CN111873592B - Degradable floor and preparation method thereof - Google Patents

Degradable floor and preparation method thereof Download PDF

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Publication number
CN111873592B
CN111873592B CN202010737426.0A CN202010737426A CN111873592B CN 111873592 B CN111873592 B CN 111873592B CN 202010737426 A CN202010737426 A CN 202010737426A CN 111873592 B CN111873592 B CN 111873592B
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China
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parts
layer
weight
roller
temperature
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CN111873592A (en
Inventor
韦余康
李进
倪清兰
董玉娇
陆伟
鲍晨
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Digaoli Decoration Materials Jiangsu Co ltd
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Digaoli Decoration Materials Jiangsu Co ltd
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Abstract

The invention belongs to the technical field of floors, and particularly relates to a degradable floor and a preparation method thereof. The invention provides a degradable floor, which sequentially comprises a surface layer, a density board and a first bottom layer from top to bottom; the skin layer sequentially comprises a TPU wear-resistant layer, a decorative layer and a second bottom layer from top to bottom, wherein the second bottom layer is in contact with the density board. The wear-resistant layer and the bottom layer of the degradable floor are both prepared by degradable TPU (thermoplastic polyurethane), the main component of the density board is wood fiber, and the degradable part of the whole floor accounts for 95-100%; the degradable floor has good fireproof performance.

Description

Degradable floor and preparation method thereof
Technical Field
The invention belongs to the technical field of floors, and particularly relates to a degradable floor and a preparation method thereof.
Background
At present, two main types of wood floors and PVC plastic floors are mainly used in the floor industry, wherein the PVC plastic floor is a novel light floor decoration material which is very popular in the world at present and is also called as a light floor material. The beverage is a widely popular product in the European, American and Asia in the Japanese and Korean, is popular abroad, enters the Chinese market from the beginning of the 80 s, is generally accepted in domestic large and medium cities so far, and is widely used. However, since PVC contains a large amount of chlorine, hydrochloric acid and other toxic gases are released from the floor in the combustion process, which affects the health safety of people, and PVC is a non-degradable plastic, which also provides a great challenge to the environmental problems which people pay more attention to, therefore, research on a novel material to replace PVC to prepare the elastic environment-friendly floor meets the requirements of the current market.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a degradable floor comprising, in order from top to bottom, a skin layer, a density board, a first backsheet layer; the skin layer sequentially comprises a TPU wear-resistant layer, a decorative layer and a second bottom layer from top to bottom, wherein the second bottom layer is in contact with the density board.
As a preferred technical scheme, the preparation raw materials of the TPU wear-resistant layer and the second backsheet layer both comprise, by weight: 100 parts of TPU resin, 2-25 parts of plasticizer, 1-10 parts of soybean oil and 1.5-3.5 parts of heat stabilizer; the first bottom layer is a TPU layer or a foaming layer; the foaming layer is made of one of IXPE, PS, EVA, PU, PP, PO and rubber. As a preferable technical scheme, the TPU wear-resistant layer is prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 2-5 parts of plasticizer, 1-5 parts of soybean oil, 1.5-3.5 parts of heat stabilizer, 0.5-1 part of acrylate monomer and 0.2-0.3 part of ultraviolet absorbent.
As a preferable technical scheme, the first bottom sheet layer and the second bottom sheet layer are made of the same raw materials and respectively comprise 100 parts by weight of TPU resin, 20-25 parts by weight of plasticizer, 5-10 parts by weight of soybean oil, 1.5-3.5 parts by weight of heat stabilizer, 480 parts by weight of stone powder 350-containing materials, 5-10 parts by weight of carbon black and 5-7 parts by weight of lubricant.
As a preferable technical scheme, the density board is one selected from fiber density boards, glass magnesium boards and calcium silicate fiber boards.
As a preferable technical scheme, the raw materials for preparing the fiber density board comprise, by weight, 30-40 parts of crop straws, 40-45 parts of wood leftover materials, 2-5 parts of inorganic alkali, 7-15 parts of magnesium-containing compounds and 10-15 parts of adhesives.
As a preferable technical scheme, the glass magnesium board comprises the following raw materials in parts by weight: 100-120 parts of light-burned magnesium oxide, 1-4 parts of magnesium sulfate heptahydrate, 0-25 parts of magnesium chloride, 4-10 parts of perlite, 2-5 parts of talcum powder, 1-5 parts of montmorillonite, 2-9 parts of KH550, 10-30 parts of wood fiber and water, wherein: the water-cement ratio is 0.2-0.5.
As a preferred technical scheme, the calcium silicate fiber board comprises the following raw materials in parts by weight: 20-30 parts of slaked lime, 21-23 parts of diatomite, 10-20 parts of coal ash, 4.5-5.5 parts of silica fume, 2-5 parts of bentonite, 5-10 parts of plant fiber, 2-5 parts of filler and water, wherein: the water-cement ratio is 0.2-0.5.
The second aspect of the present invention provides a method for preparing the degradable floor, comprising the following steps:
(1) carrying out UV heat treatment on the surface layer;
(2) attaching the skin layer subjected to UV heat treatment to the surface of the density plate through a first adhesive to obtain a semi-finished product;
(3) stacking the semi-finished product on a tray, and slotting by a multi-blade saw according to the specification requirement;
(4) and (3) sticking the first bottom layer to the back of the density board through a second adhesive to obtain the degradable floor.
As a preferred technical solution, the thickness of the skin layer is 0.5-1.5 mm; the thickness of the density plate is 3-12 mm; the thickness of the first backsheet layer is 0.5-1.5 mm.
Has the beneficial effects that: the wear-resistant layer and the bottom layer of the degradable floor are both prepared by degradable TPU (thermoplastic polyurethane), the main component of the density board is wood fiber, and the degradable part of the whole floor accounts for 95-100%; the degradable floor has good fireproof performance, is suitable for various places such as indoor places, outdoor places and the like, and has good application prospect.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the problems, the invention provides a degradable floor which comprises a skin layer, a density board and a first bottom layer from top to bottom.
The skin layer sequentially comprises a TPU wear-resistant layer, a decorative layer and a second bottom sheet layer from top to bottom, wherein the second bottom sheet layer is in contact with the density board.
The TPU wear-resistant layer and the second bottom layer are prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 2-25 parts of plasticizer, 1-10 parts of soybean oil and 1.5-3.5 parts of heat stabilizer; the first bottom layer is a TPU layer or a foaming layer; the foaming layer is made of one of IXPE, PS, EVA, PU, PP, PO and rubber. When the first bottom sheet layer is a TPU layer, the preparation raw materials of the TPU wear-resistant layer, the first bottom sheet layer and the second bottom sheet layer respectively comprise the following components in parts by weight: 100 parts of TPU resin, 2-25 parts of plasticizer, 1-10 parts of soybean oil and 1.5-3.5 parts of heat stabilizer.
The TPU resin is thermoplastic polyurethane resin; the TPU resins of the TPU abrasion resistant layer, the first backsheet layer and the second backsheet layer are all commercially available products, and the purchase manufacturers are not particularly limited, for example, the leri plastic co.
The plasticizer of the TPU abrasion resistant layer, first backsheet layer and second backsheet layer is not particularly limited as long as it can increase the plasticity of the TPU resin, such as dioctyl terephthalate (DOTP).
Preferably, the soybean oil is epoxidized soybean oil.
The epoxidized soybean oil is composed of a plurality of fatty acids: epoxy linoleate (51-57%), epoxy oleate (32-36%), epoxy palmitate (2.4-6.8%), and the like.
Preferably, the heat stabilizer of the TPU wear layer, the first backsheet layer and the second backsheet layer each comprises at least one of a calcium-zinc composite heat stabilizer, an organotin stabilizer and a lead stabilizer; on the premise of meeting different requirements, different heat stabilizers can be selected; for example, for environmental protection, environmentally friendly heat stabilizers may be used.
Further preferably, the preparation raw materials of the TPU wear-resistant layer comprise, by weight: 100 parts of TPU resin, 2-5 parts of plasticizer, 1-5 parts of soybean oil, 1.5-3.5 parts of heat stabilizer, 0.5-1 part of acrylate monomer and 0.2-0.3 part of ultraviolet absorbent.
Preferably, the acrylate monomer comprises at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-butyl octyl methacrylate, hexyl methacrylate, octyl methacrylate and 2-ethyl acrylate. And the acrylic ester monomer is added, so that the material is easier to discharge in the preparation process.
The ultraviolet absorbent is at least one selected from ultraviolet absorbent UV-P, ultraviolet absorbent UV-O, ultraviolet absorbent UV-9, ultraviolet absorbent UV-531, ultraviolet absorbent UVP-327, ultraviolet absorbent RMB, light stabilizer AM-101 and light stabilizer 744; the ultraviolet absorber UV-531 is preferred.
The preparation method of the TPU wear-resistant layer comprises the following steps: the raw materials are fed into a mixing machine for mixing, then an extruder is used for plasticizing, the plasticizing temperature is controlled to be 110-170 ℃, a filter is used for filtering, the filtering temperature is 110-170 ℃, the materials are rolled and molded by a five-roller rolling machine, the temperature of a No. 1 roller of the five-roller rolling machine is 110-165 ℃, the temperature of a No. 2 roller of the five-roller rolling machine is 105-160 ℃, the temperature of a No. 4 roller of the five-roller rolling machine is 100-155 ℃, the temperature of a No. 5 roller of the five-roller rolling machine is 100-155 ℃, and cooling and winding are carried out.
Preferably, the preparation method of the TPU wear-resistant layer comprises the following steps: the raw materials are fed into a mixing machine for mixing, then an extruder is used for plasticizing, the plasticizing temperature is controlled to be 110-fold-120 ℃, a filter is used for filtering, the filtering temperature is 110-fold-120 ℃, the materials are subjected to calendaring molding by a five-roller calendar, the temperature of a No. 1 roller of the five-roller calendar is 110-fold-130 ℃, the temperature of a No. 2 roller is 110-fold-115 ℃, the temperature of a No. 3 roller is 105-fold-110 ℃, the temperature of a No. 4 roller is 100-fold-105 ℃, and the temperature of a No. 5 roller is 100-fold-105 ℃, and cooling and winding are carried out.
Further preferably, when the first bottom layer is a TPU layer, the first bottom layer and the second bottom layer are prepared from the same raw materials, and comprise 100 parts by weight of TPU resin, 20-25 parts by weight of plasticizer, 5-10 parts by weight of soybean oil, 1.5-3.5 parts by weight of heat stabilizer, 480 parts by weight of stone powder 350-.
The lubricant is at least one selected from stearic acid, calcium stearate and zinc stearate.
The stone powder comprises at least one of medical stone powder, triple superphosphate powder, talcum powder, dolomite powder and putty powder.
When the first bottom film layer is a TPU layer, the preparation methods of the first bottom film layer and the second bottom film layer are the same, and the preparation method comprises the following steps: the raw materials are fed into a mixing machine to be mixed, then an internal mixer is used for plasticizing, the plasticizing temperature is controlled to be 130-plus-200 ℃, the mixture is subjected to calendering molding through a four-roller calender, the temperature of a roller 1 of the four-roller calender is 130-plus-195 ℃, the temperature of a roller 2 of the four-roller calender is 130-plus-195 ℃, the temperature of a roller 3 is 120-plus-180 ℃, and the temperature of a roller 4 is 115-plus-170 ℃, and the mixture is cooled and cut to obtain the substrate layer.
Preferably, the first and second backsheet layers are prepared in the same manner, including the steps of: the raw materials are fed into a mixing machine to be mixed, then an internal mixer is used for plasticizing, the plasticizing temperature is controlled to be 130-fold-150 ℃, the mixture is subjected to calendering molding through a four-roller calender, the temperature of a roller 1 of the four-roller calender is 130-fold-145 ℃, the temperature of a roller 2 of the four-roller calender is 130-fold-145 ℃, the temperature of a roller 3 is 120-fold-130 ℃, and the temperature of a roller 4 is 115-fold-120 ℃, and the mixture is cooled and cut to obtain the substrate layer.
With the enhancement of environmental awareness of people, the degradable floor becomes one of the hot spots of research, the application adopts the density board made of TPU resin and straw crops to replace PVC resin to make the degradable floor, is safe and environment-friendly, and can be naturally oxidized and degraded along with time after being buried in soil; but because the degradable floor contains thermoplastic linear structures with different degrees, the floor becomes difficult to use at higher temperature, the TPU wear-resistant layer is calendered and formed by a five-roller calender, and the first bottom sheet layer and the second bottom sheet layer are calendered and formed by a four-roller calender; then forming the degradable floor with the density board, wherein the thermal expansion coefficient is far smaller than that of the traditional SPC; presumably, through specific procedures, some groups in the TPU wear layer, the first backsheet layer and the second backsheet layer are oriented towards a specific direction, so that the order of chain segments is increased, the acting force among molecular chain segments in the resin is enhanced, and the TPU wear layer, the first backsheet layer and the second backsheet layer are not easy to expand when heated.
The foaming layer is made of one of IXPE, PS, EVA, PU, PP, PO and rubber. The foaming layer can be made by a user or purchased; the foaming layer is prepared by reacting one of IXPE, PS, EVA, PU, PP, PO and rubber with a foaming agent and a filler; the blowing agent is not particularly limited and is a blowing agent commonly used in the art.
Wherein IXPE refers to a crosslinked polyethylene foam material, and is a foam plastic with excellent performance. For example, the foaming agent is prepared by using low-density polyethylene as a main material, bridging through a crosslinking agent and foaming through an azo type foaming agent. The IXPE layer has closed and independent foam pores, does not absorb water, is environment-friendly, flame retardant, insulating, moisture-proof, shock-absorbing, buffering, rebounding, heat-insulating, weather-resistant, ageing-resistant, chemical-resistant, light in weight, easy to machine and form and pollution-free.
The PE has light weight, high chemical stability, good impact resistance and good insulativity, and can not be rusted; fireproof and moistureproof, and low water absorption; the PS has good surface gloss, high hardness, good rigidity, and good water resistance and chemical resistance. The EVA is light in weight, wear-resistant and shock-resistant; the PP layer has the advantages of sound insulation, moisture resistance, wear resistance, long service life and the like. The PO has the advantages of sound insulation, good chemical stability, corrosion resistance and the like. The rubber can be natural rubber or synthetic rubber; has the advantages of good buffering, shock resistance, heat insulation, moisture resistance and the like. A skin layer is obtained by laminating the TPU wear-resistant layer, the decorative layer and the second substrate layer in sequence, and the preparation method of the skin layer is not particularly limited and can be prepared by the method I; the first method comprises the following steps: stacking the TPU wear-resistant layer, the decorative layer and the second bottom sheet; pushing the laminated material into a press after the material stacking is finished, wherein the hot pressing temperature is 120-150 ℃, the hot pressing time is 20-40min, the cold pressing temperature is lower than 40 ℃, the cold pressing time is 20-40min, and discharging to obtain a skin layer; the decorative layer is a color film.
Can also be prepared by the method two; the second method comprises the following steps: the second bottom layer is attached to the decorative layer through a hot roller at the temperature of 100-120 ℃ at the speed of 10-15 m/min; after the second bottom layer is attached to the decorative layer, the TPU wear-resistant layer is attached to the surface of the decorative layer through a hot roller at the temperature of 105-125 ℃ and at the speed of 10-15 m/min; obtaining a surface layer; the bonded surface skin can also be embossed at the bonding temperature of 100-120 ℃ and at the speed of 10-15 m/min.
The density board is selected from one of fiber density board, glass magnesium board and calcium silicate fiber board.
The components of the glass magnesium board comprise active high-purity magnesium oxide, high-quality magnesium chloride, alkali-resistant glass fiber cloth, plant fiber, non-combustible light perlite, chemically stable lithopone, high polymer and high-performance modifier. The glass magnesium board has the advantages of high temperature resistance, flame retardance, sound absorption, shock resistance, insect prevention, corrosion resistance, no toxicity, no odor, no pollution, capability of being directly painted and veneered, capability of being directly nailed by air and directly plastered by tiles, better colorability on the surface, high strength, bending resistance, toughness, nailability, sawability, adhesivity and convenience in decoration.
The glass magnesium board comprises the following raw materials in parts by weight: 100-120 parts of light-burned magnesium oxide, 1-4 parts of magnesium sulfate heptahydrate, 0-25 parts of magnesium chloride, 4-10 parts of perlite, 2-5 parts of talcum powder, 1-5 parts of montmorillonite, 2-9 parts of KH550, 10-30 parts of wood fiber and water, wherein: the water-cement ratio is 0.2-0.5.
The calcium silicate fiber board is a board prepared by taking loose short fibers such as inorganic mineral fibers or cellulose fibers and the like as reinforcing materials and taking siliceous-calcareous materials as main body cementing materials, pulping, forming and accelerating a curing reaction in high-temperature high-pressure saturated steam to form calcium silicate gel. The product is fireproof, moistureproof, soundproof, mothproof and durable, and is an ideal decorative plate for suspended ceilings and partitions.
The calcium silicate fiberboard comprises the following raw materials in parts by weight: 20-30 parts of slaked lime, 21-23 parts of diatomite, 10-20 parts of coal ash, 4.5-5.5 parts of silica fume, 2-5 parts of bentonite, 5-10 parts of plant fiber, 2-5 parts of filler and water, wherein: the water-cement ratio is 0.2-0.5.
Wherein the filler includes, but is not limited to, kaolin.
The preparation method of the glass magnesium board and the calcium silicate fiber board is not particularly limited, and is a preparation method commonly used in the field.
Preferably, the raw materials for preparing the fiber density board comprise, by weight, 30-40 parts of crop straws, 40-45 parts of wood leftover materials, 2-5 parts of inorganic alkali, 7-15 parts of magnesium-containing compounds and 10-15 parts of adhesives;
the crop straw is selected from at least one of wheat straw, rice straw, corn straw, potato straw, rape straw, cotton straw and sugarcane straw; the crop straw in this application is not particularly limited;
the wood leftover materials are leftover materials generated in the processing process of a wood factory, a furniture factory and a floor factory, and are not particularly limited;
the inorganic base is at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate; preferably, the inorganic base is sodium hydroxide and sodium bicarbonate; the weight ratio of the sodium hydroxide to the sodium bicarbonate is 1-3: 1.
Further preferably, before the density board is prepared, the sodium hydroxide is prepared into a sodium hydroxide aqueous solution with a mass concentration of 1-5%.
The magnesium-containing compound comprises at least one of magnesium oxide, magnesium hydroxide, magnesium sulfate and magnesium sulfate heptahydrate. Preferably, the magnesium-containing compound comprises magnesium oxide and magnesium sulfate; the weight ratio of the magnesium oxide to the magnesium sulfate is 1: 1-5; preferably, the weight ratio of the magnesium oxide to the magnesium sulfate is 1: 1-3.
The adhesive is pre-gelatinized starch and/or a ball pressing adhesive. The viscosity of the pre-gelatinized starch is 300-800mPa & s; preferably, the viscosity of the pregelatinized starch is 500mPa · s, wherein the viscosity refers to the viscosity at 23 ℃. The pregelatinized starch can be made by self or purchased, and the method and the manufacturer are not particularly limited.
The preparation method of the density board comprises the following steps: adding crop straws, wood leftover materials, magnesium-containing compounds and sodium bicarbonate into a sodium hydroxide aqueous solution, heating to 90-110 ℃, soaking for 2-4h, and filtering to obtain a mixture 1; and (3) transferring the adhesive and the mixture 1 into a high-speed mixer, uniformly mixing, standing for 4-6h, transferring into a plate extrusion device, and carrying out extrusion molding to obtain the density plate. Preferably, the temperature of each section in the extrusion equipment is 140-150 ℃, 150-160 ℃, 160-170 ℃ and 170-180 ℃ respectively.
In order to improve the fireproof performance of the degradable floor, flame retardants such as magnesium hydroxide are often required to be added, but the magnesium hydroxide flame retardant needs a large filling amount (generally 50%), and the mechanical performance of the product is reduced; according to research, a certain amount of magnesium oxide, magnesium sulfate, sodium hydroxide and sodium bicarbonate are added in the process of preparing the density board, so that the smoke density of the prepared degradable floor without smoke combustion is less than 260; the bending strength was increased, and it is presumed that: in the process of preparing the density board, active components such as magnesium hydroxide, magnesium sulfate whiskers and the like which are uniformly distributed and interact with crop straws are generated, so that on one hand, external energy can be absorbed, the stress value of cracks can be increased, the dissipation of energy can be accelerated, and the extension of the cracks can be inhibited; on the other hand, the MgO layer formed by burning has a better carbon forming effect, the carbon layer is continuous and compact, and combustible gas generated by decomposing cellulose can escape from the surface of the carbon layer to form burning after passing through the tortuous tiny gaps in the carbon layer.
The second aspect of the present application provides a preparation method of the degradable floor, comprising the following steps:
(1) carrying out UV heat treatment on the surface layer;
(2) attaching the surface layer to the surface of the density board through a first adhesive to obtain a semi-finished product;
(3) stacking the semi-finished product on a tray, and slotting by a multi-blade saw according to the specification requirement;
(4) and (3) sticking the first bottom layer to the back of the density board through a second adhesive to obtain the degradable floor.
Wherein the light intensity of the UV heat treatment is 400-2(ii) a The speed is 14-18 m/min.
The first adhesive and the second adhesive are not particularly limited, and may be applied to bond each layer, and preferably, the first adhesive and the second adhesive are adhesives cured at low temperature, such as hot melt adhesives. More preferably, the glue amount of the first adhesive and the glue amount of the second adhesive are both 5-10g/m2。
Preferably, the thickness of the skin layer is 0.5-1.5 mm; the thickness of the density plate is 3-12 mm; the thickness of the first backsheet layer is 0.5-1.5 mm.
The degradable floor comprises a TPU wear-resistant layer, a decorative layer, a second bottom layer, a density board and a first bottom layer, wherein the surface layer, the density board and the first bottom layer are bonded through an adhesive, but the floor warps under a high-temperature condition due to the fact that the adhesive is weak in strength in the market at present, and research shows that the preparation raw materials of the first bottom layer and the second bottom layer comprise stone powder, soybean oil and a calcium-zinc composite stabilizer; when the density board comprises crop straws and wood leftover materials, even if the degradable floor is heated to 80 ℃, the warpage of the fireproof floor is small due to weak nonlinear vibration inside each layer of matrix and between layers of the fireproof floor systemAt 0.8mm, and density of 1.2-1.3g/cm3。
And the specific layer-to-layer stacking sequence and thickness enable the bending strength of the degradable floor to be larger than 2800 psi.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A degradable floor comprises a surface layer, a density board and a first bottom layer from top to bottom in sequence; the skin layer sequentially comprises a TPU wear-resistant layer, a decorative layer and a second bottom sheet layer from top to bottom, wherein the second bottom sheet layer is in contact with the density board.
Epidermal layer
The TPU wear-resistant layer is prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 2 parts of plasticizer DOTP, 1 part of epoxidized soybean oil, 1.5 parts of calcium-zinc composite heat stabilizer, 0.5 part of methyl methacrylate and 78 parts of ultraviolet absorbent UV-5310.2. Among them, TPU resin is available from leri plastics limited of guan city, under a trade name of "highly abrasion resistant TPU"; the calcium-zinc composite heat stabilizer is purchased from Hefei Rongguang chemical Co., Ltd; the preparation method of the TPU wear-resistant layer comprises the following steps: the raw materials are fed into a mixing machine for mixing, and then plasticized by an extruder, the plasticizing temperature is controlled to be 110 ℃, the filtering machine is used for filtering, the filtering temperature is 110-.
The decorative layer is a color film layer.
The second bottom sheet layer is prepared from 100 parts by weight of TPU resin, 20 parts by weight of plasticizer DOTP, 5 parts by weight of epoxidized soybean oil, 1.5 parts by weight of calcium-zinc composite heat stabilizer, 350 parts by weight of talcum powder, 5 parts by weight of carbon black and 5 parts by weight of lubricant stearic acid. Among them, TPU resin is available from gory plastic limited, trade name of which is "highly abrasion resistant TPU"; the calcium-zinc composite heat stabilizer is purchased from Hefei Rong photo chemical Co., Ltd; the method for preparing the second backsheet layer comprises the following steps: the raw materials are fed into a mixing machine to be mixed, then an internal mixer is used for plasticizing, the plasticizing temperature is controlled to be 140 ℃, the mixture is subjected to calendering molding through a four-roller calender, the temperature of a roller 1 of the four-roller calender is 130-plus-135 ℃, the temperature of a roller 2 of the four-roller calender is 130-plus-135 ℃, the temperature of a roller 3 of the four-roller calender is 125-plus-130 ℃, the temperature of a roller 4 of the four-roller calender is 115-plus-120 ℃, and cooling and cutting are carried out to obtain a second bottom sheet layer.
The preparation method of the epidermal layer comprises the following steps: stacking the TPU wear-resistant layer, the color film and the second bottom layer; and pushing the laminated material into a press after the material stacking is finished, wherein the hot pressing temperature is 120-125 ℃, the hot pressing time is 30min, the cold pressing temperature is 30 ℃, the cold pressing time is 30min, and discharging to obtain the epidermal layer.
Density board
The raw materials for preparing the fiber density board comprise, by weight, 30 parts of crop straws, 40 parts of wood leftover materials, 2 parts of inorganic alkali, 7 parts of magnesium-containing compounds and 10 parts of adhesives; the crop straw is wheat straw; the inorganic alkali is sodium hydroxide and sodium bicarbonate; the weight ratio of the sodium hydroxide to the sodium bicarbonate is 2: 1; the magnesium-containing compound comprises magnesium oxide and magnesium sulfate; the weight ratio of the magnesium oxide to the magnesium sulfate is 1: 2; the adhesive is pregelatinized starch, the viscosity of the pregelatinized starch is 500mPa · s, and the pregelatinized starch is purchased from Beijing Hongchang Macro science and technology Limited liability company. The preparation method of the density board comprises the following steps: adding crop straws, wood leftover materials, magnesium-containing compounds and sodium bicarbonate into a sodium hydroxide aqueous solution (the mass concentration is 2 percent), heating to 100 ℃, soaking for 2 hours, and filtering to obtain a mixture 1; and (3) transferring the adhesive and the mixture 1 into a high-speed mixer, uniformly mixing, standing for 5h, transferring into a plate extrusion device, and carrying out extrusion molding to obtain the density plate. The temperature of each section in the extrusion equipment is respectively 140-145 ℃, 150-155 ℃, 160-165 ℃ and 170-175 ℃.
The first bottom layer raw material and the preparation method are the same as those of the second bottom layer.
The preparation method of the degradable floor comprises the following steps:
(1) carrying out UV heat treatment on the surface layer; the illumination intensity of the UV heat treatment is 500mJ/cm2(ii) a The speed is 15 m/min;
(2) passing the skin layer through a first adhesive (glue amount 8 g/m)2) Attaching the powder to the surface of a density board to obtain a semi-finished product;
(3) stacking the semi-finished product on a tray, slotting by a multi-blade saw according to the specification requirement, and standing;
(4) passing the first backsheet layer through a second adhesive (glue amount 8 g/m)2) And (5) attaching the floor to the back of the density board to obtain the degradable floor.
Wherein the first adhesive and the second adhesive are available as LE-548 from Wuxi Laien technologies, Inc.
The thickness of the skin layer is 0.5 mm; the thickness of the density plate is 6 mm; the thickness of the first backsheet layer is 1 mm.
Example 2
The specific implementation of the degradable floor is the same as that of the embodiment 1, but the different point is that,
the TPU wear-resistant layer is prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 5 parts of plasticizer DOTP, 5 parts of epoxidized soybean oil, 3.5 parts of calcium-zinc composite heat stabilizer, 1 part of methyl methacrylate and 1 part of ultraviolet absorbent UV-5310.3.
The second bottom sheet layer is prepared from the following raw materials, by weight, 100 parts of TPU resin, 25 parts of plasticizer DOTP, 10 parts of epoxidized soybean oil, 3.5 parts of calcium-zinc composite heat stabilizer, 480 parts of talcum powder, 10 parts of carbon black and 7 parts of lubricant stearic acid.
The preparation raw materials of the density board comprise, by weight, 40 parts of crop straws, 45 parts of wood leftover materials, 5 parts of inorganic alkali, 15 parts of magnesium-containing compounds and 15 parts of adhesives; the weight ratio of the sodium hydroxide to the sodium bicarbonate is 1: 1; the magnesium-containing compound comprises magnesium oxide and magnesium sulfate; the weight ratio of the magnesium oxide to the magnesium sulfate is 1: 1;
the thickness of the skin layer is 1.5 mm; the thickness of the density plate is 6 mm; the thickness of the first backsheet layer is 0.5 mm.
Example 3
The specific implementation of the degradable floor is the same as that of the embodiment 1, but the different point is that,
the TPU wear-resistant layer is prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 3.5 parts of plasticizer DOTP, 3 parts of epoxidized soybean oil, 2 parts of calcium-zinc composite heat stabilizer, 0.8 part of methyl methacrylate and 0.78 part of ultraviolet absorbent UV-5310.25.
The second bottom sheet layer is prepared from 100 parts by weight of TPU resin, 23 parts by weight of plasticizer DOTP, 8 parts by weight of epoxidized soybean oil, 2.5 parts by weight of calcium-zinc composite heat stabilizer, 4000 parts by weight of talcum powder, 8 parts by weight of carbon black and 6 parts by weight of lubricant stearic acid.
The raw materials for preparing the density board comprise, by weight, 35 parts of crop straws, 42 parts of wood leftover materials, 3 parts of inorganic alkali, 10 parts of magnesium-containing compounds and 12 parts of adhesives; the weight ratio of the sodium hydroxide to the sodium bicarbonate is 2: 1; the magnesium-containing compound comprises magnesium oxide and magnesium sulfate; the weight ratio of the magnesium oxide to the magnesium sulfate is 1: 2;
the thickness of the skin layer is 1.0 mm; the thickness of the density plate is 7 mm; the thickness of the first backsheet layer is 1 mm.
Example 4
The specific implementation mode of the degradable floor is the same as that of the embodiment 3, and the difference is that the density board is a glass magnesium board, and the glass magnesium board comprises the following raw materials in parts by weight: 100-120 parts of light-burned magnesium oxide, 1-4 parts of magnesium sulfate heptahydrate, 0-25 parts of magnesium chloride, 4-10 parts of perlite, 2-5 parts of talcum powder, 1-5 parts of montmorillonite, 2-9 parts of silane coupling agent KH550, 10-30 parts of wood fiber and water, wherein: the water-cement ratio is 0.2-0.5.
Example 5
The specific implementation manner of the degradable floor is the same as that in example 3, and the difference is that the calcium silicate fiber board comprises the following raw materials in parts by weight: 20-30 parts of slaked lime, 21-23 parts of diatomite, 10-20 parts of coal ash, 4.5-5.5 parts of silica fume, 2-5 parts of bentonite, 5-10 parts of plant fiber, 2-5 parts of filler and water, wherein: the water-cement ratio is 0.2-0.5.
Comparative example 1
The specific implementation mode of the degradable floor is the same as that of example 3, and the difference is that the preparation method of the TPU wear-resistant layer comprises the following steps: the raw materials are fed into a mixing machine for mixing, then an extruder is used for plasticizing, the plasticizing temperature is controlled to be 140 ℃, a filter is used for filtering, the filtering temperature is 110-fold-over-120 ℃, the raw materials are subjected to calendaring molding by a five-roller calendar, the temperature of a roller 1 of the five-roller calendar is 130-fold-over-135 ℃, the temperature of a roller 2 of the five-roller calendar is 130-fold-over-135 ℃, the temperature of a roller 3 of the five-roller calendar is 125-fold-over-130 ℃, the temperature of a roller 4 of the five-roller calendar is 120-fold-over-125 ℃, and the temperature of a roller 5 of the five-roller is 120-fold-over-125 ℃, and cooling and rolling are carried out.
Comparative example 2
The specific implementation mode of the degradable floor is the same as that of example 3, and the difference is that the preparation method of the TPU wear-resistant layer comprises the following steps: the raw materials are fed into a mixing machine to be mixed, then the mixture is plasticized by an extruder, the plasticizing temperature is controlled to be 110 ℃, the filter is used for filtering, the filtering temperature is 110-120 ℃, the mixture is subjected to calendaring molding by a five-roller calendar, the temperature of a No. 1 roller of the five-roller calendar is 95-100 ℃, the temperature of a No. 2 roller of the five-roller calendar is 95-100 ℃, the temperature of a No. 3 roller of the five-roller calendar is 90-95 ℃, the temperature of a No. 4 roller of the five-roller calendar is 90-95 ℃, and the temperature of a No. 5 roller of the five-roller calendar is 90-95 ℃, and the mixture is cooled and rolled.
Comparative example 3
A degradable floor, the specific implementation manner is the same as that in example 3, except that the preparation method of the first substrate layer comprises the following steps: the raw materials are fed into a mixing machine to be mixed, then an internal mixer is used for plasticizing, the plasticizing temperature is controlled to be 140 ℃, the mixture is subjected to calendering molding through a four-roller calender, the temperature of a roller 1 of the four-roller calender is 110-115 ℃, the temperature of a roller 2 is 110-115 ℃, the temperature of a roller 3 is 115-110 ℃, the temperature of a roller 4 is 95-100 ℃, and cooling and cutting are carried out to obtain a second bottom sheet layer.
Comparative example 4
The specific implementation mode of the degradable floor is the same as that of example 3, but the weight ratio of the sodium hydroxide to the sodium bicarbonate is 6: 1.
Comparative example 5
The specific implementation mode of the degradable floor is the same as that of example 3, except that the weight ratio of the sodium hydroxide to the sodium bicarbonate is 1: 2.
Comparative example 6
The specific implementation mode of the degradable floor is the same as that of example 3, but the magnesium oxide is replaced by magnesium hydroxide.
Comparative example 7
The specific implementation mode of the degradable floor is the same as that of example 3, and the difference is that magnesium oxide is replaced by aluminum oxide.
Comparative example 8
The specific implementation mode of the degradable floor is the same as that of example 3, and the difference is that the preparation raw materials of the density board comprise, by weight, 0 part of crop straws, 70 parts of wood scraps, 2 parts of inorganic alkali, 7 parts of magnesium-containing compounds and 10 parts of adhesives.
Comparative example 9
The specific implementation mode of the degradable floor is the same as that of example 3, and the difference is that the preparation raw materials of the density board comprise, by weight, 70 parts of crop straws, 0 part of wood leftover materials, 2 parts of inorganic alkali, 7 parts of magnesium-containing compounds and 10 parts of adhesives;
performance testing
Warping after heating: the heating temperature is 80 ℃, and the unit is mm;
coefficient of thermal expansion (24 h): MD means direction along the color film; CD refers to the direction perpendicular to the color film; the coefficient of thermal expansion is the rate at which the floor changes in size with increasing temperature. The test temperature is 0-40 ℃.
Bending strength: in psi.
Smoke density (smokeless combustion): reference is made to astm e 662-03. The unit of smoke density is Dm.
Table 1 conventional SPC flooring and degradable flooring performance tests as described in examples 1-3
Figure BDA0002605478490000131
Wherein, the traditional SPC refers to PVC stone plastic floor, and the manufacturer is Jiangaoli decorative material (Jiangsu) Limited.
In order to better embody the technical effect of the invention, good, medium and bad are adopted for scoring; wherein the warpage after heating is preferably 0.6-0.8 (including 0.6 and 0.8), and the warpage after heating is preferably 0.8-1.5 (including 1.5); warpage after heating greater than 1.5 is poor;
the coefficient of thermal expansion is preferably between 0.6 and 0.8 (including 0.6 and 0.8), and is preferably between 0.8 and 1.5 (including 1.5); greater than 1.5 is a difference;
the bending strength is excellent in 2800 and 2900 (including 2800 and 2900), and in 2500 and 2800 (including 2500); less than 2500 is a difference;
densities of 1.2-1.4 (including 1.2 and 1.4) are preferred, and densities greater than 1.4 are medium;
the smoke density is preferably at 240- & ltSUB & gt 260- & ltSUB & gt 240- & ltSUB & gt and 260- & ltSUB & gt 300- & ltSUB & gt; greater than 300 is a difference;
table 2 comparative example floor performance testing
Figure BDA0002605478490000141
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (3)

1. The degradable floor is characterized by comprising a surface layer, a density board and a first bottom layer from top to bottom in sequence; the skin layer sequentially comprises a TPU wear-resistant layer, a decorative layer and a second bottom layer from top to bottom, wherein the second bottom layer is in contact with the density board;
the preparation method of the TPU wear-resistant layer comprises the following steps: the raw materials are fed into a mixing machine for mixing, then an extruder is used for plasticizing, the plasticizing temperature is controlled to be 110-fold-120 ℃, a filter is used for filtering, the filtering temperature is 110-fold-120 ℃, the materials are subjected to calendaring molding by a five-roller calendar, the temperature of a No. 1 roller of the five-roller calendar is 110-fold-130 ℃, the temperature of a No. 2 roller is 110-fold-115 ℃, the temperature of a No. 3 roller is 105-fold-110 ℃, the temperature of a No. 4 roller is 100-fold-105 ℃, the temperature of a No. 5 roller is 100-fold-105 ℃, and cooling and winding are carried out;
the TPU wear-resistant layer is prepared from the following raw materials in parts by weight: 100 parts of TPU resin, 2-5 parts of plasticizer, 1-5 parts of soybean oil, 1.5-3.5 parts of heat stabilizer, 0.5-1 part of acrylate monomer and 0.2-0.3 part of ultraviolet absorbent;
the density board is a fiber density board;
the raw materials for preparing the fiber density board comprise, by weight, 30-40 parts of crop straws, 40-45 parts of wood leftover materials, 2-5 parts of inorganic alkali, 7-15 parts of magnesium-containing compounds and 10-15 parts of adhesives;
the magnesium-containing compound comprises magnesium oxide and magnesium sulfate; the weight ratio of the magnesium oxide to the magnesium sulfate is 1: 1-5;
the inorganic alkali is sodium hydroxide and sodium bicarbonate; the weight ratio of the sodium hydroxide to the sodium bicarbonate is 1-3: 1;
the first bottom sheet layer and the second bottom sheet layer are made of the same raw materials and respectively comprise 100 parts by weight of TPU resin, 20-25 parts by weight of plasticizer, 5-10 parts by weight of soybean oil, 1.5-3.5 parts by weight of heat stabilizer, 480 parts by weight of stone powder 350-containing materials, 5-10 parts by weight of carbon black and 5-7 parts by weight of lubricant.
2. The degradable floor of claim 1, wherein the skin layer has a thickness of 0.5 to 1.5 mm; the thickness of the density plate is 3-12 mm; the thickness of the first backsheet layer is 0.5-1.5 mm.
3. The method for preparing the degradable floor of claim 1, comprising the steps of:
(1) carrying out UV heat treatment on the surface layer;
(2) attaching the skin layer subjected to UV heat treatment to the surface of the density plate through a first adhesive to obtain a semi-finished product;
(3) stacking the semi-finished product on a tray, and slotting by a multi-blade saw according to the specification requirement;
(4) and (3) attaching the first bottom layer to the back of the density board through a second adhesive to obtain the degradable floor.
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