier; 4-8 parts of color master batch. Further, an SPC stone flooring layer and an SPC stone flooring comprising the flooring material are disclosed. The SPC stone plastic floor not only has better mechanical property, but also has lower size deformation rate.
Description
Technical Field
The invention belongs to the technical field of stone plastic floors; relates to an SPC stone plastic floor material and a floor thereof.
Background
SPC floors, also known as stone-plastic floors. The main components of SPC stone-plastic floor are PVC (polyvinyl chloride) and marble powder. The SPC stone plastic floor is green and environment-friendly, is usually installed in a locking manner, does not use an adhesive containing formaldehyde, is nontoxic and harmless, has no radioactive pollution and no pollution to the environment, belongs to a green and environment-friendly product, and can be recycled. The SPC stone plastic floor has a special transparent wear-resistant layer processed by high technology on the surface, has super-strong wear resistance, and is more and more popular among people in hospitals, markets, high-speed railway stations and other places with large pedestrian volume. In addition, the SPC stone plastic floor is waterproof and moistureproof and does not deform when meeting water; meanwhile, the flame retardant cable is insulating, flame retardant, resistant to acid and alkali corrosion and high in safety.
The SPC stone-plastic floor has novel design and color, multiple designs and colors can be selected, the color is gorgeous, natural and vivid, the design and color can be randomly spliced and combined, and the individual color is highlighted. In order to give different designs and colors to the floor, color concentrates with different properties are generally selected. The color master batch has good compatibility with an SPC floor material mainly comprising PVC resin and heavy calcium carbonate powder, and auxiliary agents such as a dispersing agent, a compatilizer and the like are usually required to be added.
Zhang Cai et al (plastics science and technology, 2019, 47(7), 111) disclose a wood-plastic composite comprising sisal cellulose crystallites MCF and a non-polar resin PP. In order to improve the interface bonding strength of the composite material, an RA-g-PEPA hyperdispersant modified by abietic acid is used. The results show that: the impact strength of the PP/MCF wood-plastic composite material can reach 16.8kJ/m at most2And shows better mechanical property and processing flow property. Microscopic morphology analysis shows that after the RA-g-PEPA hyperdispersant is added, the interfacial adhesion force of MCF and PP resin is enhanced, and the fracture mode of the wood-plastic composite material is changed. The above documents do not describe whether the hyperdispersant can be applied to PVC resins.
In the prior art, the mechanical properties and dimensional deformation rate of the resulting SPC stone-plastic flooring are still unsatisfactory due to the unfavorable interface between the PVC resin and the triple superphosphate powder.
Therefore, there is still a need to provide an SPC stone plastic flooring and flooring thereof, which address the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The invention aims to provide an SPC stone plastic floor material and a floor thereof. Compared with the prior art, the SPC stone plastic floor not only has better mechanical property, but also has lower dimensional deformation rate.
In order to solve the technical problems, on one hand, the invention adopts the following technical scheme: an SPC stone-plastic flooring material comprising:
100 parts by weight of PVC resin;
220-260 parts of heavy calcium carbonate;
40-80 parts of nano calcium carbonate;
2-4 parts of stearic acid;
8-12 parts of impact modifier;
4-8 parts of color master batch;
it is characterized in that the preparation method is characterized in that,
the color master batch is prepared from the raw materials of PVC resin, EVA wax, C.I. pigment yellow 139, a composite dispersant and optional other additives; wherein the composite dispersant is selected from acrylpimaric acid grafted poly- (12-hydroxystearic acid) and lauric acid diethanolamide.
The SPC stone-plastic flooring material according to the present invention, wherein the PVC resin is selected from PVC resins produced by a suspension process, and the average degree of polymerization is 1000-1150.
In a specific embodiment, the PVC resin is selected from the group consisting of PVC SG-5 resin (Shandong dynasty group; average degree of polymerization 1050; CAS: 93050-82-9).
The SPC stone plastic flooring material provided by the invention is characterized in that the particle size of the heavy calcium carbonate is 300-500 meshes.
The SPC stone-plastic floor material provided by the invention is characterized in that the average particle size of the nano calcium carbonate is 15-40 nm; the specific surface area is more than or equal to 40m2/g。
The SPC stone flooring according to the present invention, wherein the impact modifier is selected from acrylate copolymers.
In a specific embodiment, the impact modifier is selected from the group consisting of ACR KM-355P (Rohm and Haas, USA).
The SPC stone flooring material according to the present invention, wherein the EVA wax is selected from EVA waxes having a weight average molecular weight of 9300 and a VA content of 13-15%.
In a specific embodiment, the EVA wax is selected from Luwax EVA3 (BASF; CAS number: 111-46-6).
The SPC stone plastic flooring material provided by the invention is characterized in that the weight ratio of the acrylpimaric acid grafted poly- (12-hydroxystearic acid) to the lauric acid diethanolamide (3-4) is 1.
In the present invention, acrylpimaric acid-grafted poly- (12-hydroxystearic acid) was synthesized and characterized according to Zhang Cai et al (plastics science, 2019, 47(7), 111).
In the present invention, other auxiliaries may be mentioned: antioxidants, ultraviolet absorbers, flame retardants, calcium stearate; and so on.
In a specific embodiment, the adjuvant is selected from the group consisting of antioxidant 1010 and calcium stearate.
The color concentrates of the present invention are prepared according to conventional techniques in the art.
In a specific embodiment, according to the formula, the PVC resin, the EVA wax, the composite dispersant and optional other additives are added into a high-speed mixer and stirred and mixed; then adding C.I. pigment yellow 139, and stirring uniformly; and adding the materials into a double-screw extruder for melting, plasticizing and granulating.
The SPC stone plastic flooring material of the present invention comprises, in the color master batch raw material, PVC resin, EVA wax, C.I. pigment yellow 139, composite dispersant and optionally other additives in a weight ratio of (30-50): 4-6): 40-60: (4-5): 0-5.
In another aspect, the present invention also provides an SPC stone-plastic floor layer, characterized in that the floor layer comprises the aforementioned SPC stone-plastic floor material according to the present invention.
Finally, the invention further provides an SPC stone floor, characterized in that the floor comprises an aforementioned SPC stone floor layer according to the invention.
The inventor finds that the color master batch prepared by using the composite dispersing agent disclosed by the invention is beneficial to improving the adverse interface effect of PVC resin and coarse whiting powder together with nano calcium carbonate under the condition of not using other dispersing agents, and the obtained SPC stone plastic floor not only has better mechanical property, but also has lower size deformation rate.
Detailed Description
The invention will be further illustrated with reference to specific embodiments.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
In the present invention, all parts are parts by weight unless otherwise specified.
In the present invention, the acrylic pimaric acid grafted poly- (12-hydroxystearic acid) is prepared as follows: heating 30 parts by weight of abietic acid to 230 ℃ under the protection of nitrogen, and dropwise adding 8.58 parts by weight of acrylic acid solution; after the dropwise addition, the reaction is continued for 2 hours, and the reaction solution is naturally cooled to 200 ℃. Acid-base titration is used for measuring the acid value, and the acid value reaches about 275mgKOH/g, namely the acrylpimaric acid. Heating 30 parts by weight of 12-hydroxystearic acid to 100 ℃ under the protection of nitrogen, adding 0.375 part by weight of p-toluenesulfonic acid as a catalyst after complete melting, heating to 130 ℃, carrying out heat preservation reaction for 6 hours, cooling and discharging, and drying at 60 ℃ for 10 hours to obtain the poly- (12-hydroxystearic acid). Heating 12.36 parts by weight of acrylpimaric acid and 167.24 parts by weight of poly- (12-hydroxystearic acid) to 130 ℃, preserving heat for reaction for 10 hours, cooling and discharging to obtain the product.
In the present invention, the mechanical properties are evaluated by tensile strength. Tensile strength was measured according to ASTM 638-.
In the present invention, the dimensional deformation ratio is performed according to the industry common practice. The SPC stone-plastic flooring was left at 60 ℃ for 6 hours, and the dimensional deformation ratios (%) in the longitudinal direction and the width direction were measured.
Example 1
The formula of the color master batch comprises the following components:
40 parts of PVC SG-5 resin;
5 parts of BASF Luwax EVA3 wax;
13948 parts of pigment yellow;
3.5 parts of acrylic pimaric acid grafted poly- (12-hydroxystearic acid);
1 part of lauric acid diethanolamide;
10101 parts of antioxidant;
1.5 parts of calcium stearate;
according to the formula, the PVC resin, the EVA wax, the composite dispersant and other additives are added into a high-speed mixer and stirred and mixed; adding C.I. pigment yellow 139, and stirring uniformly; adding the materials into a double-screw extruder for melting, plasticizing and granulating; the temperatures of the first zone to the fifth zone of the double-screw extruder are respectively 170 ℃, 175 ℃ and 180 ℃; the rotating speed of the main machine is 100 rpm; the feeding speed is 20 rpm; the melt pressure was 2 MPa.
Example 2
The formula of the SPC stone plastic floor material comprises the following components:
100 parts by weight of PVC SG-5 resin;
240 parts of 400-mesh heavy calcium carbonate;
nano calcium carbonate (average grain diameter is 15-40 nm; specific surface area is greater than or equal to 40 m)2Per gram) 60 parts by weight;
3 parts of stearic acid;
10 parts of ACR KM-355P;
color masterbatch of example 16 parts by weight.
According to the formula, firstly, adding the color master batch and the nano calcium carbonate into a high-speed mixer, and stirring and mixing; then adding heavy calcium carbonate, stirring and mixing; finally, adding PVC SG-5 resin stearic acid and ACR KM-355P, and stirring the mixture evenly under the heating condition; adding the materials into a double-screw extruder for melting and plasticizing; the temperatures of the first zone to the fifth zone of the double-screw extruder are 190 ℃, 195 ℃, 200 ℃ and 200 ℃ respectively; the rotating speed of the main machine is 120 rpm; the feeding speed is 30 rpm; the melt pressure was 1.5 MPa. And finally, inputting the plasticized material into a mold while the plasticized material is hot, and performing extrusion molding to obtain the SPC stone-plastic floor layer.
Using a four-roller calender to shape the SPC stone-plastic floor layer, wherein the thickness is 1 mm; and then adhering a color film and a wear-resistant layer, cooling and cutting edges to obtain the SPC stone plastic floor.
Comparative example 1
In the same manner as in example 2, the acrylic pimaric acid grafted poly- (12-hydroxystearic acid) was replaced by lauric acid diethanolamide.
Comparative example 2
In the same manner as in example 2, lauric acid diethanolamide was replaced by acrylic pimaric acid grafted poly- (12-hydroxystearic acid).
Comparative example 3
In the same manner as in example 2, the acrylic pimaric acid grafted poly- (12-hydroxystearic acid) was replaced by abietic acid.
Performance testing
The tensile strength and dimensional deformation rate of the SPC stone flooring of example 2 and comparative examples 1 to 3 were measured according to the aforementioned methods. See table 1 for results.
TABLE 1
As can be seen from Table 1, the SPC stone-plastic flooring of example 2 of the present invention has not only better mechanical properties (tensile strength ≥ 39MPa) but also lower dimensional deformation (≤ 0.05%) than those of comparative examples 1-3.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. An SPC stone-plastic flooring material comprising:
100 parts by weight of PVC resin;
220-260 parts of heavy calcium carbonate;
40-80 parts of nano calcium carbonate;
2-4 parts of stearic acid;
8-12 parts of impact modifier;
4-8 parts of color master batch;
it is characterized in that the preparation method is characterized in that,
the raw materials of the color master batch comprise PVC resin, EVA wax, C.I. pigment yellow 139, a composite dispersant and optionally other additives; wherein the composite dispersant is selected from acrylpimaric acid grafted poly- (12-hydroxystearic acid) and lauric acid diethanolamide;
the PVC resin is selected from PVC resin produced by a suspension method, and the average degree of polymerization is 1000-1150;
the weight ratio of the acrylpimaric acid grafted poly- (12-hydroxystearic acid) to the lauric acid diethanolamide (3-4) is 1;
in the color master batch raw material, the weight ratio of PVC resin, EVA wax, C.I. pigment yellow 139, composite dispersant and optional other auxiliary agents is (30-50): 4-6): 40-60: (4-5): 0-5.
2. The SPC stone-plastic flooring material as claimed in claim 1, wherein the particle size of the heavy calcium carbonate is 300-500 mesh.
3. The SPC stone flooring material according to claim 1, wherein the nano calcium carbonate has an average particle size of 15 to 40 nm; the specific surface area is more than or equal to 40m2/g。
4. An SPC stone flooring material according to claim 1, wherein the impact modifier is selected from acrylate copolymers.
5. An SPC stone flooring material according to claim 1, wherein the EVA wax is selected from EVA waxes having a weight average molecular weight of 9300 and a VA content of 13-15%.
6. An SPC stone flooring layer, wherein the flooring layer comprises the SPC stone flooring material according to any one of claims 1 to 5.
7. An SPC stone-plastic flooring, characterized in that the flooring comprises an SPC stone-plastic flooring layer according to claim 6.
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| CN202010725836.3A CN111792876B (en) | 2020-07-24 | 2020-07-24 | SPC stone plastic floor material and floor thereof |
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| CN202010725836.3A CN111792876B (en) | 2020-07-24 | 2020-07-24 | SPC stone plastic floor material and floor thereof |
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| WO2022143913A1 (en) * | 2020-12-31 | 2022-07-07 | 浙江永裕家居股份有限公司 | Multi-layer co-extruded stone plastic floor and manufacturing method therefor |
| CN113150466A (en) * | 2021-04-22 | 2021-07-23 | 苏州美诺护新材料科技研发有限公司 | SPC floor |
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| CN103483717A (en) * | 2013-08-22 | 2014-01-01 | 金发科技股份有限公司 | Wood-grain-like color master batch, and preparation method and application thereof |
| CN109294157A (en) * | 2018-09-28 | 2019-02-01 | 青岛摩岩新材料科技有限公司 | A kind of stone modeling SPC composite floor board and preparation method thereof |
| CN111635602A (en) * | 2020-07-23 | 2020-09-08 | 山东诺森塑胶有限公司 | Color master batch with high heat resistance and dispersibility |
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| JP4438998B2 (en) * | 2004-11-24 | 2010-03-24 | ダイワボウホールディングス株式会社 | Thermal adhesive composite fiber, fiber structure using the same, and heterogeneous object composite molded body |
| DE102010011191A1 (en) * | 2010-03-11 | 2011-09-15 | Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg | Stabilizer mixtures for halogenated plastics by underwater granulation |
| CN106496875B (en) * | 2016-11-21 | 2019-01-25 | 广西华纳新材料科技有限公司 | A kind of PVC wood plastic foamed material and preparation method thereof |
| CN108192235A (en) * | 2017-12-26 | 2018-06-22 | 上海邦中高分子材料有限公司 | A kind of PVC hose special color master batch and preparation method thereof |
| CN109057241B (en) * | 2018-08-06 | 2020-06-16 | 安徽扬子地板股份有限公司 | Stone-plastic floor and preparation method thereof |
| US11633339B2 (en) * | 2018-09-07 | 2023-04-25 | L'oreal | Cleansing compositions free of sodium chloride and sulfate-based surfactants |
| CN109535599A (en) * | 2018-11-29 | 2019-03-29 | 安徽可尔海思塑业有限公司 | A kind of PVC stone plastic floor and preparation method thereof |
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|---|---|---|---|---|
| CN103483717A (en) * | 2013-08-22 | 2014-01-01 | 金发科技股份有限公司 | Wood-grain-like color master batch, and preparation method and application thereof |
| CN109294157A (en) * | 2018-09-28 | 2019-02-01 | 青岛摩岩新材料科技有限公司 | A kind of stone modeling SPC composite floor board and preparation method thereof |
| CN111635602A (en) * | 2020-07-23 | 2020-09-08 | 山东诺森塑胶有限公司 | Color master batch with high heat resistance and dispersibility |
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