CN114645608B - Laminate flooring and preparation method thereof - Google Patents

Laminate flooring and preparation method thereof Download PDF

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Publication number
CN114645608B
CN114645608B CN202210566051.5A CN202210566051A CN114645608B CN 114645608 B CN114645608 B CN 114645608B CN 202210566051 A CN202210566051 A CN 202210566051A CN 114645608 B CN114645608 B CN 114645608B
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magnesium
agent
modified
magnesium chloride
cement
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CN114645608A (en
Inventor
程凡
杨亮庆
刘展翅
佘学彬
欧阳倩雯
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Guangdong Nature Home Technology Research Co ltd
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Guangdong Nature Home Technology Research Co ltd
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Classifications

    • 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
    • E04F15/102—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 fibrous or chipped materials, e.g. bonded with synthetic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
    • B27M3/00—Manufacture or reconditioning of specific semi-finished or finished articles
    • B27M3/0013—Manufacture or reconditioning of specific semi-finished or finished articles of composite or compound articles
    • B27M3/0086—Manufacture or reconditioning of specific semi-finished or finished articles of composite or compound articles characterised by connecting using glue
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
    • B27M3/00—Manufacture or reconditioning of specific semi-finished or finished articles
    • B27M3/04—Manufacture or reconditioning of specific semi-finished or finished articles of flooring elements, e.g. parqueting blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/04—Magnesium cements containing sulfates, nitrates, phosphates or fluorides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/18—Separately-laid insulating layers; Other additional insulating measures; Floating floors
    • E04F15/181—Insulating layers integrally formed with the flooring or the flooring elements
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

The invention discloses a laminate flooring and a preparation method thereof, and relates to the technical field of laminate flooring. The laminate flooring comprises a substrate and a cured layer, wherein raw materials of the substrate comprise a first base material and modified magnesium chloride cement, raw materials of the cured layer comprise a second base material and a flame-retardant modified resin, the first base material is selected from a cellulose material and/or an inorganic mineral material, and the second base material is selected from an organic material or an inorganic material. Correspondingly, the invention also provides a preparation method of the reinforced floor. The laminate flooring provided by the invention has the characteristics of water resistance, flame retardance, no formaldehyde and high bonding strength.

Description

Laminate flooring and preparation method thereof
Technical Field
The invention relates to the technical field of laminate flooring, in particular to a laminate flooring and a preparation method thereof.
Background
Currently, there are three major types of flooring substrates on the market: fibreboard, plywood and solid wood. Among them, the solid wood floor is the most expensive and belongs to a high-grade product. The plywood is a composite floor made by bonding veneers with glue, and the price is medium. And the fiber board is made of wood fibers which are bonded by glue. The current laminate flooring has the largest sales volume and is the cheapest. However, most of the existing laminate flooring uses formaldehyde-containing urea-formaldehyde glue, and the product has no flame retardant function, the urea-formaldehyde glue has poor water resistance, and moisture is easy to cause floor foaming.
In order to solve the problems of formaldehyde contained in the glue, no flame retardant property and poor water resistance, in the prior art, the formaldehyde-free MDI glue is adopted to replace urea-formaldehyde glue, and the MDI glue pressing plate glue has good water resistance naturally, so that the problems of formaldehyde contained and poor water resistance are solved at the same time. In order to improve the flame retardant property, a flame retardant is often added during pressing the plate or a flame retardant liquid is painted or sprayed on the surface of the plate after pressing the plate.
However, this solution has the following problems: first, MDI adhesives are expensive and require a release agent to be applied to the steel belt during the pressing process, resulting in increased manufacturing costs. Moreover, since MDI adhesives are particularly sensitive to moisture, water-soluble flame retardants cannot be used because they react with MDI adhesives when pressed into boards, resulting in board burst and the like. Therefore, the powdery flame retardant is often compounded with MDI, but the addition amount of the powdery flame retardant needs to be increased in order to achieve good flame retardant effect, and the addition amount of the powdery flame retardant is up to 40 percent, which causes great adverse effect on the strength of the plate and also causes the glue application amount to be increased greatly. Furthermore, the method of spraying or brushing the flame retardant liquid after pressing the board cannot achieve good flame retardant effect, and firstly, the surface of the laminate flooring substrate often has residual release agent, and the roughness of the surface of the laminate flooring substrate is generally low, which results in low adhesive force and adhesion of the sprayed flame retardant liquid. In addition, due to the environmental protection requirement, hydrophilic flame retardants are often used, an inorganic flame retardant layer can be formed on the surface of the flame retardants after moisture is evaporated, and when the veneering is pressed, the bonding force of glue and the inorganic flame retardant layer is far less than that of the direct pressing of veneering paper and a fiber board, so that the strength performance is reduced, and the veneering is influenced.
In order to solve the problems that the glue contains formaldehyde, does not have flame retardant property and has poor water resistance, another idea is to adopt magnesium chloride cement to replace urea-formaldehyde glue. However, the use of the chloromagnesium cement also has several technical problems, firstly, the chloromagnesium cement has a problem of halogen return, which makes the surface of the laminate flooring substrate unsightly. In order to solve the problem of halogen return, the chlorine magnesium cement needs to be modified, and the traditional modification method generally adds fly ash, diatomite, red brick powder and the like into a chlorine magnesium binder to reduce the halogen return phenomenon. However, the introduction of these modifiers results in a reduced hydration level of the magnesium chloride binder and an overall brittleness of the board, which makes it impossible to groove the board and even to prepare the board as a floor. More importantly, the board added with the modifier can not be pressed, because the modifier can often form more calcium silicate hydrate, and the calcium silicate hydrate can be decomposed to release crystallization water during pressing (pressing temperature is 210 ℃) to form vapor, so that the board is pressed and exploded, and the existing board based on the magnesium chloride binder is mainly applied to wall materials and occasions with lower requirements on strength.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a reinforced floor which has the characteristics of water resistance, flame retardance, no formaldehyde and high bonding strength.
The technical problem to be solved by the invention is to provide a preparation method of the reinforced floor, which has simple process, can use a high-temperature pressing process in the later period, and can stably produce the reinforced floor with the characteristics of water resistance, flame retardance, no formaldehyde and high bonding strength.
In order to solve the technical problems, the invention provides a laminate flooring, comprising a substrate and a cured layer, wherein the raw materials of the substrate comprise a first base material and modified magnesium chloride cement, the raw materials of the cured layer comprise a second base material and a flame-retardant modified resin, the first base material is selected from a cellulose material and/or an inorganic mineral material, and the second base material is selected from an organic material or an inorganic material;
wherein, the modified magnesium chloride cement comprises the following raw materials: magnesium sulfate, magnesium oxide, magnesium chloride hexahydrate and an anti-halogen agent;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the halogen-resistant agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide.
In one embodiment, the raw material of the modified magnesium chloride cement further comprises a water-proofing agent;
the addition amount of the waterproof agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate.
The waterproof agent is one or a combination of styrene-acrylic emulsion, paraffin emulsion and an organic silicon compound.
In one embodiment, the raw material of the modified magnesium chloride cement further comprises a crystal form control agent;
the addition amount of the crystal form control agent is 1 to 5 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the crystal form control agent comprises an organic acid.
In one embodiment, the raw materials of the flame-retardant modified resin comprise, by weight: 90-110 parts of epoxy resin, 5-15 parts of flame retardant, 1-5 parts of toughening agent and 1-50 parts of curing agent.
In one embodiment, the flame retardant comprises one or a combination of an organophosphorus flame retardant, an inorganic phosphorus flame retardant, melamine cyanurate, zinc borate, magnesium hydroxide, melamine, pentaerythritol;
the curing agent comprises one or a combination of a dicyandiamide curing agent, a diamino imidazole triazine complex, an organic hydrazide curing agent and a boron trifluoride-amine curing agent;
the toughening agent comprises one or a combination of polyamide resin, polysulfide rubber, polybutadiene and polypropylene oxide rubber.
In one embodiment, the flame retardant is an organic phosphorus flame retardant and/or an inorganic phosphorus flame retardant.
In one embodiment, the flame retardant is selected from one or a combination of bisphenol A diphosphate, dimethyl toluene phosphate and ammonium polyphosphate.
In order to solve the problems, the invention also provides a preparation method of the reinforced floor, which comprises the following steps:
preparing modified magnesium chloride cement and flame-retardant modified resin;
uniformly mixing the modified magnesium chloride cement with a first base material, and then pressing and forming to obtain a substrate;
covering the surface of a second base material with the flame-retardant modified resin, and drying to obtain a cured material;
laying the cured material on the upper layer of the substrate, and pressing and forming to obtain the laminate flooring, wherein the laminate flooring comprises the substrate and the cured layer;
wherein the first substrate is selected from a cellulosic material and/or an inorganic mineral material and the second substrate is selected from an organic material or an inorganic material;
the modified magnesium chloride cement comprises the following raw materials: magnesium sulfate, magnesium oxide, magnesium chloride hexahydrate and an anti-halogen agent;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the anti-halogen agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide.
In one embodiment, the raw material of the modified magnesium chloride cement further comprises a water-proofing agent and/or a crystal form control agent;
the waterproof agent is one or a combination of styrene-acrylic emulsion, paraffin emulsion and an organic silicon compound;
the crystal form control agent comprises an organic acid.
In one embodiment, the modified magnesium chloride cement is prepared by the following method:
mixing and stirring magnesium oxide and magnesium chloride hexahydrate, adding magnesium sulfate during stirring, and grinding and filtering after the magnesium sulfate is added to obtain a magnesium chloride cement-based binder;
and heating the chloromagnesium cement-based binder, adding a crystal form control agent, an anti-halogen agent and a waterproof agent respectively, and stirring uniformly to obtain the modified chloromagnesium cement.
In one embodiment, the mass ratio of the magnesium oxide to the magnesium chloride hexahydrate is (5 to 16): 1;
the addition amount of the magnesium sulfate is 10 to 20 percent of the total mass of the magnesium oxide and the magnesium chloride hexahydrate;
the addition amount of the crystal form control agent is 1 to 5 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the addition amount of the waterproof agent is 1-10% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate.
In one embodiment, the flame retardant modified resin is prepared by the following method:
and heating the epoxy resin, respectively adding a flame retardant, a toughening agent and a curing agent, and mixing to obtain the flame-retardant modified resin.
In one embodiment, the flame retardant is selected from one or a combination of organic phosphorus flame retardant, inorganic phosphorus flame retardant, melamine cyanurate, zinc borate, magnesium hydroxide, melamine and pentaerythritol;
the curing agent is one or a combination of a dicyandiamide curing agent, a diamino imidazole triazine complex, an organic hydrazide curing agent and a boron trifluoride-amine curing agent;
the toughening agent is one or a combination of polyamide resin, polysulfide rubber, polybutadiene and polypropylene oxide rubber;
the addition amount of the flame retardant is 5 to 15 percent of the mass of the epoxy resin;
the addition amount of the toughening agent is 1 to 5 percent of the mass of the epoxy resin;
the addition amount of the curing agent is 1 to 50 percent of the mass of the epoxy resin.
In one embodiment, the modified magnesium chloride cement and a first base material are uniformly mixed, and then are subjected to rolling treatment and hot pressing treatment to obtain a substrate;
in the hot pressing treatment process: the hot pressing temperature is 100 to 200 ℃, and the hot pressing time is 1 to 3min/mm;
the mass ratio of the first base material to the modified magnesium chloride cement is 100: (10 to 50).
In one embodiment, a second base material is soaked in the flame-retardant modified resin, and then the second base material is dried for 10 to 20s under the environment of 150 to 300 ℃ to obtain a cured material;
in the cured material, the mass of the flame-retardant modified resin is 20 to 50 percent of the total mass of the second base material and the flame-retardant modified resin;
the temperature of the pressing and forming is 200 to 220 ℃, the pressure is 5 to 10Mpa, and the time is 16 to 23s.
The implementation of the invention has the following beneficial effects:
the laminate flooring provided by the invention has the characteristics of water resistance, flame retardance, no formaldehyde and high bonding strength.
Specifically, the laminate flooring adopts the modified magnesium chloride cement as the binder, and the modified magnesium chloride cement adopts the specific halogen-resistant agent, so that the problem of halogen return is relieved, the strength of the magnesium chloride binder is not weakened while micropores are sealed, and the mineral substance which releases crystal water in the later period is not generated, so that the high-temperature pressing process can be used in the later period, the internal bonding strength of the base plate is ensured, and the processing performance of the base plate is greatly improved.
In addition, a specific waterproof agent is added into the raw materials of the modified magnesium chloride cement, and the waterproof agent not only can improve the waterproofness of the laminate flooring, but also can be combined with specific components in the flame-retardant modified resin to form an interpenetrating network structure, so that the affinity and the binding force in the laminate flooring are improved, and the overall strength of the laminate flooring is further improved.
Moreover, a specific crystal form control agent is added into the raw materials of the modified chloromagnesite cement, and the crystal form control agent can stabilize a specific crystal form, so that the bonding strength of the modified chloromagnesite cement is improved.
Further, the laminate flooring incorporates the flame retardant modified resin so that a laminate flooring having a certain flame retardant property is finally obtained. The flame-retardant modified resin takes the epoxy resin as a main raw material, and compared with other resins, the epoxy resin can improve the adhesive force between organic matters and inorganic matters and has high strength.
Moreover, the flame retardant is introduced into the flame-retardant modified resin, the flame retardant not only can endow a certain flame-retardant effect to the cured layer, but also can combine phosphate ions in a specific flame retardant with magnesium ions in the modified chlorine-magnesium cement in the substrate to form an insoluble magnesium phosphate salt, and the insoluble magnesium phosphate salt is covered on the particle surface of 5-phase or 3-phase crystals, so that the water resistance of the reinforced floor is further improved.
In addition, a toughening agent is introduced into the flame-retardant modified resin, and the toughening agent can recover the fluidity under the hot-pressing condition, and permeates into the microporous structure of the modified chloromagnesia cement along with the epoxy resin liquid to further seal the microporous structure of the modified chloromagnesia cement, so that the problem of halogen return of the modified chloromagnesia cement is solved. And the toughening agent can be combined with specific components in the modified magnesium chloride cement to form an interpenetrating network structure, so that the affinity and the binding force between the substrate and the cured layer are further improved, the overall strength of the reinforced floor is further improved, and the problem of easy tearing caused by the inconsistent thermal expansion coefficients of the substrate and the cured layer is solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below.
In order to solve the technical problems, the invention provides a laminate flooring, comprising a substrate and a cured layer, wherein the raw materials of the substrate comprise a first base material and modified magnesium chloride cement, the raw materials of the cured layer comprise a second base material and a flame-retardant modified resin, the first base material is selected from a cellulose material and/or an inorganic mineral material, and the second base material is selected from an organic material or an inorganic material;
wherein, the modified magnesium chloride cement comprises the following raw materials: magnesium sulfate, magnesium oxide, magnesium chloride hexahydrate and a halogen-resistant agent;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the halogen-resistant agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide.
The modified chlorine magnesium cement in the substrate has the characteristic of no formaldehyde, has high bonding strength and few halogen return problems, not only ensures the internal bonding strength of the substrate, but also greatly improves the processing performance of the substrate.
In one embodiment, the first substrate comprises wood fibers, wood strands, wood flakes, wood particles, mineral fibers. And mixing the first base material with the modified magnesium chloride cement, and bonding the first base material by the modified magnesium chloride cement to obtain the substrate. The second base material comprises aluminum silicate non-woven fabric, aluminum silicate fiber paper, glass fiber paper and plant fiber paper. Covering the surface of the second base material with the flame-retardant modified resin, or impregnating the inside of the second base material with the flame-retardant modified resin to obtain a cured layer. The manner of obtaining the cured layer includes, but is not limited to, spraying and dipping.
Preferably, the first substrate is a plant fiber; the second base material is aluminum silicate fiber paper or aluminum silicate non-woven fabric. In one embodiment, the mass ratio of the first substrate to the modified chloromagnesite is 100: (10 to 50), but not limited to the above range. The mass of the flame-retardant modified resin is 20 to 50% of the total mass of the second base material and the flame-retardant modified resin, but not limited to the above range.
In the prior art, the traditional modification method for the chlorine-magnesium cement is to add fly ash, diatomite, red brick powder and the like into a chlorine-magnesium binder so as to reduce the phenomenon of halogen return. However, the introduction of these modifiers results in a reduced hydration level of the magnesium chloride binder and an overall brittleness of the board, which makes it impossible to groove the board and even to prepare the board as a floor. More importantly, the board added with the modifiers cannot be pressed and pasted, because the modifiers usually form more calcium silicate hydrate, and the calcium silicate hydrate can be decomposed to release crystallization water during pressing (pressing temperature is 210 ℃) to form water vapor, so that the board is pressed and exploded, and the existing board based on the chlorine-magnesium binder is mainly applied to wall materials and occasions with lower requirements on strength.
In order to solve the problems, the modified magnesium chloride cement is added with an anti-halogen agent with a specific component, and in one embodiment, the anti-halogen agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide. Preferably, the anti-halogen agent is ferric chloride. In one embodiment, the anti-halogen agent has a mass of 1 to 10% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate. The anti-halogen agent can seal the fine channel and block the porous channel, thereby reducing the phenomenon that free magnesium chloride migrates to the surface of the plate along with the pore channel, further avoiding the migration phenomenon formed by capillary phenomenon and concentration difference, and finally relieving the problem of halogen return of the chlorine-magnesium cement. Moreover, the halogen-resistant agent provided by the invention does not cause the reduction of the hydration degree of the chlorine-magnesium cement, and does not generate mineral substances with crystal water, thereby improving the processing performance of the substrate.
Further, in order to improve the water resistance of the laminate flooring, a water-proofing agent is introduced into the modified chloromagnesium cement, and in one embodiment, the water-proofing agent is one or a combination of a styrene-acrylic emulsion, a paraffin wax emulsion and an organic silicon compound. In one embodiment, the mass of the waterproofing agent is 1 to 10% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate. Compared with the pure chlorine magnesium cement system binder, the modified chlorine magnesium cement obviously improves the water resistance and slows down the halogen return effect. And the modified flame-retardant resin can be combined with specific components in the flame-retardant modified resin to form an interpenetrating network structure, so that the affinity and the binding force in the reinforced floor are improved, and the integral strength of the reinforced floor is further improved.
Furthermore, in the prior art, the magnesium chloride cements, after drying, form a certain hydrated crystal structure which has a plurality of morphologies, some of which are more stable, but this stabilization is reversible, in which the needle-like 5 phases (5 Mg (OH) are cross-linked with one another 2 ·MgCl 2 ·8H 2 O) and phases 3（3Mg(OH) 2 ·MgCl 2 ·8H 2 O) can impart high mechanical properties to the chloromagnesium cement, and in order to ensure the stability of the 5-phase and the 3-phase, the present invention adds the crystal form control agent to the chloromagnesium cement system, and in one embodiment, the crystal form control agent comprises an organic acid, such as one or a combination of formic acid, citric acid, tartaric acid and oxalic acid, but is not limited thereto. In one embodiment, the mass of the crystal form control agent is 1 to 5% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate. The crystal form control agent can stabilize the crystal forms of 5-phase and 3-phase, thereby improving the bonding strength and the self strength of the modified magnesium chloride cement.
In conclusion, the invention introduces the specific halogen-resistant agent, the waterproof agent and the crystal form control agent into the modified magnesium chloride cement, mixes the modified magnesium chloride cement with the first base material and then molds, and obtains the substrate which has no formaldehyde, good water resistance, good processing performance, less halogen return phenomenon and high internal bonding strength.
In order to enable a final finished product to have good flame retardance, a solidified layer is arranged on the substrate, and raw materials of the solidified layer comprise a second base material and a flame-retardant modified resin.
In one embodiment, a flame retardant is added to the resin to obtain the flame retardant modified resin. The resin is selected from one or a combination of isocyanurate resin, urea-formaldehyde resin, phenolic glue, animal hide glue, melamine-formaldehyde resin and epoxy resin. The flame retardant is selected from one or a combination of organic phosphorus flame retardant, inorganic phosphorus flame retardant, melamine cyanurate, zinc borate, magnesium hydroxide, melamine and pentaerythritol. The introduction of the flame-retardant modified resin can endow the laminate flooring with certain flame-retardant performance.
Preferably, the flame-retardant modified resin comprises the following raw materials in parts by weight: 90-110 parts of epoxy resin, 5-15 parts of flame retardant, 1-5 parts of toughening agent and 1-50 parts of curing agent.
It should be noted that, in the prior art, melamine formaldehyde resin is adopted, but the compatibility between melamine formaldehyde resin and magnesium chloride cement-based binder is poor, and the press-fitting molding cannot be realized subsequently. Compared with melamine formaldehyde resin, the epoxy resin can improve the adhesive force between organic matters and inorganic matters and has high strength.
Further, the raw material of the flame-retardant modified resin comprises a flame retardant, and in one embodiment, the flame retardant comprises one or a combination of an organic phosphorus flame retardant, an inorganic phosphorus flame retardant, melamine cyanurate, zinc borate, magnesium hydroxide, melamine and pentaerythritol; preferably, the flame retardant is an organic phosphorus flame retardant and/or an inorganic phosphorus flame retardant. More preferably, the flame retardant comprises one or a combination of bisphenol A diphosphate, dimethyl toluene phosphate and ammonium polyphosphate. In one embodiment, the mass of the flame retardant is 5 to 15% of the mass of the epoxy resin, but is not limited to the above range. The flame retardant not only can endow the solidified layer with a certain flame retardant effect, but also can release phosphate ions by a specific inorganic phosphorus flame retardant or release phosphate ions by a specific organic phosphorus flame retardant under the action of a crystal form control agent in the modified chlorine-magnesium cement, the phosphate ions can be combined with magnesium ions in the modified chlorine-magnesium cement in a substrate to form an insoluble magnesium phosphate salt, and the insoluble magnesium phosphate salt covers the particle surface of a 5-phase or 3-phase crystal, so that the water resistance of the modified chlorine-magnesium cement is further improved.
In addition, the flame retardant modified resin includes a toughening agent, in one embodiment, the toughening agent is selected from one or a combination of polyamide resin, polysulfide rubber, polybutadiene, polypropylene oxide rubber, but not limited to the above list; the mass of the toughening agent is 1 to 5 percent of the mass of the epoxy resin, but the mass is not limited to the range. The toughening agent can recover the fluidity under the hot pressing condition, and the toughening agent permeates into the microporous structure of the modified magnesium chloride cement along with the epoxy resin liquid to further seal the microporous structure of the modified magnesium chloride cement, so that the problem of halogen return of the modified magnesium chloride cement is solved. The toughening agent can be combined with specific components in the modified magnesium chloride cement to form an interpenetrating network structure, so that the affinity and the binding force between the substrate and the cured layer are further improved, the overall strength of the reinforced floor is further improved, and the problem of easy tearing caused by the inconsistent thermal expansion coefficients of the substrate and the cured layer is solved.
Further, the flame retardant modified resin includes a curing agent, which in one embodiment is selected from one or a combination of dicyandiamide curing agents, diaminoimidazole triazine complexes, organic hydrazide curing agents, boron trifluoride-amine curing agents, but is not limited to the above list; in one embodiment, the mass of the curing agent is 1 to 50% of the mass of the epoxy resin, but is not limited to the above range. Preferably, the curing agent is a high-temperature latent curing agent, the latent curing agent is used for production by directly utilizing the existing melamine formaldehyde resin impregnation production line, the melamine formaldehyde resin adopts a partial curing mode, and the latent curing agent can also realize partial curing, so that a Wenconna press is convenient to finally press and stick together with a plate again so as to be completely cured.
In conclusion, the reinforced floor provided by the invention has the characteristics of water resistance, flame retardance, no formaldehyde and high bonding strength.
Correspondingly, the invention also provides a preparation method of the reinforced floor, which comprises the following steps:
s1, preparing modified magnesium chloride cement and flame-retardant modified resin;
specifically, the preparation methods of the modified magnesium chloride cement and the flame-retardant modified resin are explained in sequence.
First, in one embodiment, the modified chloromagnesia cement comprises, as raw materials: magnesium sulfate, magnesium oxide, magnesium chloride hexahydrate and an anti-halogen agent; the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate; the halogen-resistant agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide. Preferably, the raw materials of the modified magnesium chloride cement also comprise a waterproof agent and/or a crystal form control agent; the waterproof agent is one or a combination of styrene-acrylic emulsion, paraffin emulsion and an organic silicon compound; the crystal form control agent comprises an organic acid. The specific description of the components of the modified chloromagnesium cement is referred to above and will not be repeated herein.
In one embodiment, the modified chloromagnesia cement is prepared by the following method:
mixing and stirring magnesium oxide and magnesium chloride hexahydrate, adding magnesium sulfate during stirring, and grinding and filtering after the magnesium sulfate is added to obtain a magnesium chloride cement-based binder;
and heating the chloromagnesium cement-based binder, adding a crystal form control agent, an anti-halogen agent and a waterproof agent respectively, and stirring uniformly to obtain the modified chloromagnesium cement.
Preferably, the temperature of the magnesium chloride cement-based binder is raised to 30 to 80 ℃.
In one embodiment, the mass ratio of magnesium oxide to magnesium chloride hexahydrate is (5 to 16): 1;
the addition amount of the magnesium sulfate is 10 to 20 percent of the total mass of the magnesium oxide and the magnesium chloride hexahydrate;
the addition amount of the crystal form control agent is 1 to 5 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate; the addition amount of the waterproof agent is 1-10% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate.
Preferably, the flame-retardant modified resin and the preparation method thereof are as follows:
and heating the epoxy resin, respectively adding a flame retardant, a toughening agent and a curing agent, and mixing to obtain the flame-retardant modified resin.
Preferably, the epoxy resin is heated to 40 to 80 ℃, and then a flame retardant, a toughening agent and a curing agent are respectively added.
In one embodiment, the addition amount of the flame retardant is 5 to 15 percent of the mass of the epoxy resin;
the addition amount of the toughening agent is 1 to 5 percent of the mass of the epoxy resin;
the addition amount of the curing agent is 1 to 50 percent of the mass of the epoxy resin.
The specific description of the components of the flame-retardant modified resin is referred to above and will not be repeated herein.
S2, uniformly mixing the modified magnesium chloride cement with a first base material, and then pressing and forming to obtain a substrate;
in one embodiment, the first substrate is selected from a cellulosic material and/or an inorganic mineral material. The first substrate comprises wood fibers, wood strands, wood flakes, wood particles, mineral fibers. Preferably, the first substrate is a plant fiber, including wood fiber and bamboo fiber, such plant fiber materials being widely available from various sources well known to those skilled in the art.
In one embodiment, the mass ratio of the first substrate to the modified chloromagnesite is 100: (10 to 50), but not limited to the above range.
In one embodiment, the modified magnesium chloride cement and a first base material are uniformly mixed, and then are subjected to rolling treatment and hot pressing treatment to obtain a substrate; the hot pressing treatment process comprises the following steps: the hot pressing temperature is 100 to 200 ℃, and the hot pressing time is 1 to 3min/mm.
S3, covering the surface of the second base material with the flame-retardant modified resin, and drying to obtain a cured material;
in one embodiment, the second substrates are each selected from cellulosic materials and/or inorganic mineral materials. The second base material comprises aluminum silicate non-woven fabric, aluminum silicate fiber paper, glass fiber paper and plant fiber paper. Preferably, the second substrate is an aluminum silicate fiber paper or an aluminum silicate nonwoven fabric.
In one embodiment, the second substrate is impregnated with the flame retardant modified resin to achieve coverage of the flame retardant modified resin on the surface of the second substrate; in another embodiment, the flame retardant modified resin is spray coated onto the surface of the second substrate to achieve coverage of the flame retardant modified resin on the surface of the second substrate.
In one embodiment, a second base material is soaked in the flame-retardant modified resin, and then the second base material is dried for 10 to 20s under the environment of 150 to 300 ℃ to obtain a cured material;
in one embodiment, the mass of the flame-retardant modified resin is 20 to 50% of the total mass of the second base material and the flame-retardant modified resin, but is not limited to the above range.
S4, laying the curing material on the upper layer of the substrate, and pressing and forming to obtain a finished product.
In one embodiment, the temperature of the press molding is 200 to 220 ℃, the pressure is 5 to 10Mpa, and the time is 16 to 23s.
In one embodiment, the bottom layer of the substrate is paved with balance paper, the upper layer of the substrate is respectively paved with the curing material, the decorative paper and the wear-resistant paper, and the finished product is obtained after pressing and forming.
The invention is further illustrated by the following specific examples:
example 1
The embodiment provides a reinforced floor and a preparation method thereof:
the laminate flooring comprises a substrate and a cured layer, wherein raw materials of the substrate comprise plant fibers and modified magnesium chloride cement, and raw materials of the cured layer comprise aluminum silicate fiber paper and flame-retardant modified resin.
The modified chlorine magnesium cement comprises the following raw materials: magnesium oxide, magnesium chloride hexahydrate, magnesium sulfate, tartaric acid, cobalt chloride and styrene-acrylic emulsion;
the flame-retardant modified resin comprises the following raw materials: epoxy resin, bisphenol A diphosphate, polyamide resin and dicyandiamide curing agent.
The preparation method of the reinforced floor comprises the following steps:
s1, preparing modified magnesium chloride cement and flame-retardant modified resin;
s11, preparing the modified magnesium chloride cement by adopting the following method:
mixing and stirring magnesium oxide and magnesium chloride hexahydrate according to the mass ratio of 5;
heating the chloromagnesite cement-based binder to 80 ℃, respectively adding tartaric acid, cobalt chloride and styrene-acrylic emulsion, and uniformly stirring to obtain the modified chloromagnesite cement;
the addition amount of the tartaric acid is 1 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate;
the addition amount of the cobalt chloride is 10 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate;
the adding amount of the styrene-acrylic emulsion is 3 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate.
S12, preparing the flame-retardant modified resin by adopting the following method:
heating the epoxy resin to 60 ℃, respectively adding bisphenol A diphosphate, polyamide resin and dicyandiamide curing agent, and mixing for 0.5h to obtain the flame-retardant modified resin;
the addition amount of the bisphenol A diphosphate is 15% of the mass of the epoxy resin;
the adding amount of the polyamide resin is 5% of the mass of the epoxy resin;
the adding amount of the dicyandiamide curing agent is 10% of the mass of the epoxy resin.
S2, mixing the modified magnesium chloride cement and the plant fiber according to the proportion of 20;
s3, dipping the aluminum silicate non-woven fabric into the flame-retardant modified resin, wherein the dipping and gluing amount is that the mass of the flame-retardant modified resin is 50% of the total mass of the aluminum silicate fiber paper and the flame-retardant modified resin, and then drying for 150 seconds at 150 ℃ to obtain a cured material;
s4, laying the curing material, the decorative paper and the wear-resistant paper on the upper layer of the substrate, and pressing and forming to obtain a finished product.
The pressing and forming temperature is 200 ℃, the pressure is 8Mpa, and the time is 23s.
Example 2
The embodiment provides a reinforced floor and a preparation method thereof:
the laminate flooring comprises a substrate and a cured layer, wherein raw materials of the substrate comprise plant fibers and modified magnesium chloride cement, and raw materials of the flame-retardant cured layer comprise aluminum silicate fiber paper and flame-retardant modified resin.
The modified magnesium chloride cement comprises the following raw materials: magnesium oxide, magnesium chloride hexahydrate, magnesium sulfate, formic acid, ferric chloride and paraffin emulsion;
the flame-retardant modified resin comprises the following raw materials: epoxy resins, dimethyl toluene phosphate, polysulfide rubber and diaminoimidazole triazine complexes.
The preparation method of the reinforced floor comprises the following steps:
s1, preparing modified magnesium chloride cement and flame-retardant modified resin;
s11, preparing the modified magnesium chloride cement by adopting the following method:
mixing and stirring magnesium oxide and magnesium chloride hexahydrate according to the mass ratio of 16 to 1, adding magnesium sulfate during stirring, wherein the magnesium sulfate accounts for 20% of the total mass of the magnesium oxide and the magnesium chloride hexahydrate, stirring at the speed of 500r/min for 1h, stirring, transferring into a pulping machine for further treatment for 30min, and filtering by using 200-mesh gauze to obtain a magnesium chloride cement-based binder;
heating the chloromagnesite cement-based binder to 80 ℃, respectively adding formic acid, ferric chloride and paraffin emulsion, and uniformly stirring to obtain the modified chloromagnesite cement;
the addition amount of the formic acid is 5 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate;
the adding amount of the ferric chloride is 1 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate;
the amount of the paraffin wax emulsion added was 1% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate.
S12, preparing the flame-retardant modified resin by adopting the following method:
heating the epoxy resin to 60 ℃, respectively adding dimethyl methyl toluenesulfonate, polysulfide rubber and a diamino imidazole triazine complex, and mixing for 0.5h to obtain the flame-retardant modified resin;
the adding amount of the dimethyl toluene phosphate is 5 percent of the mass of the epoxy resin;
the addition amount of the polysulfide rubber is 1 percent of the mass of the epoxy resin;
the addition amount of the diamino imidazole triazine complex is 20% of the mass of the epoxy resin.
S2, mixing the modified magnesium chloride cement and the plant fiber according to the proportion of 10;
s3, dipping the aluminum silicate fiber paper into the flame-retardant modified resin, wherein the dipping and gluing amount is that the mass of the flame-retardant modified resin is 20% of the total mass of the aluminum silicate fiber paper and the flame-retardant modified resin, and then drying for 150 seconds at 150 ℃ to obtain a cured material;
s4, laying the curing material, the decorative paper and the wear-resistant paper on the upper layer of the substrate, and pressing and forming to obtain a finished product.
The pressing and forming temperature is 200 ℃, the pressure is 8Mpa, and the time is 23s.
Example 3
The embodiment provides a reinforced floor and a preparation method thereof:
the laminate flooring comprises a substrate and a cured layer, wherein raw materials of the substrate comprise plant fibers and modified magnesium chloride cement, and raw materials of the flame-retardant cured layer comprise aluminum silicate fiber paper and flame-retardant modified resin.
The modified chlorine magnesium cement comprises the following raw materials: magnesium oxide, magnesium chloride hexahydrate, magnesium sulfate, citric acid, calcium sulfate and styrene-acrylic emulsion;
the flame-retardant modified resin comprises the following raw materials: epoxy resin, ammonium polyphosphate, polybutadiene and an organic hydrazide curing agent.
The preparation method of the reinforced floor comprises the following steps:
s1, preparing modified magnesium chloride cement and flame-retardant modified resin;
s11, preparing the modified magnesium chloride cement by adopting the following method:
mixing and stirring magnesium oxide and magnesium chloride hexahydrate according to the mass ratio of 10 to 1, adding magnesium sulfate during stirring, wherein the magnesium sulfate accounts for 15% of the total mass of the magnesium oxide and the magnesium chloride hexahydrate, stirring at the speed of 500r/min for 1h, stirring, transferring into a pulping machine for further treatment for 30min, and filtering by using 200-mesh gauze to obtain a magnesium chloride cement-based binder;
heating the magnesium chloride cement-based binder to 80 ℃, respectively adding citric acid, calcium sulfate and styrene-acrylic emulsion, and uniformly stirring to obtain the modified magnesium chloride cement;
the addition amount of the citric acid is 3 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate;
the addition amount of the calcium sulfate is 5 percent of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate;
the adding amount of the styrene-acrylic emulsion is 5% of the total mass of the magnesium sulfate, the magnesium oxide and the magnesium chloride hexahydrate.
S12, preparing the flame-retardant modified resin by adopting the following method:
heating the epoxy resin to 60 ℃, respectively adding ammonium polyphosphate, polybutadiene and an organic hydrazide curing agent, and mixing for 0.5h to obtain the flame-retardant modified resin;
the adding amount of the ammonium polyphosphate is 10 percent of the mass of the epoxy resin;
the addition amount of the polybutadiene is 3% of the mass of the epoxy resin;
the addition amount of the organic hydrazide curing agent is 30% of the mass of the epoxy resin.
S2, mixing the modified magnesium chloride cement and the plant fiber according to the proportion of 10;
s3, impregnating the aluminum silicate fiber paper in the flame-retardant modified resin, wherein the impregnating and gluing amount is that the mass of the flame-retardant modified resin is 40% of the total mass of the aluminum silicate fiber paper and the flame-retardant modified resin, and then drying for 150S at 150 ℃ to obtain a cured material;
s4, laying the curing material, the decorative paper and the wear-resistant paper on the upper layer of the substrate, and pressing and forming to obtain a finished product.
The pressing and forming temperature is 200 ℃, the pressure is 8Mpa, and the time is 23s.
The physical properties of the laminate flooring obtained in examples 1 to 3 were measured, and the test standards were referred to industry standard LY/T2880-2007, and the test results are shown in Table 1.
Figure 726234DEST_PATH_IMAGE001
In addition, the flame retardant performance of the laminate flooring prepared in examples 1 to 3 was tested, the flame retardant performance adopted the test standard of the flooring material of GB 8624-2012, and the test results are shown in table 2.
Figure 568288DEST_PATH_IMAGE002
As can be seen from the data in the tables 1 and 2, the reinforced floor provided by the invention can simultaneously meet the industrial standard LY/T2880-2007 and the national standard GB 8624-2012, and has the characteristics of water resistance, flame retardance, no formaldehyde and high bonding strength.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (13)

1. The laminate flooring is characterized by comprising a substrate and a cured layer, wherein the raw materials of the substrate comprise a first base material and modified magnesium chloride cement, the raw materials of the cured layer comprise a second base material and a flame-retardant modified resin, the first base material is selected from cellulose materials and/or inorganic mineral materials, and the second base material is selected from organic materials or inorganic materials;
wherein, the modified magnesium chloride cement comprises the following raw materials: magnesium sulfate, magnesium oxide, magnesium chloride hexahydrate and an anti-halogen agent;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the anti-halogen agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide;
the raw materials of the modified chlorine magnesium cement also comprise a waterproof agent;
the waterproof agent is one or a combination of styrene-acrylic emulsion, paraffin emulsion and an organic silicon compound;
the flame-retardant modified resin comprises the following raw materials in parts by weight: 90-110 parts of epoxy resin, 5-15 parts of flame retardant, 1-5 parts of toughening agent and 1-50 parts of curing agent;
the toughening agent is one or a combination of polyamide resin, polysulfide rubber, polybutadiene and polypropylene oxide rubber.
2. The laminate flooring according to claim 1, wherein the water repellent is added in an amount of 1 to 10% by mass based on the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate.
3. The laminate flooring according to claim 1, wherein the modified chloromagnesium cement further comprises a crystal form control agent;
the addition amount of the crystal form control agent is 1 to 5 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the crystal form control agent comprises an organic acid.
4. The laminate flooring of claim 1, wherein the flame retardant is one or a combination of an organic phosphorus flame retardant, an inorganic phosphorus flame retardant, melamine cyanurate, zinc borate, magnesium hydroxide, melamine, and pentaerythritol;
the curing agent is one or a combination of dicyandiamide curing agent, diamino imidazole triazine complex, organic hydrazide curing agent and boron trifluoride-amine curing agent.
5. The laminate flooring according to claim 4, wherein the flame retardant is an organic phosphorus flame retardant and/or an inorganic phosphorus flame retardant.
6. The laminate flooring of claim 5, wherein the flame retardant is selected from one or a combination of bisphenol A diphosphate, dimethyl toluene phosphate and ammonium polyphosphate.
7. The preparation method of the laminate flooring is characterized by comprising the following steps of:
preparing modified magnesium chloride cement and flame-retardant modified resin;
uniformly mixing the modified magnesium chloride cement with a first base material, and then performing compression molding to obtain a substrate;
covering the surface of a second base material with the flame-retardant modified resin, and drying to obtain a cured material;
laying the cured material on the upper layer of the substrate, and pressing and forming to obtain the laminate flooring, wherein the laminate flooring comprises the substrate and the cured layer;
wherein the first substrate is selected from a cellulosic material and/or an inorganic mineral material and the second substrate is selected from an organic material or an inorganic material;
the modified magnesium chloride cement comprises the following raw materials: magnesium sulfate, magnesium oxide, magnesium chloride hexahydrate and an anti-halogen agent;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the anti-halogen agent is one or a combination of cobalt chloride, calcium sulfate, ferric chloride and ferroferric oxide;
the raw materials of the modified magnesium chloride cement also comprise a waterproof agent;
the waterproof agent is one or a combination of styrene-acrylic emulsion, paraffin emulsion and an organic silicon compound;
the flame-retardant modified resin is prepared by the following method:
heating the epoxy resin, respectively adding a flame retardant, a toughening agent and a curing agent, and mixing to obtain the flame-retardant modified resin;
the toughening agent is one or a combination of polyamide resin, polysulfide rubber, polybutadiene and polypropylene oxide rubber.
8. The method for manufacturing a laminate flooring according to claim 7, wherein the modified chloromagnesite cement further comprises a crystal form controlling agent;
the crystal form control agent comprises an organic acid.
9. The method of manufacturing a laminate flooring according to claim 8, wherein the modified chloromagnesium cement is manufactured by the method comprising:
mixing and stirring magnesium oxide and magnesium chloride hexahydrate, adding magnesium sulfate during stirring, and grinding and filtering after the magnesium sulfate is added to obtain a magnesium chloride cement-based binder;
and heating the chloromagnesium cement-based binder, adding a crystal form control agent, an anti-halogen agent and a waterproof agent respectively, and stirring uniformly to obtain the modified chloromagnesium cement.
10. The method for manufacturing a laminate flooring according to claim 9, wherein the mass ratio of the magnesium oxide to the magnesium chloride hexahydrate is (5 to 16): 1;
the addition amount of the magnesium sulfate is 10 to 20 percent of the total mass of the magnesium oxide and the magnesium chloride hexahydrate;
the addition amount of the crystal form control agent is 1 to 5 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the addition amount of the halogen-resistant agent is 1 to 10 percent of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate;
the addition amount of the waterproof agent is 1-10% of the total mass of magnesium sulfate, magnesium oxide and magnesium chloride hexahydrate.
11. The method for preparing the laminate flooring of claim 7, wherein the flame retardant is one or a combination of organic phosphorus flame retardant, inorganic phosphorus flame retardant, melamine cyanurate, zinc borate, magnesium hydroxide, melamine and pentaerythritol;
the curing agent is one or a combination of a dicyandiamide curing agent, a diamino imidazole triazine complex, an organic hydrazide curing agent and a boron trifluoride-amine curing agent;
the addition amount of the flame retardant is 5 to 15 percent of the mass of the epoxy resin;
the addition amount of the toughening agent is 1 to 5 percent of the mass of the epoxy resin;
the addition amount of the curing agent is 1 to 50 percent of the mass of the epoxy resin.
12. The method for manufacturing a laminate flooring according to claim 7, wherein the modified magnesium chloride cement is uniformly mixed with the first base material, and then the mixture is subjected to rolling and hot pressing to obtain a base plate;
the hot pressing treatment process comprises the following steps: the hot pressing temperature is 100 to 200 ℃, and the hot pressing time is 1 to 3min/mm;
the mass ratio of the first base material to the modified magnesium chloride cement is 100: (10 to 50).
13. The method for preparing the reinforced floor as claimed in claim 7, wherein a second base material is dipped in the flame-retardant modified resin, and then dried at 150 to 300 ℃ for 10 to 20s to obtain a cured material;
in the cured material, the mass of the flame-retardant modified resin is 20 to 50 percent of the total mass of the second base material and the flame-retardant modified resin;
the temperature of the pressing and forming is 200 to 220 ℃, the pressure is 5 to 10Mpa, and the time is 16 to 23s.
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