WO2020078096A1 - Synthesized wallpaper base having improved fire resistance and printability, and preparation method therefor - Google Patents

Synthesized wallpaper base having improved fire resistance and printability, and preparation method therefor Download PDF

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Publication number
WO2020078096A1
WO2020078096A1 PCT/CN2019/101281 CN2019101281W WO2020078096A1 WO 2020078096 A1 WO2020078096 A1 WO 2020078096A1 CN 2019101281 W CN2019101281 W CN 2019101281W WO 2020078096 A1 WO2020078096 A1 WO 2020078096A1
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Prior art keywords
parts
layer
wallpaper
materials
skeleton
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PCT/CN2019/101281
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French (fr)
Chinese (zh)
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求秋平
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求秋平
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Publication of WO2020078096A1 publication Critical patent/WO2020078096A1/en

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of synthetic wallpaper, in particular to a synthetic synthetic inorganic environmental protection wallpaper base paper which can replace plant fibers and has improved flame retardancy and printability.
  • Wallpaper is a common interior decoration material.
  • the usual wallpaper is composed of a surface of polyvinyl chloride and other films and traditional fiber paper or traditional fiber paper and inorganic materials and other base materials.
  • the wallpaper substrate produced with paper pulp and wood pulp as raw materials consumes a lot of water and discharges a lot of waste water in the papermaking process.
  • the prepared wallpaper is not only flame-retardant, but also consumes a lot of natural materials such as trees. Resources.
  • the surface of this wallpaper usually contains a relatively high content of organic film components.
  • the synthetic paper produced by the blown film method and the casting method has better physical and mechanical properties than traditional paper, and it is resistant to moisture, water, corrosion, and stability. Good, there is no three waste emissions in the production process, no pollution to the environment, and can recycle synthetic paper repeatedly, is an excellent environmentally friendly material. However, this type of material has low strength, poor curlability and printability, and is suitable as a hard material base material, and is not suitable as a beautiful and decorative flexible wallpaper material.
  • the improved environmental protection wallpaper base paper is mainly produced by using environmentally friendly resin polymers such as polyethylene and polypropylene as the base material for inorganic filling, and then blowing and foaming.
  • the resin material not only has poor flame resistance, but also has poor adhesion and low compatibility in the production process of multilayer composites.
  • the related art of wallpaper can be exemplified as follows.
  • CN201711298871 discloses an environmentally friendly antibacterial wallpaper, including the following parts by weight of uraca fiber 11-17, sodium alginate 23-34, antioxidant 6-11, compatibilizer 2-7, flame retardant 0.8-3.4 , Alfalfa fiber 26-43, nano graphene particles 22-35, polylactic acid fiber 6-13, glutinous rice slurry 36-49; the soluble solid content of the glutinous rice slurry is 45% -55%; the polylactic acid The monofilament diameter of the fiber is 0.1-0.3 mm, and the monofilament length of the polylactic acid fiber is 22-34 mm.
  • the utility model CN201720735485 discloses a PVC environmental protection wallpaper, which includes a main body layer and a safety layer.
  • the safety layer covers the main body layer.
  • the safety layer includes a flame retardant layer and a waterproof layer arranged in order from top to bottom, and the flame retardant layer is covered with a protective film ,
  • the protective film is evenly provided with protrusions on the four corners
  • the main body layer includes a decorative layer, a base layer and an adhesive layer which are arranged in order from top to bottom.
  • a thermosensitive color-changing layer is arranged above the decorative layer.
  • the waterproof layer is connected, and the base layer includes a temperature control layer, a PVC resin layer, a moisture-proof layer, and an adhesive layer arranged in order from top to bottom, and the temperature control layer includes an ultraviolet absorption layer and an insulation layer.
  • CN201710766696 discloses a production method of environmentally friendly flame retardant wallpaper, which is characterized by the following steps: base paper sending, coating, drying, cooling, printing gravure, drying between the plates, softening, and embossing.
  • Multi-layer paper is used as the base paper, the transverse water-immersion elongation of the base paper is controlled at 1.3-1.5%, and the sending tension of the base paper is controlled within the range of 12-16KGF.
  • the coated coating formulation mainly includes: bamboo charcoal fiber material and environmental protection adhesive, environmental protection flame retardant coating, PVC, DOP, calcium carbonate, stabilizer, titanium dioxide, viscosity reducing agent.
  • bamboo charcoal fiber materials and environmentally friendly adhesives are 20PHR
  • environmentally friendly flame retardant coatings are 10PHR
  • PVC is 100PHR
  • DOP is 60PHR
  • calcium super acid 75PHR titanium dioxide is 15-18PHR
  • stabilizer is 3PHR
  • viscosity reducer is 10 -20PHR
  • the above coating is formulated into a paste in the above ratio, and the paste is evenly coated on the surface of the base paper with a coating knife.
  • CN201710540751 discloses an environmentally friendly antibacterial wallpaper, which is made of base paper and base paper coated with PVC paste by heating, embossing, and printing patterns.
  • the PVC paste includes the following raw materials to make PVC 450 resin powder , Modified attapulgite powder, modified bamboo fiber, nano titanium dioxide, nano barium sulfate, guar gum, polyacrylate, epoxy soybean oil, phthalate, dispersant, foaming agent, foam stabilization Agent and flame retardant.
  • the preparation method is prepared by adding water to the raw materials, stirring and mixing and grinding.
  • CN201710410601 discloses a modified diatomite antibacterial and environmentally friendly interior room wallpaper, which relates to the field of wallpaper.
  • the wallpaper is made of base paper and base paper coated with PVC paste by heating, embossing and printing patterns.
  • the PVC paste Materials include the following raw materials SG-2 PVC powder, modified diatomaceous earth, attapulgite powder, nanometer calcium carbonate, anatase titanium dioxide, cellulose, gum arabic, ethyl acrylate, dimethyl fumarate, palm oil , Zinc oxide, aluminum nitride, sodium oleate, isopropyl paraben, ethyltrimethoxysilane, N-methylolacrylamide, polyhexamethylene adipate, plasticizer, dispersant , Foaming agent, foam stabilizer, mildew inhibitor.
  • CN201510398290 discloses a bio-based environmentally friendly flame-retardant wallpaper and a preparation method thereof. It first selects algae fiber and wood pulp for mixing and beating to obtain a mixed slurry, and adds a dispersant to the mixed slurry for papermaking and drying to obtain base paper; then in turn The alginate colloid, PVC, calcium carbonate and DOP paste are evenly coated on the surface of the base paper obtained in step a; finally, after drying, cooling, printing and other steps, it is cut into the required specifications to obtain wallpaper.
  • the invention uses chopped seaweed fibers as pulp fibers, and the metal ions inside the seaweed fibers play a catalytic cracking role, thereby reducing the generation of flammable gases, forming an alkaline environment, and generating CO2 And dilute the flammable gas, form a metal oxide and metal carbonate solid barrier on the fiber surface, and finally achieve the flame retardant effect of less smoke (essentially no smoke) and no melting drops.
  • CN201611012520 discloses an environmental protection wallpaper, including a bottom layer, a self-adhesive layer, a waterproof layer, a base layer, a sound absorption layer, an absorption layer, and a decorative layer; the sound absorption layer is a wood wool layer, and the absorption layer is a nano-montmorillonite layer
  • the adhesive of the adhesive layer is made of rosin, acetic acid, ethylene, starch and straw ethanol gasoline.
  • the diatomite wallpaper includes a bottom layer (1), a diatomite layer (2), a pattern color layer (3), and a wear-resistant layer arranged in this order from bottom to top. 4); wherein, the wear-resistant layer (4) is made of polytetrafluoroethylene.
  • the thickness of the diatomite layer (2) is 0.1mm-0.3mm.
  • the bottom layer (1) is glass fiber fabric, non-woven fabric or chemical fiber fabric. Bamboo carbon black is provided on the wear-resistant layer (4).
  • the diatomaceous earth in the diatomaceous earth layer (2) is to add the raw diatomaceous earth with a particle size of 800-3000 mesh and the surface treatment agent accounting for 0.5-1% of the weight of the raw soil together into the temperature-increasing high-speed mixer, Under the condition of 80-120 °C, it can be obtained by high-speed stirring treatment for 90min.
  • the patent CN102444055A discloses an environmentally friendly wall decoration wallpaper material and its preparation method.
  • the published wallpaper uses the base paper layer as the base layer and then coats it on one or both sides; the coating layer contains 60-90 parts by weight of PE plastic and 15-25 parts by weight of thermoplastic EPDM rubber.
  • the production process of this wallpaper is complicated, and it still needs to use the plant fiber layer as the base layer.
  • This wallpaper is resistant to temperature differences and is not easy to process rich three-dimensional patterns.
  • Patent CN202826606U published an environmentally friendly flame retardant wallpaper, in which the polymer composite material with fillers was prepared into the base layer of the wallpaper through the calendering process, and then the flame retardant was coated on both sides or one side of the base paper to prepare flame retardant wallpaper.
  • the utility model patent discloses the molding process of the wallpaper, but does not involve the composition and preparation method of the base material.
  • the general flame-retardant materials are aluminum hydroxide and magnesium hydroxide, which are in the form of white powder, which are cheap, have good thermal stability, and have the characteristics of smoke elimination, flame retardancy, low toxicity, and no secondary pollution during combustion. Fuel can also be used as filler.
  • the paper produced by using it as a flame retardant has good flame retardant performance and high whiteness. Its flame retardant mechanism mainly utilizes the endothermic effect and dilution effect: endothermic heat during decomposition, which suppresses the rise of polymer temperature and makes the polymer The rate of degradation to low molecules slows down, reducing the production of combustible gases and easing the burning of polymers.
  • wallpaper as a carrier for printing patterns, in addition to environmental protection and flame retardancy, also needs excellent coloring and other printing and dyeing properties.
  • excellent bending resistance is also one of the current needs, which requires new composite materials with high melt strength and molecular chain flexibility.
  • the technical problem to be solved by the present invention is mainly to overcome the existing wallpaper base paper with high plant fiber content, high inorganic synthetic wallpaper plasticizer content, high density, poor flexibility, poor flame retardancy and printability, and poor integrity, Moreover, the manufacturing process is complicated.
  • the first object of the present invention is to provide a polymer-inorganic material composite synthetic wallpaper base paper with low density, high flexibility, good flame retardancy and excellent printing and dyeing performance.
  • Another object of the present invention is to provide a method for preparing the above-mentioned wallpaper base paper without a large number of plasticizer addition steps, the process is simple, the cost is low, and it is suitable for large-scale industrial production.
  • a polymer-inorganic material composite wallpaper base paper which includes a fiber web skeleton layer and a surface material bonding layer; the fiber mesh skeleton layer and the surface material bonding layer are composed of the same matrix composite material and corresponding additives,
  • the matrix composite material includes polymer materials, inorganic materials and other components. Specifically, the matrix composite material is composed of the following components by weight:
  • the skeleton layer further contains the following parts by weight of skeleton layer auxiliary agent A on the basis of the above matrix composite material:
  • the bonding layer further contains the following parts by weight of bonding layer auxiliary agent B:
  • the particle size of the ultrafine inorganic ore powder does not exceed 5 microns, preferably the particle size is 0.1 to 2 microns.
  • the titanate coupling agent is preferably an alkoxy type coupling agent, which is usually commercially available, for example, NDZ series titanate coupling agent, NDZ-201 and the like.
  • the maleic anhydride copolymer is a graft copolymer, which can be selected from those common in the art with compatibility effects, such as polyethylene-based and polypropylene-based graft copolymers.
  • the antioxidant may be selected from those commonly used in the papermaking field, such as tris (di-tert-butylphenyl) phosphite, DSTDP and the like.
  • the modified carboxymethyl cellulose is prepared by modifying epichlorohydrin, and is specifically prepared by the following steps:
  • the amphoteric modified polyacrylamide is a polyacrylamide containing zwitterions in its molecules, and the long polymer chains can penetrate through the paper fibers through physical cross-linking and adsorption, thereby improving the paper The role of strength.
  • amphoteric polyacrylamide also retains other excellent properties of polyacrylamide, such as cementing properties, and is particularly suitable for enhancing the adhesion between composite inorganic materials; more importantly, in the printing and dyeing industry, polyacrylamide is an excellent pigment Auxiliary agent, can enhance the fastness of dye attachment, improve coloring and high vividness.
  • the modified polyacrylamide can be prepared by water dispersion polymerization technology, and the specific steps are as follows:
  • the layered composite metal oxide is an anionic layered compound whose main structure is generally a hydroxide of two metals of magnesium and aluminum, and the structure is usually [M 1-x 2+ M x 3+ ( OH) 2 ] x + A x / n n- , where M 2+ refers to a divalent metal ion, M 3+ refers to a trivalent metal ion, and A refers to an interlayer anion with a valence of n.
  • M 2+ refers to a divalent metal ion
  • M 3+ refers to a trivalent metal ion
  • A refers to an interlayer anion with a valence of n.
  • Magnesium hydroxide and aluminum hydroxide are commonly used inorganic flame retardants. Compared with them, the layered composite metal oxide has a wider thermal decomposition temperature range and better flame retardant performance. It is a more efficient class developed in recent years.
  • the flame retardant mechanism is: when heated to 450 ⁇ 550 °C, most of the composite metal oxide CO32- converted to CO2, and decomposed into loose and porous magnesium aluminum bimetallic oxide, in the process of thermal decomposition, absorb a lot of heat, Reduces the temperature of the combustion system, and at the same time releases non-combustible gases, such as CO2, etc., dilutes the oxygen and flammable gases around the combustion system; the metal oxide produced by the decomposition coats the surface of the combustibles, blocking the communication between oxygen and flammable gases And has a smoke suppressant effect.
  • the layered composite metal oxide of the present invention is prepared by the following method: in 1000 ml of deionized water, 1 mol ⁇ -Al2O3 nano molecular sieve is added as a reaction carrier, and 1-1.5 mol magnesium chloride powder, 0.5-1 mol aluminum chloride and Optional zinc borate 0.3-0.5mol, after stirring evenly, slowly add an alkaline solution containing 3-6mol sodium hydroxide or potassium hydroxide with a mass fraction of 30-50% under stirring at room temperature, after adding the alkaline solution After continuing to stir the reaction for 0.5-1 hour, followed by crystallization treatment at 80-90 ° C in a sealed polytetrafluoroethylene-lined reaction kettle for 3-5 hours, the precipitate was filtered, washed with alcohol, vacuum dried, and ground to prepare the Layered composite metal oxide as a flame retardant component.
  • the present invention also provides a preparation method of the polymer-inorganic material composite wallpaper base paper, which mainly includes the construction of a web skeleton and the bonding of surface materials.
  • the specific steps are as follows:
  • S1 Prepare the raw materials of the main materials according to the proportion, and add the appropriate amounts of additives A and B respectively to obtain the raw materials required for the skeleton layer and the bonding layer. Mix them separately at room temperature. After mixing evenly, perform the vacuum drying process. Heating and granulating in the granulator;
  • the prepared wallpaper base paper can then be subjected to corona treatment, gumming, surface coating and other treatments to form various wallpapers.
  • the thickness of the wallpaper base paper prepared by the present invention may be 0.02 to 1.0 mm, preferably 0.05 to 0.8 mm.
  • the screw extruder of the present invention may be a twin screw extruder or a single screw extruder.
  • the wallpaper base paper of the present invention introduces a directional artificial fiber network skeleton with a pseudo-nonwoven fabric structure, which is formed by hot-melt tiling and surface lamination process. Compared with ordinary wallpaper base paper, it enhances the strength of the skeleton and other physical and mechanical properties. The density of the product drops and the gram weight is reduced, and the rough mesh bottom and a large number of voids provide better adhesion to the wallpaper after being glued.
  • the surface layer of the wallpaper-based paper of the present invention has a higher content of organic materials, which does not require a film, that is, has good waterproof and oil-proof effects, is easy to clean, and has improved tearing and folding resistance.
  • the surface layer of the wallpaper base paper of the present invention has better flame retardancy under the premise of a lower content of flame retardant, and has better ink absorption than ordinary wallpaper, and improves the coloring of the pigment, and has better Pattern decorative effect.
  • the wallpaper base paper surface layer and the skeleton layer of the present invention have basically the same main material, good compatibility, and firm bonding, avoiding the defects of a large amount of plasticizer pollutants in the existing wallpaper.
  • the wallpaper base paper of the present invention improves the strength of the paper by adding modified polyacrylamide, and also enhances the fastness of dye attachment, improves the coloring, has high vividness and good durability.
  • the preparation method of the wallpaper base paper of the present invention is simple, the operation is convenient, and it is suitable for large-scale industrial production.
  • compositions, step, method, article, or device that includes the listed elements need not be limited to those elements, but may include other elements not specifically listed or inherent to such a composition, step, method, article, or device Elements.
  • the raw material components of the skeleton layer are as follows:
  • the raw material components of the bonding layer are as follows:
  • S7 Heat-bonded synthetic type: Place the coarse product of the bonding layer on the skeleton web of the non-woven fabric structure in the bonding machine, heat to 120 °C for hot-melt bonding, and roll-bond to a suitable thickness of 200 microns , Leveling, cooling and cooling, that is to obtain the polymer-inorganic material composite wallpaper base paper.
  • the wallpaper base paper prepared in this example has a coloring bond strength (ASTM 633-2001) value of 35N at room temperature and 50% humidity; its flame retardant performance is 4s for flame retention time and 14s for ignition time.
  • the requirements of GB / T 14656-2009 (according to the definition of GB / T14656-2009, the flame retention time is the time that the sample continues to burn flamingly after the flame of the Bunsen burner is removed.
  • the burning time refers to the time after the flame goes out Flameless burning time).
  • the flame retention time of the wallpaper-based paper is 5s and the burning time is as high as 26s.
  • Copolymer polypropylene 30 parts thermoplastic polyester PET 10 parts, polyethylene 5 parts, ultrafine inorganic mineral powder calcium carbonate or talc 70 parts, anatase titanium dioxide 5 parts, titanate coupling agent 2 parts, twelve Sodium alkyl sulfate 0.5 parts, maleic anhydride copolymer 1.5 parts, epoxy modified carboxymethyl cellulose 3 parts, stearic acid 1 part, paraffin 1.5 parts, nano titanium dioxide 3 parts, antioxidant DSTDP 0.2 parts; And auxiliary A: 5 parts of chopped aramid fiber, 0.2 parts of foaming agent ADC, and 5 parts of chopped polyimide fiber;
  • the raw material component of the bonding layer is the raw material component of the bonding layer
  • S7 Heat-bonded synthetic type: Place the coarse product of the bonding layer on the skeleton web of the non-woven fabric structure in the bonding machine, heat to 120 °C for hot-melt bonding, and roll-bond to a suitable thickness of 300 microns , Leveling, cooling and cooling, that is to obtain the polymer-inorganic material composite wallpaper base paper.
  • the wallpaper base paper prepared in Example 2 was tested at room temperature and 50% humidity to test the coloring bond strength (ASTM 633-2001) value is 37N; its flame retardant properties are: flame time 3s, burning time 10s , Meet the requirements of GB / T 14656-2009.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

A synthesized wallpaper base having improved fire resistance and printability, and preparation method therefor. The base comprises a fiber web framework layer and a surface material bonding layer. The fiber web framework layer and the surface material bonding layer consist of a same matrix composite and corresponding additives. The matrix composite specifically consists of the following components in parts by weight: 20-30 parts of copolypropylene, 5‑10 parts of thermoplastic polyester PET, 3-5 parts of polyethylene, 50-70 parts of ultramicro inorganic mineral powder, i.e., calcium carbonate or talcum powder, 3-5 parts of anatase titanium dioxide, or the like. The framework layer further comprises a framework layer additive A, and the bonding layer further comprises a bonding layer additive B.

Description

一种改善阻燃性和适印性的合成壁纸基纸及制备方法Synthetic wallpaper base paper with improved flame retardancy and printability and preparation method 技术领域Technical field
本发明涉及合成壁纸技术领域，具体涉及一种可代替植物纤维的改善阻燃性、适印性的人工合成无机环保壁纸基纸。The invention relates to the technical field of synthetic wallpaper, in particular to a synthetic synthetic inorganic environmental protection wallpaper base paper which can replace plant fibers and has improved flame retardancy and printability.
背景技术Background technique
壁纸是常见的室内装饰材料，通常的壁纸是有由表面的聚氯乙烯等薄膜与传统纤维纸或者由传统纤维纸与无机材料等基材复合而成。以纸浆、木浆为原料生产的壁纸基材，在造纸过程中要消耗大量的水，并排放大量的废水，所制备得到的壁纸不仅具有阻燃性，而且还要耗料大量的树木等自然资源。另外，这种壁纸表面通常含有较高含量的有机薄膜组分，这种高含量的有机组份不仅易燃，而且难于着色，因此在其中添加大量的增塑剂(例如邻苯二甲酸二辛酯等)及大量的含有重金属铅和铬的助染剂才能够使得壁纸易于着色，随着提高了着色性和印刷性，但是使得壁纸环保性差，对身体健康造成隐患。随着人们对于环保的要求日益提高，该类壁纸逐渐不能满足目前市场上环保的需求。Wallpaper is a common interior decoration material. The usual wallpaper is composed of a surface of polyvinyl chloride and other films and traditional fiber paper or traditional fiber paper and inorganic materials and other base materials. The wallpaper substrate produced with paper pulp and wood pulp as raw materials consumes a lot of water and discharges a lot of waste water in the papermaking process. The prepared wallpaper is not only flame-retardant, but also consumes a lot of natural materials such as trees. Resources. In addition, the surface of this wallpaper usually contains a relatively high content of organic film components. This high content of organic components is not only flammable, but also difficult to color, so a large amount of plasticizer (such as dioctyl phthalate) is added to it Ester, etc.) and a large amount of dyes containing heavy metals lead and chromium can make the wallpaper easy to color, with the improvement of coloring and printability, but the environmental protection of the wallpaper is poor, causing hidden dangers to health. With the increasing requirements for environmental protection, this type of wallpaper is gradually unable to meet the needs of environmental protection in the current market.
虽然市场上出现了以塑料、碳酸钙及多种助剂为原料，用吹膜法、流延法生产的人工合成纸，物理机械性能优于传统纸，耐潮湿、防水，耐腐蚀，稳定性好，生产过程中无三废排放，对环境无污染，并可将合成纸重复循环利用，是优良的环保型材料。但是，该类材料强度低，卷曲性和印刷性差，适合作为硬质材料基材，不适合作为美观装饰性的柔性壁纸材料。Although there are plastics, calcium carbonate and various additives as raw materials, the synthetic paper produced by the blown film method and the casting method has better physical and mechanical properties than traditional paper, and it is resistant to moisture, water, corrosion, and stability. Good, there is no three waste emissions in the production process, no pollution to the environment, and can recycle synthetic paper repeatedly, is an excellent environmentally friendly material. However, this type of material has low strength, poor curlability and printability, and is suitable as a hard material base material, and is not suitable as a beautiful and decorative flexible wallpaper material.
目前改善的环保性壁纸基纸，主要是利用环保树脂聚合物例如聚乙烯聚丙烯等为基材进行无机填充，然后吹塑发泡生产得到。但是树脂材料不仅耐燃性差，而且在多层复合的生产工艺中具有较差的贴合性以及低相容性。壁纸的相关现有技术可举例如下。At present, the improved environmental protection wallpaper base paper is mainly produced by using environmentally friendly resin polymers such as polyethylene and polypropylene as the base material for inorganic filling, and then blowing and foaming. But the resin material not only has poor flame resistance, but also has poor adhesion and low compatibility in the production process of multilayer composites. The related art of wallpaper can be exemplified as follows.
CN201711298871公开了一种环保抗菌壁纸，包括以下重量份数的组分乌拉草纤维11-17、海藻酸钠23-34、抗氧化剂6-11、相容剂2-7、阻燃剂0.8-3.4、苜蓿纤维26-43、纳米石墨烯颗粒22-35、聚乳 酸纤维6-13、糯米浆料36-49；所述糯米浆料的可溶性固形物含量为45％-55％；所述聚乳酸纤维的单丝直径为0.1-0.3mm，所述聚乳酸纤维的单丝长度为22-34mm。CN201711298871 discloses an environmentally friendly antibacterial wallpaper, including the following parts by weight of uraca fiber 11-17, sodium alginate 23-34, antioxidant 6-11, compatibilizer 2-7, flame retardant 0.8-3.4 , Alfalfa fiber 26-43, nano graphene particles 22-35, polylactic acid fiber 6-13, glutinous rice slurry 36-49; the soluble solid content of the glutinous rice slurry is 45% -55%; the polylactic acid The monofilament diameter of the fiber is 0.1-0.3 mm, and the monofilament length of the polylactic acid fiber is 22-34 mm.
实用新型CN201720735485公开了PVC环保壁纸，包括主体层和安全层，安全层覆盖在主体层上，安全层包括从上往下依次设置的阻燃层和防水层，阻燃层的上方覆有保护膜，保护膜的四周角上均匀设置有凸起部，主体层包括从上往下依次设置的装饰层、基底层和粘黏层，装饰层的上方设置有感温变色层，感温变色层与防水层相连接，基底层包括从上往下依次设置的温控层、PVC树脂层、防潮层和粘黏层，温控层包括紫外线吸收层和保温层。The utility model CN201720735485 discloses a PVC environmental protection wallpaper, which includes a main body layer and a safety layer. The safety layer covers the main body layer. The safety layer includes a flame retardant layer and a waterproof layer arranged in order from top to bottom, and the flame retardant layer is covered with a protective film , The protective film is evenly provided with protrusions on the four corners, the main body layer includes a decorative layer, a base layer and an adhesive layer which are arranged in order from top to bottom. A thermosensitive color-changing layer is arranged above the decorative layer. The waterproof layer is connected, and the base layer includes a temperature control layer, a PVC resin layer, a moisture-proof layer, and an adhesive layer arranged in order from top to bottom, and the temperature control layer includes an ultraviolet absorption layer and an insulation layer.
CN201710766696公开了一种环保阻燃壁纸的生产方法，其特征在于，包括如下步骤原纸发送、涂布、干燥、冷却、印刷凹版、版间干燥、软化、压花。原纸采用多层纸，原纸的横向浸水伸长率控制在1.3-1.5％，原纸发送张力控制在12-16KGF范围内。所述涂布的涂料配方主要包括：竹炭纤维材料和环保粘合剂、环保阻燃涂料、PVC，DOP，碳酸钙、安定剂，钛白粉，降粘剂。其中，竹炭纤维材料和环保粘合剂为20PHR、环保阻燃涂料为10PHR、PVC为100PHR，DOP为60PHR，太酸钙75PHR，钛白粉为15-18PHR，安定剂为3PHR、降粘剂为10-20PHR，将上述涂料按上述比例配制成糊料，用涂布刀将糊料均匀涂在原纸表面。CN201710766696 discloses a production method of environmentally friendly flame retardant wallpaper, which is characterized by the following steps: base paper sending, coating, drying, cooling, printing gravure, drying between the plates, softening, and embossing. Multi-layer paper is used as the base paper, the transverse water-immersion elongation of the base paper is controlled at 1.3-1.5%, and the sending tension of the base paper is controlled within the range of 12-16KGF. The coated coating formulation mainly includes: bamboo charcoal fiber material and environmental protection adhesive, environmental protection flame retardant coating, PVC, DOP, calcium carbonate, stabilizer, titanium dioxide, viscosity reducing agent. Among them, bamboo charcoal fiber materials and environmentally friendly adhesives are 20PHR, environmentally friendly flame retardant coatings are 10PHR, PVC is 100PHR, DOP is 60PHR, calcium super acid 75PHR, titanium dioxide is 15-18PHR, stabilizer is 3PHR, viscosity reducer is 10 -20PHR, the above coating is formulated into a paste in the above ratio, and the paste is evenly coated on the surface of the base paper with a coating knife.
CN201710540751公开了一种环保型抗菌壁纸，该壁纸是由基层纸和基层纸上覆涂PVC糊料经加热、压花、印制图案制成，该PVC糊料包括以下原料制成PVC 450树脂粉、改性凹土粉、改性竹纤维、纳米钛白粉、纳米硫酸钡、瓜尔胶、聚丙烯酸酯、环氧大豆油、邻苯二甲丁苄酯、分散剂、发泡剂、稳泡剂和阻燃剂。其制备方法是通过对原料的加水搅拌混匀及研磨制得的。CN201710540751 discloses an environmentally friendly antibacterial wallpaper, which is made of base paper and base paper coated with PVC paste by heating, embossing, and printing patterns. The PVC paste includes the following raw materials to make PVC 450 resin powder , Modified attapulgite powder, modified bamboo fiber, nano titanium dioxide, nano barium sulfate, guar gum, polyacrylate, epoxy soybean oil, phthalate, dispersant, foaming agent, foam stabilization Agent and flame retardant. The preparation method is prepared by adding water to the raw materials, stirring and mixing and grinding.
CN201710410601公开了一种改性硅藻土抗菌环保内室壁纸，涉及壁纸领域，该壁纸是由基层纸和基层纸上覆涂PVC糊料经加热、压花、印制图案制成，该PVC糊料包括以下原料SG-2 PVC粉、改性硅藻土、凹土粉、纳米级碳酸钙、锐钛型钛白粉、纤维素、***胶、丙烯酸乙酯、富马酸二甲酯、棕榈油、氧化锌、氮化铝、油酸钠、 对羟苯甲酸异丙酯、乙基三甲氧基硅烷、N-羟甲基丙烯酰胺、聚己二酸己二醇酯、增塑剂、分散剂、发泡剂、稳泡剂、防霉剂。CN201710410601 discloses a modified diatomite antibacterial and environmentally friendly interior room wallpaper, which relates to the field of wallpaper. The wallpaper is made of base paper and base paper coated with PVC paste by heating, embossing and printing patterns. The PVC paste Materials include the following raw materials SG-2 PVC powder, modified diatomaceous earth, attapulgite powder, nanometer calcium carbonate, anatase titanium dioxide, cellulose, gum arabic, ethyl acrylate, dimethyl fumarate, palm oil , Zinc oxide, aluminum nitride, sodium oleate, isopropyl paraben, ethyltrimethoxysilane, N-methylolacrylamide, polyhexamethylene adipate, plasticizer, dispersant , Foaming agent, foam stabilizer, mildew inhibitor.
CN201510398290公开了一种生物基环保型阻燃壁纸及其制备方法，其首先选用海藻纤维与木浆进行混合打浆得混合浆液，向该混合浆液中加入分散剂进行抄纸、干燥得到原纸；然后依次将海藻酸盐胶体、PVC、碳酸钙和DOP糊料均匀涂覆在步骤a所得原纸的表面；最后经过干燥、冷却、印花等步骤将其裁剪成所需规格即得壁纸。本发明在不添加任何阻燃剂的前提下，以短切海藻纤维作为纸浆纤维，通过海藻纤维内部的金属离子起到催化裂解作用，减少了可燃性气体的生成、形成碱性环境、生成CO2并稀释可燃性气体、在纤维表面形成金属氧化物和金属碳酸盐固态屏障，最终达到发烟少(基本不发烟)、无融滴等阻燃的效果。CN201510398290 discloses a bio-based environmentally friendly flame-retardant wallpaper and a preparation method thereof. It first selects algae fiber and wood pulp for mixing and beating to obtain a mixed slurry, and adds a dispersant to the mixed slurry for papermaking and drying to obtain base paper; then in turn The alginate colloid, PVC, calcium carbonate and DOP paste are evenly coated on the surface of the base paper obtained in step a; finally, after drying, cooling, printing and other steps, it is cut into the required specifications to obtain wallpaper. Under the premise of not adding any flame retardant, the invention uses chopped seaweed fibers as pulp fibers, and the metal ions inside the seaweed fibers play a catalytic cracking role, thereby reducing the generation of flammable gases, forming an alkaline environment, and generating CO2 And dilute the flammable gas, form a metal oxide and metal carbonate solid barrier on the fiber surface, and finally achieve the flame retardant effect of less smoke (essentially no smoke) and no melting drops.
CN201611012520公开了一种环保壁纸，包括底层、不干胶层、防水层、基层、吸音层、吸附层和装饰层；所述的吸音层为木丝层，所述吸附层为纳米蒙脱石层，所述不干胶层的不干胶由松香、乙酸、乙烯、淀粉和秸秆乙醇汽油制成。CN201611012520 discloses an environmental protection wallpaper, including a bottom layer, a self-adhesive layer, a waterproof layer, a base layer, a sound absorption layer, an absorption layer, and a decorative layer; the sound absorption layer is a wood wool layer, and the absorption layer is a nano-montmorillonite layer The adhesive of the adhesive layer is made of rosin, acetic acid, ethylene, starch and straw ethanol gasoline.
CN201611013856公开了一种抗菌隔音环保硅藻土壁纸，所述硅藻土壁纸包括从下向上依次设置的底层(1)、硅藻土层(2)、图案颜色层(3)以及耐磨层(4)；其中，所述耐磨层(4)采用聚四氟乙烯材料。所述硅藻土层(2)的厚度为0.1mm-0.3mm。所述底层(1)为玻璃纤维织物、无纺布织物或者化纤布。所述耐磨层(4)上设置有竹炭黑。所述硅藻土层(2)中的硅藻土是将粒径为800-3000目的硅藻土原土和占原土重量0.5-1％的表面处理剂一起加入到可升温高速搅拌机内，在80-120℃条件下，高速搅拌处理90min得到。CN201611013856 discloses an antibacterial soundproof and environmentally friendly diatomite wallpaper. The diatomite wallpaper includes a bottom layer (1), a diatomite layer (2), a pattern color layer (3), and a wear-resistant layer arranged in this order from bottom to top. 4); wherein, the wear-resistant layer (4) is made of polytetrafluoroethylene. The thickness of the diatomite layer (2) is 0.1mm-0.3mm. The bottom layer (1) is glass fiber fabric, non-woven fabric or chemical fiber fabric. Bamboo carbon black is provided on the wear-resistant layer (4). The diatomaceous earth in the diatomaceous earth layer (2) is to add the raw diatomaceous earth with a particle size of 800-3000 mesh and the surface treatment agent accounting for 0.5-1% of the weight of the raw soil together into the temperature-increasing high-speed mixer, Under the condition of 80-120 ℃, it can be obtained by high-speed stirring treatment for 90min.
此外，专利CN 102444055 A公布了一种环保墙壁装饰壁纸材料及其制备方法，公布的壁纸由原纸层做为基层，然后在其单面或双面进行涂覆；所述的涂覆层包含有60-90重量份的PE塑料和15-25重量份的热塑性三元乙丙动态硫化橡胶。这种壁纸生产工艺复杂，仍然需要利用植物纤维层作为基层，这种壁纸耐温差，不易加工丰富的立体图案。In addition, the patent CN102444055A discloses an environmentally friendly wall decoration wallpaper material and its preparation method. The published wallpaper uses the base paper layer as the base layer and then coats it on one or both sides; the coating layer contains 60-90 parts by weight of PE plastic and 15-25 parts by weight of thermoplastic EPDM rubber. The production process of this wallpaper is complicated, and it still needs to use the plant fiber layer as the base layer. This wallpaper is resistant to temperature differences and is not easy to process rich three-dimensional patterns.
专利CN 202826606 U公布了一种环保阻燃壁纸，其中将添加填 料的聚合物复合材料通过压延工艺制备成壁纸的基层，然后在基纸两面或单面涂覆上阻燃剂，从而制备阻燃壁纸。该实用新型专利公布了该壁纸的成型工艺，但没有涉及基层材料的成分和制备方法。Patent CN202826606U published an environmentally friendly flame retardant wallpaper, in which the polymer composite material with fillers was prepared into the base layer of the wallpaper through the calendering process, and then the flame retardant was coated on both sides or one side of the base paper to prepare flame retardant wallpaper. The utility model patent discloses the molding process of the wallpaper, but does not involve the composition and preparation method of the base material.
可以看出，现有技术中，仍有大量的壁纸基纸仍然含有高含量的植物纤维或有机易燃组分，不仅耐燃性差，而且现有的含有植物纤维的壁纸基材，易发霉腐烂，尤其当空气湿度过大时，吸潮发霉，尤其是湿度大的地域和季节环境；而当空气中的湿度过低时，植物纤维收缩，起皱甚至剥落。为了提高阻燃性，需要添加大量的阻燃剂成分，导致壁纸密度高，克重高，以及升高的成本。一般的阻燃材料为氢氧化铝和氢氧化镁，为白色粉末状，价格便宜，热稳定性好，具有消烟、阻燃、低毒、燃烧时无二次污染等特点，既能做阻燃剂又可做填料。以其作为阻燃剂生产出的纸阻燃性能好、白度高，其阻燃机理主要是利用了吸热效应和稀释效应：分解时吸热，抑制了聚合物温度的上升，使聚合物降解为低分子的速度减慢，减少了可燃气体的产生，缓和了聚合物的燃烧。分解时释放出水蒸气，使可燃性气体和氧气被稀释、冷却，而且分解物覆盖在可燃物表面，阻断氧气和可燃性气体的流动。但是，该类材料的缺陷是，若要阻燃效果明显，填充量比较高，甚至高达60％，因此大大影响了纸的其他性能。It can be seen that in the prior art, a large amount of wallpaper base paper still contains a high content of plant fibers or organic flammable components, which not only has poor flame resistance, but also the existing wallpaper substrates containing plant fibers are prone to mold and rot. Especially when the humidity of the air is too high, it absorbs moisture and mildew, especially in regions and seasonal environments with high humidity; and when the humidity in the air is too low, the plant fibers shrink, wrinkle or even flake. In order to improve flame retardancy, a large amount of flame retardant ingredients need to be added, resulting in high density wallpaper, high grammage, and increased cost. The general flame-retardant materials are aluminum hydroxide and magnesium hydroxide, which are in the form of white powder, which are cheap, have good thermal stability, and have the characteristics of smoke elimination, flame retardancy, low toxicity, and no secondary pollution during combustion. Fuel can also be used as filler. The paper produced by using it as a flame retardant has good flame retardant performance and high whiteness. Its flame retardant mechanism mainly utilizes the endothermic effect and dilution effect: endothermic heat during decomposition, which suppresses the rise of polymer temperature and makes the polymer The rate of degradation to low molecules slows down, reducing the production of combustible gases and easing the burning of polymers. During decomposition, water vapor is released, so that the combustible gas and oxygen are diluted and cooled, and the decomposition product covers the surface of the combustible material, blocking the flow of oxygen and combustible gas. However, the defect of this kind of material is that if the flame retardant effect is obvious, the filling amount is relatively high, even as high as 60%, so it greatly affects other properties of the paper.
虽然现有技术中出现了将高分子材料与无机材料结合的合成壁纸，但是这类壁纸更多的是多层复合贴合结构，整体性差，易分离，而且制作工艺复杂，不易操作、生产成本高，效率低，不适应大范围的工业化生产。Although there are synthetic wallpapers that combine polymer materials and inorganic materials in the prior art, such wallpapers are more of a multi-layer composite lamination structure, which has poor integrity and easy separation, and the manufacturing process is complicated, difficult to operate, and the production cost High, low efficiency, not suitable for large-scale industrial production.
重要的是，壁纸作为印刷图案的载体，除了环保性和阻燃性，还需要优良的着色性等印染性能。另外，由于壁纸用途特性，优良的抗弯曲性也是目前需求之一，这就需要新的具有高熔体强度和分子链的柔韧性的复合材料。It is important that wallpaper as a carrier for printing patterns, in addition to environmental protection and flame retardancy, also needs excellent coloring and other printing and dyeing properties. In addition, due to the characteristics of wallpaper applications, excellent bending resistance is also one of the current needs, which requires new composite materials with high melt strength and molecular chain flexibility.
发明内容Summary of the invention
基于上述需求，本发明所要解决的技术问题主要在于克服现有壁纸基纸植物纤维含量高，无机合成壁纸增塑剂含量高、密度高、柔性差、阻燃性和适印性差，整体性差，而且制作工艺复杂的缺陷。Based on the above requirements, the technical problem to be solved by the present invention is mainly to overcome the existing wallpaper base paper with high plant fiber content, high inorganic synthetic wallpaper plasticizer content, high density, poor flexibility, poor flame retardancy and printability, and poor integrity, Moreover, the manufacturing process is complicated.
为了克服现有技术的不足，本发明的第一个目的在于提供一种低密度高柔性、阻燃性好并具有优良印染性能的高分子-无机材料复合型合成壁纸基纸。In order to overcome the deficiencies of the prior art, the first object of the present invention is to provide a polymer-inorganic material composite synthetic wallpaper base paper with low density, high flexibility, good flame retardancy and excellent printing and dyeing performance.
本发明的另一目的在于提供一种上述壁纸基纸的制备方法，无大量增塑剂添加步骤，工艺简单，成本低，适用于大规模的工业化生产。Another object of the present invention is to provide a method for preparing the above-mentioned wallpaper base paper without a large number of plasticizer addition steps, the process is simple, the cost is low, and it is suitable for large-scale industrial production.
为实现上述目的，本发明所采用的技术方案如下：To achieve the above objectives, the technical solutions adopted by the present invention are as follows:
一种高分子-无机材料复合壁纸基纸，其包括纤网骨架层和表面材料贴合层；所述纤网骨架层和表面材料贴合层由相同的基质复合材料及相应的助剂组成，所述基质复合材料包括高分子材料、无机材料和其他组分，具体地，所述基质复合材料由下列重量份数的组分组成：A polymer-inorganic material composite wallpaper base paper, which includes a fiber web skeleton layer and a surface material bonding layer; the fiber mesh skeleton layer and the surface material bonding layer are composed of the same matrix composite material and corresponding additives, The matrix composite material includes polymer materials, inorganic materials and other components. Specifically, the matrix composite material is composed of the following components by weight:
共聚聚丙烯20-30份，热塑性聚酯PET 5-10份，聚乙烯3-5份，超微无机矿粉碳酸钙或滑石粉50-70份，锐钛型钛白粉3-5份，钛酸酯偶联剂0.5-2份，十二烷基硫酸钠0.2-0.5份，顺丁烯二酸酐共聚物1-1.5份，环氧改性羧甲基纤维素1.5-3份，硬脂酸或硬脂酸酯0.5-1份，石蜡1-1.5份，纳米二氧化钛1-3份，抗氧化剂0.1-0.2份；Copolymer polypropylene 20-30 parts, thermoplastic polyester PET 5-10 parts, polyethylene 3-5 parts, ultra-fine inorganic mineral powder calcium carbonate or talc 50-70 parts, anatase titanium dioxide 3-5 parts, titanium Acid ester coupling agent 0.5-2 parts, sodium lauryl sulfate 0.2-0.5 parts, maleic anhydride copolymer 1-1.5 parts, epoxy modified carboxymethyl cellulose 1.5-3 parts, stearic acid Or 0.5-1 part of stearate, 1-1.5 parts of paraffin, 1-3 parts of nano titanium dioxide, 0.1-0.2 parts of antioxidant;
其中，所述骨架层在上述基质复合材料的基础上，还含有以下重量份的骨架层助剂A：Wherein, the skeleton layer further contains the following parts by weight of skeleton layer auxiliary agent A on the basis of the above matrix composite material:
短切芳纶纤维2-5份；2-5 copies of chopped aramid fiber;
起泡剂ADC 0.1-0.3份，Foaming agent ADC 0.1-0.3 servings,
短切聚酰亚胺纤维2-5份；2-5 copies of chopped polyimide fiber;
所述贴合层在上述基质复合材料的基础上，还含有以下重量份的贴合层助剂B：Based on the above matrix composite material, the bonding layer further contains the following parts by weight of bonding layer auxiliary agent B:
聚乙烯醇1-3份；1-3 parts of polyvinyl alcohol;
两性改性的聚丙烯酰胺增强剂3-5份；3-5 parts of amphoteric modified polyacrylamide reinforcement;
层状复合金属氧化物或改性的层状复合金属氧化物类阻燃剂5-10份。5-10 parts of layered composite metal oxide or modified layered composite metal oxide flame retardant.
其中，所述超微无机矿粉粒径不超过5微米，优选粒径0.1～2微米。Wherein, the particle size of the ultrafine inorganic ore powder does not exceed 5 microns, preferably the particle size is 0.1 to 2 microns.
本发明中，所述钛酸酯偶联剂优选为烷氧基型偶联剂，通常可商购得到，例如NDZ系列钛酸酯偶联剂，NDZ-201等。In the present invention, the titanate coupling agent is preferably an alkoxy type coupling agent, which is usually commercially available, for example, NDZ series titanate coupling agent, NDZ-201 and the like.
本发明中，所述顺丁烯二酸酐共聚物为接枝型共聚物，可选自本领域常见的具有相容性效果的那些，例如聚乙烯基、聚丙烯基接枝共聚物等。In the present invention, the maleic anhydride copolymer is a graft copolymer, which can be selected from those common in the art with compatibility effects, such as polyethylene-based and polypropylene-based graft copolymers.
本发明中，所述抗氧剂可选自造纸领域常用的那些，例如三(二叔丁基苯基)亚磷酸酯，DSTDP等。In the present invention, the antioxidant may be selected from those commonly used in the papermaking field, such as tris (di-tert-butylphenyl) phosphite, DSTDP and the like.
本发明中，所述改性的羧甲基纤维素由环氧氯丙烷改性制得，具体通过如下步骤制备得到：In the present invention, the modified carboxymethyl cellulose is prepared by modifying epichlorohydrin, and is specifically prepared by the following steps:
在带有搅拌的三口烧瓶中，加入200ml水以及20g的羧甲基纤维素溶液，滴加1-1.5g环氧氯丙烷，在室温下搅拌反应2h。反应过程中用氨水调节pH，维持体系pH8-9。反应结束后，用稀释的盐酸中和，调节体系至pH 5，所得产物经醇洗、烘干即可得到环氧改性的羧甲基纤维素，超微粉碎后用作树脂相容剂和高分子分散稳定剂，还具有纸面平滑效果和优良的着色效果。In a three-necked flask with stirring, 200 ml of water and 20 g of carboxymethyl cellulose solution were added, 1-1.5 g of epichlorohydrin was added dropwise, and the reaction was stirred at room temperature for 2 h. During the reaction, the pH was adjusted with ammonia water to maintain the system pH 8-9. After the reaction is completed, neutralize with diluted hydrochloric acid to adjust the system to pH5. The resulting product can be washed with alcohol and dried to obtain epoxy-modified carboxymethyl cellulose, which is used as a resin compatibilizer and The polymer dispersion stabilizer also has paper surface smoothing effect and excellent coloring effect.
本发明中，所述两性改性的聚丙烯酰胺为分子中含有两性离子的聚丙烯酰胺类物质，其中的高分子长链可通过物理交结和吸附作用贯穿于纸张纤维中，从而起到提高纸张强度的作用。In the present invention, the amphoteric modified polyacrylamide is a polyacrylamide containing zwitterions in its molecules, and the long polymer chains can penetrate through the paper fibers through physical cross-linking and adsorption, thereby improving the paper The role of strength.
另外两性聚丙烯酰胺还保留了聚丙烯酰胺的其他优良性能，例如胶结性能，尤其适合增强复合无机材料之间的贴合性；更重要的是，在印染行业中，聚丙烯酰胺是优良的颜料助剂，可增强染料附着牢度，提高着色性，鲜艳度高。In addition, amphoteric polyacrylamide also retains other excellent properties of polyacrylamide, such as cementing properties, and is particularly suitable for enhancing the adhesion between composite inorganic materials; more importantly, in the printing and dyeing industry, polyacrylamide is an excellent pigment Auxiliary agent, can enhance the fastness of dye attachment, improve coloring and high vividness.
具体地，所述改性聚丙烯酰胺可通过水分散聚合技术制备得到，具体步骤如下：Specifically, the modified polyacrylamide can be prepared by water dispersion polymerization technology, and the specific steps are as follows:
将一定比例量的丙烯酰胺、羧甲基纤维素、甲基丙烯酰氧乙基三甲基氯化铵、亚甲基琥珀酸和甲基丙烯酸二甲氨基乙酯单体，溶解在适量水中，并加入过硫铵引发剂、甲基丙烯磺酸盐转移剂，控制其聚合单体质量分数分别为：18-20％、10-12％、4-5％、3-5％和1-2％，引发剂和转移剂质量分数分别为0.2-0.3％、0.5-0.6％，调节pH至3-4，70-75℃搅拌反应1-2小时，反应结束后蒸干溶剂，烘干产物，研磨，即可得到改性的聚丙烯酰胺聚合物。Dissolve a certain amount of acrylamide, carboxymethyl cellulose, methacryloyloxyethyl trimethyl ammonium chloride, methylene succinic acid, and dimethylaminoethyl methacrylate monomer in the appropriate amount of water, Add ammonium persulfate initiator and methacrylic acid sulfonate transfer agent to control the mass fraction of its polymerized monomers: 18-20%, 10-12%, 4-5%, 3-5% and 1-2 %, The mass fractions of initiator and transfer agent are 0.2-0.3% and 0.5-0.6% respectively, adjust the pH to 3-4, stir and react at 70-75 ° C for 1-2 hours, after the reaction is over, evaporate the solvent and dry the product, After grinding, the modified polyacrylamide polymer can be obtained.
本发明中，所述层状复合金属氧化物是一类主体结构一般为镁铝两种金属的氢氧化物的阴离子型层状化合物，结构通常为 [M 1-x 2+M x 3+(OH) 2] x+A x/n n-，式中M 2+指二价金属离子，M 3+指三价属离子，A指价数为n的层间阴离子。氢氧化镁、氢氧化铝等是常用的无机阻燃剂，与它们相比，层状复合金属氧化物的热分解温度范围更宽、阻燃性能更好，是近年来开发的一类更高效环保的无机阻燃剂。其阻燃机理为：加热到450～550℃时，复合金属氧化物大部分CO32-转变为CO2，并分解成为疏松多孔的镁铝双金属氧化物，在热分解过程中，吸收大量的热，降低了燃烧体系的温度，同时释放出不燃的气体，如CO2等，冲淡燃烧体系周围的氧气和可燃性气体；分解产生的金属氧化物包覆在燃烧物表面，隔绝氧气与可燃性气体的交流，并具有抑烟作用。 In the present invention, the layered composite metal oxide is an anionic layered compound whose main structure is generally a hydroxide of two metals of magnesium and aluminum, and the structure is usually [M 1-x 2+ M x 3+ ( OH) 2 ] x + A x / n n- , where M 2+ refers to a divalent metal ion, M 3+ refers to a trivalent metal ion, and A refers to an interlayer anion with a valence of n. Magnesium hydroxide and aluminum hydroxide are commonly used inorganic flame retardants. Compared with them, the layered composite metal oxide has a wider thermal decomposition temperature range and better flame retardant performance. It is a more efficient class developed in recent years. Environmentally friendly inorganic flame retardant. The flame retardant mechanism is: when heated to 450 ~ 550 ℃, most of the composite metal oxide CO32- converted to CO2, and decomposed into loose and porous magnesium aluminum bimetallic oxide, in the process of thermal decomposition, absorb a lot of heat, Reduces the temperature of the combustion system, and at the same time releases non-combustible gases, such as CO2, etc., dilutes the oxygen and flammable gases around the combustion system; the metal oxide produced by the decomposition coats the surface of the combustibles, blocking the communication between oxygen and flammable gases And has a smoke suppressant effect.
具体地，本发明所述层状复合金属氧化物通过如下方法制备：在1000ml去离子水中，加入1molγ-Al2O3纳米分子筛作为反应载体，并加入1-1.5mol氯化镁粉末、0.5-1mol氯化铝以及任选的硼酸锌0.3-0.5mol，搅拌均匀后，室温下在搅拌条件下缓慢加入含3-6mol氢氧化钠或氢氧化钾的质量分数为30-50％的碱性溶液，加入碱液完毕后继续搅拌反应0.5-1小时，随后在聚四氟乙烯内衬的密闭反应釜中80-90℃下晶化处理3-5h，将沉淀过滤，醇洗，真空干燥，研磨，制得所述层状复合金属氧化物，作为阻燃组分。Specifically, the layered composite metal oxide of the present invention is prepared by the following method: in 1000 ml of deionized water, 1 mol γ-Al2O3 nano molecular sieve is added as a reaction carrier, and 1-1.5 mol magnesium chloride powder, 0.5-1 mol aluminum chloride and Optional zinc borate 0.3-0.5mol, after stirring evenly, slowly add an alkaline solution containing 3-6mol sodium hydroxide or potassium hydroxide with a mass fraction of 30-50% under stirring at room temperature, after adding the alkaline solution After continuing to stir the reaction for 0.5-1 hour, followed by crystallization treatment at 80-90 ° C in a sealed polytetrafluoroethylene-lined reaction kettle for 3-5 hours, the precipitate was filtered, washed with alcohol, vacuum dried, and ground to prepare the Layered composite metal oxide as a flame retardant component.
另一方面，本发明还提供所述高分子-无机材料复合壁纸基纸的制备方法，其主要包括纤网骨架构建和表面材料贴合，具体步骤如下：On the other hand, the present invention also provides a preparation method of the polymer-inorganic material composite wallpaper base paper, which mainly includes the construction of a web skeleton and the bonding of surface materials. The specific steps are as follows:
S1：按比例配制主材料各原料，并分别加入适当量的助剂A、B以得到骨架层和贴合层所需原料，室温下分别混匀，混合均匀后进行真空烘干处理，并于造粒机中加热、造粒；S1: Prepare the raw materials of the main materials according to the proportion, and add the appropriate amounts of additives A and B respectively to obtain the raw materials required for the skeleton layer and the bonding layer. Mix them separately at room temperature. After mixing evenly, perform the vacuum drying process. Heating and granulating in the granulator;
S2：将两种原料颗粒分别在各自混炼机中加热到170-200℃进行充分混炼，使有机材料和各种助剂与无机矿粉熔融均质；S2: The two raw material particles are heated to 170-200 ° C in their respective mixers to be fully mixed, so that the organic materials and various additives are melted and homogenized with the inorganic ore powder;
S3：将均质后的材料分别通过管道输送至各自捏合密炼机中加温至210-230℃捏合密炼，使物料进一步混合，形成均匀的熔融物料；S3: Transfer the homogenized materials to the respective kneading mixers through pipelines and heat them to 210-230 ° C to knead and knead them to further mix the materials to form uniform molten materials;
S4：将密炼机挤出的骨架层熔融物料经管道输送至温度不低于200℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后，再经均压处理形成均压熔融物料；S4: The molten material of the skeleton layer extruded by the internal mixer is transported to the screw extruder whose temperature is not lower than 200 ℃ through the pipeline. After the molten material is extruded by the screw extruder, it is then processed by pressure equalization to form a uniform pressure molten material ;
S5：均压物料喷丝构建纤网骨架：将均压熔融物料均匀地通过 热熔喷丝装置的定向喷丝孔进行纵横喷丝并热熔粘结，从而热铺成网，冷却，形成拟无纺布结构的人工纤维纺丝网，从而得到纤网骨架粗品，控制纤维间隔在50-100微米，并控制纤维直径小于100微米；S5: Spinning the pressure-equalized material to construct the fiber web skeleton: The pressure-equalized molten material is evenly and horizontally sprayed through the directional spinneret of the hot-melt spinning device and hot-melt bonded, so as to be thermally laid into a net, cooled, and formed Artificial fiber spinning net of non-woven fabric structure to obtain coarse web skeleton, control fiber interval between 50-100 microns, and control fiber diameter less than 100 microns;
S6：将密炼机挤出的贴合层熔融物料经管道输送至温度不低于210℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后输送至压延机辊筒，压延，得到厚度不大于500微米的贴合层粗品；S6: The molten material of the laminating layer extruded from the internal mixer is transported to the screw extruder whose temperature is not lower than 210 ° C through the pipeline. After the molten material is extruded by the screw extruder, it is transported to the roller of the calender and calendered to obtain Coarse products with a thickness not greater than 500 microns;
S7：加热贴合成型：在贴合机中将得到的贴合层粗品置于拟无纺布结构的骨架纤网上，加热至120-150℃进行热熔粘结，滚压贴合至合适厚度，整平，冷却降温，即得到所述的高分子-无机材料复合壁纸基纸。S7: Heat-bonded synthetic type: Place the obtained coarse layer of bonding layer on the skeleton web of the non-woven fabric structure in the bonding machine, heat to 120-150 ℃ for hot-melt bonding, and roll bonding to the appropriate thickness , Leveling, cooling and cooling, that is to obtain the polymer-inorganic material composite wallpaper base paper.
所制备的壁纸基纸随后可进行电晕处理或涂胶、表面涂布等处理以形成各种壁纸。The prepared wallpaper base paper can then be subjected to corona treatment, gumming, surface coating and other treatments to form various wallpapers.
本发明所制备的壁纸基纸厚度可为0.02～1.0mm，优选0.05～0.8mm。The thickness of the wallpaper base paper prepared by the present invention may be 0.02 to 1.0 mm, preferably 0.05 to 0.8 mm.
本发明所述螺杆挤出机可以为双螺杆挤出机或单螺杆挤出机。The screw extruder of the present invention may be a twin screw extruder or a single screw extruder.
相比现有技术，本发明的有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
1.本发明壁纸基纸引入拟无纺布结构的定向人工纤维网状骨架，通过热熔平铺成型、表层贴合工艺，相比一般壁纸原纸，在增强骨架强度等物理机械性能的基础上，产品密度下降，降低了克重，而且粗糙的网状底层和大量的空隙给涂胶后的壁纸提供了更好的附着性。1. The wallpaper base paper of the present invention introduces a directional artificial fiber network skeleton with a pseudo-nonwoven fabric structure, which is formed by hot-melt tiling and surface lamination process. Compared with ordinary wallpaper base paper, it enhances the strength of the skeleton and other physical and mechanical properties. The density of the product drops and the gram weight is reduced, and the rough mesh bottom and a large number of voids provide better adhesion to the wallpaper after being glued.
2.本发明壁纸基纸表层具有更高含量的有机材料，无需覆膜，即具有良好的防水、防油效果，易清洁；而且具有提高的撕裂度、耐折度好。2. The surface layer of the wallpaper-based paper of the present invention has a higher content of organic materials, which does not require a film, that is, has good waterproof and oil-proof effects, is easy to clean, and has improved tearing and folding resistance.
3.本发明壁纸基纸表层在较低含量的阻燃剂的前提下，具有更好的阻燃性，而且相比一般壁纸，吸墨性好，而且提高了颜料的着色性，具有更好的图案装饰效果。3. The surface layer of the wallpaper base paper of the present invention has better flame retardancy under the premise of a lower content of flame retardant, and has better ink absorption than ordinary wallpaper, and improves the coloring of the pigment, and has better Pattern decorative effect.
4.本发明壁纸基纸表层和骨架层具有基本相同的主材料，相容性好，贴合牢固，避免了现有壁纸大量增塑剂污染物的缺陷。4. The wallpaper base paper surface layer and the skeleton layer of the present invention have basically the same main material, good compatibility, and firm bonding, avoiding the defects of a large amount of plasticizer pollutants in the existing wallpaper.
5.本发明壁纸基纸通过添加改性的聚丙烯酰胺，提高了纸张强度，而且增强了染料附着牢度，提高着色性，鲜艳度高，耐久度好。5. The wallpaper base paper of the present invention improves the strength of the paper by adding modified polyacrylamide, and also enhances the fastness of dye attachment, improves the coloring, has high vividness and good durability.
6.本发明壁纸基纸的制备方法简单，操作方便，适用于大规模的 工业化生产。6. The preparation method of the wallpaper base paper of the present invention is simple, the operation is convenient, and it is suitable for large-scale industrial production.
具体实施方式detailed description
下面通过具体的制备例和实施例对本发明进行详细说明，但这些例举性实施方式的用途和目的仅用来例举本发明，并非对本发明的实际保护范围构成任何形式的任何限定，更非将本发明的保护范围局限于此。The present invention will be described in detail below through specific preparation examples and examples, but the use and purpose of these exemplary embodiments are only used to exemplify the present invention, and do not constitute any limitation of the actual protection scope of the present invention in any form, let alone The scope of protection of the present invention is limited to this.
本文所用术语“由…制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。As used herein, the term "prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing" or any other variations thereof as used herein are intended to cover non-exclusive inclusions. For example, a composition, step, method, article, or device that includes the listed elements need not be limited to those elements, but may include other elements not specifically listed or inherent to such a composition, step, method, article, or device Elements.
制备例1Preparation Example 1
改性的羧甲基纤维素制备Preparation of modified carboxymethyl cellulose
在带有搅拌的三口烧瓶中，加入200ml水以及20g的羧甲基纤维素溶液，滴加1g环氧氯丙烷，反应过程中用氨水调节pH，维持体系pH 8-9。在室温下搅拌反应2h。反应结束后，用稀释的盐酸中和，调节体系至pH 5，所得产物经醇洗、烘干即可得到环氧改性的羧甲基纤维素，粉碎备用。In a three-necked flask with stirring, 200 ml of water and 20 g of carboxymethyl cellulose solution were added, and 1 g of epichlorohydrin was added dropwise. During the reaction, the pH was adjusted with ammonia water to maintain the system pH 8-9. The reaction was stirred at room temperature for 2h. After the reaction is completed, neutralize with diluted hydrochloric acid to adjust the system to pH 5, and the resulting product can be washed with alcohol and dried to obtain epoxy-modified carboxymethyl cellulose, which is crushed for use.
制备例2Preparation Example 2
改性聚丙烯酰胺制备Preparation of modified polyacrylamide
将18g丙烯酰胺、10g羧甲基纤维素、4g甲基丙烯酰氧乙基三甲基氯化铵、5g亚甲基琥珀酸和2g甲基丙烯酸二甲氨基乙酯单体，加入去离子水中，控制溶液质量100g，并加入0.2g过硫铵引发剂和0.5g甲基丙烯磺酸钠链转移剂，调节pH至4，70℃搅拌反应1小时，反应结束后蒸干溶剂，烘干产物，研磨，即可得到改性的聚丙烯酰胺聚合物粉末。Add 18g acrylamide, 10g carboxymethyl cellulose, 4g methacryloyloxyethyl trimethyl ammonium chloride, 5g methylene succinic acid and 2g dimethylaminoethyl methacrylate monomer to deionized water , Control the quality of the solution 100g, and add 0.2g ammonium persulfate initiator and 0.5g sodium methacrylic acid chain transfer agent, adjust the pH to 4, stir the reaction at 70 ℃ for 1 hour, evaporate the solvent and dry the product after the reaction , Grinding, you can get modified polyacrylamide polymer powder.
制备例3Preparation Example 3
层状复合金属氧化物制备：Preparation of layered composite metal oxide:
在1000ml去离子水中，加入1molγ-Al2O3纳米分子筛作为反 应载体，并加入1mol氯化镁粉末、0.5mol氯化铝以及硼酸锌0.3mol，搅拌均匀后，室温下在搅拌条件下缓慢加入含4mol氢氧化钠的质量分数为30％的氢氧化钠溶液，加入碱液完毕后搅拌反应1小时，随后在聚四氟乙烯内衬的密闭反应釜中80℃下晶化处理5h，然后将沉淀过滤，醇洗，真空干燥，研磨，制得所述层状复合金属氧化物阻燃组分。In 1000ml deionized water, add 1mol γ-Al2O3 nano molecular sieve as the reaction carrier, and add 1mol magnesium chloride powder, 0.5mol aluminum chloride and 0.3mol zinc borate, after stirring evenly, slowly add 4mol sodium hydroxide at room temperature under stirring The mass fraction of the sodium hydroxide solution is 30%. After the addition of the lye, the reaction is stirred for 1 hour, followed by crystallization treatment at 80 ° C for 5 hours in a closed reaction kettle lined with polytetrafluoroethylene, and then the precipitate is filtered and washed with alcohol , Vacuum drying and grinding to prepare the layered composite metal oxide flame retardant component.
实施例1Example 1
复合壁纸基纸的制备Preparation of composite wallpaper base paper
骨架层原料组份如下：The raw material components of the skeleton layer are as follows:
共聚聚丙烯20份，热塑性聚酯PET 5份，聚乙烯3份，超微无机矿粉碳酸钙或滑石粉50份，锐钛型钛白粉3份，钛酸酯偶联剂1份，十二烷基硫酸钠0.2份，顺丁烯二酸酐-聚丙烯共聚物1份，制备例1制备的环氧改性羧甲基纤维素1.5份，硬脂酸0.5份，石蜡1份，纳米二氧化钛1份，抗氧化剂0.1份；以及助剂A：短切芳纶纤维3份，起泡剂ADC 0.1份，短切聚酰亚胺纤维2份；Copolymer polypropylene 20 parts, thermoplastic polyester PET 5 parts, polyethylene 3 parts, ultrafine inorganic mineral powder calcium carbonate or talc 50 parts, anatase titanium dioxide 3 parts, titanate coupling agent 1 part, twelve 0.2 parts of sodium alkyl sulfate, 1 part of maleic anhydride-polypropylene copolymer, 1.5 parts of epoxy-modified carboxymethyl cellulose prepared in Preparation Example 1, 0.5 parts of stearic acid, 1 part of paraffin, nano titanium dioxide 1 Parts, antioxidants 0.1 parts; and auxiliary A: 3 parts chopped aramid fiber, 0.1 parts foaming agent ADC, 2 parts chopped polyimide fiber;
贴合层原料组份如下：The raw material components of the bonding layer are as follows:
共聚聚丙烯20份，热塑性聚酯PET 5份，聚乙烯3份，超微无机矿粉碳酸钙或滑石粉50份，锐钛型钛白粉3份，钛酸酯偶联剂1份，十二烷基硫酸钠0.2份，顺丁烯二酸酐-聚丙烯共聚物1份，制备例1制备的环氧改性羧甲基纤维素1.5份，硬脂酸0.5份，石蜡1份，纳米二氧化钛1份，抗氧化剂0.1份；以及助剂B：聚乙烯醇1份，上述制备的两性改性的聚丙烯酰胺增强剂3份，上述制备例制备的层状复合金属氧化物6份。Copolymer polypropylene 20 parts, thermoplastic polyester PET 5 parts, polyethylene 3 parts, ultrafine inorganic mineral powder calcium carbonate or talc 50 parts, anatase titanium dioxide 3 parts, titanate coupling agent 1 part, twelve 0.2 parts of sodium alkyl sulfate, 1 part of maleic anhydride-polypropylene copolymer, 1.5 parts of epoxy-modified carboxymethyl cellulose prepared in Preparation Example 1, 0.5 parts of stearic acid, 1 part of paraffin, nano titanium dioxide 1 Parts, antioxidants 0.1 parts; and auxiliary agent B: 1 part of polyvinyl alcohol, 3 parts of the amphoteric modified polyacrylamide reinforcement prepared above, 6 parts of the layered composite metal oxide prepared in the above preparation example.
具体制备步骤如下：The specific preparation steps are as follows:
S1：将上述骨架层和贴合层原料，室温下分别混匀，混合均匀后进行真空烘干处理，并于造粒机中加热、造粒；S1: Mix the raw materials of the above-mentioned framework layer and the bonding layer separately at room temperature. After mixing evenly, perform vacuum drying treatment, and heat and granulate in the granulator;
S2：将两种原料颗粒分别在各自混炼机中加热到180℃进行充分混炼，使有机材料和各种助剂与无机矿粉熔融均质；S2: The two raw material particles are heated to 180 ° C in their respective mixers to be fully mixed, so that the organic materials and various additives are melted and homogenized with the inorganic ore powder;
S3：将均质后的材料分别通过管道输送至各自捏合密炼机中加温至210℃捏合密炼，使物料进一步混合，形成均匀的熔融物料；S3: The homogenized materials are transferred to the respective kneading mixers by pipelines and heated to 210 ° C to knead and knead to further mix the materials to form a uniform molten material;
S4：将密炼机挤出的骨架层熔融物料经管道输送至温度220℃的 螺杆挤出机，熔融物料经螺杆挤出机挤出后，再经均压处理形成均压熔融物料；S4: The molten material of the skeleton layer extruded by the internal mixer is transported to the screw extruder at a temperature of 220 ° C through the pipeline. After the molten material is extruded by the screw extruder, it is then processed by pressure equalization to form a pressure-balanced molten material;
S5：均压物料喷丝构建纤网骨架：将均压熔融物料均匀地通过热熔喷丝装置的定向喷丝孔进行纵横喷丝并热熔粘结，从而热铺成网，冷却，形成拟无纺布结构的人工纤维纺丝网，从而得到纤网骨架粗品，控制纤维间隔在50微米，并控制纤维直径40微米；S5: Spinning the pressure-equalized material to construct the fiber web skeleton: The pressure-equalized molten material is evenly and horizontally sprayed through the directional spinneret of the hot-melt spinning device and hot-melt bonded, so as to be thermally laid into a net, cooled, and formed into a pseudo Artificial fiber spinning net of non-woven fabric structure to obtain coarse web skeleton, control fiber spacing at 50 microns, and control fiber diameter at 40 microns;
S6：将密炼机挤出的贴合层熔融物料经管道输送至温度不低于210℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后输送至压延机辊筒，压延，得到厚度400微米的贴合层粗品；S6: The molten material of the laminating layer extruded from the internal mixer is transported to the screw extruder whose temperature is not lower than 210 ° C through the pipeline. Coarse product with a thickness of 400 microns;
S7：加热贴合成型：在贴合机中将得到的贴合层粗品置于拟无纺布结构的骨架纤网上，加热至120℃进行热熔粘结，滚压贴合至合适厚度200微米，整平，冷却降温，即得到所述的高分子-无机材料复合壁纸基纸。S7: Heat-bonded synthetic type: Place the coarse product of the bonding layer on the skeleton web of the non-woven fabric structure in the bonding machine, heat to 120 ℃ for hot-melt bonding, and roll-bond to a suitable thickness of 200 microns , Leveling, cooling and cooling, that is to obtain the polymer-inorganic material composite wallpaper base paper.
本实施例所制备的壁纸基纸，在室温和50％湿度环境下测试着色粘结强度(ASTM C 633-2001)数值为35N；其阻燃性能为续焰时间4s，灼燃时间14s，达到GB/T 14656-2009的要求(按GB/T14656-2009的定义，续焰时间为本生灯火焰移开后试样持续进行有焰燃烧的时间，灼燃时间是指火焰熄灭后试样进行无焰燃烧的时间)。The wallpaper base paper prepared in this example has a coloring bond strength (ASTM 633-2001) value of 35N at room temperature and 50% humidity; its flame retardant performance is 4s for flame retention time and 14s for ignition time. The requirements of GB / T 14656-2009 (according to the definition of GB / T14656-2009, the flame retention time is the time that the sample continues to burn flamingly after the flame of the Bunsen burner is removed. The burning time refers to the time after the flame goes out Flameless burning time).
相对照的，含相同重量氢氧化镁代替所述阻燃剂时，壁纸基纸的续焰时间5s，灼燃时间高达26s。In contrast, when the same weight of magnesium hydroxide is used instead of the flame retardant, the flame retention time of the wallpaper-based paper is 5s and the burning time is as high as 26s.
实施例2Example 2
复合壁纸基纸的制备Preparation of composite wallpaper base paper
骨架层原料组份：Raw material composition of skeleton layer:
共聚聚丙烯30份，热塑性聚酯PET 10份，聚乙烯5份，超微无机矿粉碳酸钙或滑石粉70份，锐钛型钛白粉5份，钛酸酯偶联剂2份，十二烷基硫酸钠0.5份，顺丁烯二酸酐共聚物1.5份，环氧改性羧甲基纤维素3份，硬脂酸1份，石蜡1.5份，纳米二氧化钛3份，抗氧化剂DSTDP 0.2份；以及助剂A：短切芳纶纤维5份，起泡剂ADC 0.2份，短切聚酰亚胺纤维5份；Copolymer polypropylene 30 parts, thermoplastic polyester PET 10 parts, polyethylene 5 parts, ultrafine inorganic mineral powder calcium carbonate or talc 70 parts, anatase titanium dioxide 5 parts, titanate coupling agent 2 parts, twelve Sodium alkyl sulfate 0.5 parts, maleic anhydride copolymer 1.5 parts, epoxy modified carboxymethyl cellulose 3 parts, stearic acid 1 part, paraffin 1.5 parts, nano titanium dioxide 3 parts, antioxidant DSTDP 0.2 parts; And auxiliary A: 5 parts of chopped aramid fiber, 0.2 parts of foaming agent ADC, and 5 parts of chopped polyimide fiber;
所述贴合层原料组份：The raw material component of the bonding layer:
共聚聚丙烯30份，热塑性聚酯PET 10份，聚乙烯5份，超微 无机矿粉碳酸钙或滑石粉70份，锐钛型钛白粉5份，钛酸酯偶联剂2份，十二烷基硫酸钠0.5份，顺丁烯二酸酐共聚物1.5份，环氧改性羧甲基纤维素3份，硬脂酸1份，石蜡1.5份，纳米二氧化钛3份，抗氧化剂DSTDP 0.2份；以及助剂B：聚乙烯醇3份，上述制备的两性改性的聚丙烯酰胺增强剂5份；上述制备的层状复合金属氧化物阻燃剂10份。Copolymer polypropylene 30 parts, thermoplastic polyester PET 10 parts, polyethylene 5 parts, ultrafine inorganic mineral powder calcium carbonate or talc 70 parts, anatase titanium dioxide 5 parts, titanate coupling agent 2 parts, twelve Sodium alkyl sulfate 0.5 parts, maleic anhydride copolymer 1.5 parts, epoxy modified carboxymethyl cellulose 3 parts, stearic acid 1 part, paraffin 1.5 parts, nano titanium dioxide 3 parts, antioxidant DSTDP 0.2 parts; And auxiliary agent B: 3 parts of polyvinyl alcohol, 5 parts of the amphoteric modified polyacrylamide reinforcement prepared above; 10 parts of the layered composite metal oxide flame retardant prepared above.
具体制备步骤如下：The specific preparation steps are as follows:
S1：将上述骨架层和贴合层原料，室温下分别混匀，混合均匀后进行真空烘干处理，并于造粒机中加热、造粒；S1: Mix the raw materials of the above-mentioned framework layer and the bonding layer separately at room temperature. After mixing evenly, perform vacuum drying treatment, and heat and granulate in the granulator;
S2：将两种原料颗粒分别在各自混炼机中加热到190℃进行充分混炼，使有机材料和各种助剂与无机矿粉熔融均质；S2: The two raw material particles are heated to 190 ℃ in their respective mixers to be fully mixed, so that the organic materials and various additives and inorganic mineral powder are melted and homogenized;
S3：将均质后的材料分别通过管道输送至各自捏合密炼机中加温至220℃捏合密炼，使物料进一步混合，形成均匀的熔融物料；S3: The homogenized materials are transferred to the respective kneading mixers by pipes and heated to 220 ° C to knead and knead to further mix the materials to form a uniform molten material;
S4：将密炼机挤出的骨架层熔融物料经管道输送至温度230℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后，再经均压处理形成均压熔融物料；S4: The molten material of the skeleton layer extruded by the internal mixer is transported to the screw extruder at a temperature of 230 ° C through the pipeline. After the molten material is extruded by the screw extruder, it is then processed by pressure equalization to form a uniform pressure molten material;
S5：均压物料喷丝构建纤网骨架：将均压熔融物料均匀地通过热熔喷丝装置的定向喷丝孔进行纵横喷丝并热熔粘结，从而热铺成网，冷却，形成拟无纺布结构的人工纤维纺丝网，从而得到纤网骨架粗品，控制纤维间隔在70微米，并控制纤维直径50微米；S5: Spinning the pressure-equalized material to construct the fiber web skeleton: The pressure-equalized molten material is evenly and horizontally sprayed through the directional spinneret of the hot-melt spinning device and hot-melt bonded, so as to be thermally laid into a net, cooled, and formed into a pseudo Artificial fiber spinning net of non-woven fabric structure to obtain coarse web skeleton, control the fiber interval at 70 microns, and control the fiber diameter at 50 microns;
S6：将密炼机挤出的贴合层熔融物料经管道输送至温度220℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后输送至压延机辊筒，压延，得到厚度500微米的贴合层粗品；S6: The molten material of the laminating layer extruded from the internal mixer is transported to the screw extruder at a temperature of 220 ° C through the pipeline. After the molten material is extruded by the screw extruder, it is transported to the calender roll and calendered to obtain a thickness of 500 microns The rough product of the fitting layer;
S7：加热贴合成型：在贴合机中将得到的贴合层粗品置于拟无纺布结构的骨架纤网上，加热至120℃进行热熔粘结，滚压贴合至合适厚度300微米，整平，冷却降温，即得到所述的高分子-无机材料复合壁纸基纸。S7: Heat-bonded synthetic type: Place the coarse product of the bonding layer on the skeleton web of the non-woven fabric structure in the bonding machine, heat to 120 ℃ for hot-melt bonding, and roll-bond to a suitable thickness of 300 microns , Leveling, cooling and cooling, that is to obtain the polymer-inorganic material composite wallpaper base paper.
本实施例2所制备的壁纸基纸，在室温和50％湿度环境下测试着色粘结强度(ASTM C 633-2001)数值为37N；其阻燃性能为：续焰时间3s，灼燃时间10s，达到GB/T 14656-2009的要求。The wallpaper base paper prepared in Example 2 was tested at room temperature and 50% humidity to test the coloring bond strength (ASTM 633-2001) value is 37N; its flame retardant properties are: flame time 3s, burning time 10s , Meet the requirements of GB / T 14656-2009.
上述说明示出并描述了本发明的优选实施例，如前所述，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述发明构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。The above description shows and describes the preferred embodiments of the present invention. As mentioned above, it should be understood that the present invention is not limited to the form disclosed herein, and should not be regarded as an exclusion from other embodiments, but can be used in various other Combination, modification and environment, and can be modified within the scope of the inventive concept described herein, through the above teaching or technology or knowledge in related fields. Changes and changes made by those skilled in the art without departing from the spirit and scope of the present invention should fall within the protection scope of the appended claims of the present invention.

Claims (7)

  1. 一种高分子-无机材料复合壁纸基纸，其特征在于，其包括纤网骨架层和表面材料贴合层；所述纤网骨架层和表面材料贴合层由相同的基质复合材料及相应的助剂组成，所述基质复合材料包括高分子材料、无机材料和其他组分，具体由下列重量份数的组分组成：A polymer-inorganic material composite wallpaper base paper, characterized in that it comprises a web skeleton layer and a surface material bonding layer; the web skeleton layer and the surface material bonding layer are made of the same matrix composite material and corresponding Auxiliary composition, the matrix composite material includes polymer materials, inorganic materials and other components, specifically composed of the following components by weight:
    共聚聚丙烯20-30份，热塑性聚酯PET 5-10份，聚乙烯3-5份，超微无机矿粉碳酸钙或滑石粉50-70份，锐钛型钛白粉3-5份，钛酸酯偶联剂0.5-2份，十二烷基硫酸钠0.2-0.5份，顺丁烯二酸酐共聚物1-1.5份，环氧改性羧甲基纤维素1.5-3份，硬脂酸或硬脂酸酯0.5-1份，石蜡1-1.5份，纳米二氧化钛1-3份，抗氧化剂0.1-0.2份；Copolymer polypropylene 20-30 parts, thermoplastic polyester PET 5-10 parts, polyethylene 3-5 parts, ultra-fine inorganic mineral powder calcium carbonate or talc 50-70 parts, anatase titanium dioxide 3-5 parts, titanium Acid ester coupling agent 0.5-2 parts, sodium lauryl sulfate 0.2-0.5 parts, maleic anhydride copolymer 1-1.5 parts, epoxy modified carboxymethyl cellulose 1.5-3 parts, stearic acid Or 0.5-1 part of stearate, 1-1.5 parts of paraffin, 1-3 parts of nano titanium dioxide, 0.1-0.2 parts of antioxidant;
    其中，所述骨架层在上述基质复合材料的基础上，还含有以下重量份的骨架层助剂A：Wherein, the skeleton layer further contains the following parts by weight of skeleton layer auxiliary agent A on the basis of the above matrix composite material:
    短切芳纶纤维 2-5份，Short cut aramid fiber 2-5 parts,
    起泡剂ADC 0.1-0.3份，Foaming agent ADC 0.1-0.3 servings,
    短切聚酰亚胺纤维 2-5份；Short cut polyimide fiber 2-5 copies;
    其中，所述贴合层在上述基质复合材料的基础上，还含有以下重量份的贴合层助剂B：Wherein, the bonding layer further contains the following parts by weight of bonding layer auxiliary agent B on the basis of the above matrix composite material:
    聚乙烯醇 1-3份；1-3 servings of polyvinyl alcohol;
    两性改性的聚丙烯酰胺增强剂 3-5份；Amphoteric modified polyacrylamide reinforcement 3-5 parts;
    层状复合金属氧化物类阻燃剂 5-10份。Layered composite metal oxide flame retardant 5-10 parts.
  2. 如权利要求1所述的壁纸基纸，其特征在于，所述环氧改性的羧甲基纤维素由环氧氯丙烷改性制得，具体制备步骤如下：The wallpaper-based paper according to claim 1, wherein the epoxy-modified carboxymethyl cellulose is prepared by modifying epichlorohydrin, and the specific preparation steps are as follows:
    在带有搅拌的反应器中，加入水以及羧甲基纤维素溶液，滴加适量环氧氯丙烷，在室温下搅拌反应2h，反应过程中用氨水调节pH，维持体系pH8-9，反应结束后，用稀释的盐酸中和，调节体系至pH 5，所得产物经醇洗、烘干即可得到环氧改性的羧甲基纤维素。In a reactor with agitation, add water and carboxymethyl cellulose solution, drop an appropriate amount of epichlorohydrin, stir the reaction at room temperature for 2h, adjust the pH with ammonia water during the reaction, maintain the system pH 8-9, the reaction is over Afterwards, it is neutralized with diluted hydrochloric acid and the system is adjusted to pH 5, the resulting product is washed with alcohol and dried to obtain epoxy-modified carboxymethyl cellulose.
  3. 如权利要求1所述的壁纸基纸，其特征在于，所述改性聚丙烯酰胺通过水分散聚合技术制备得到，具体步骤如下：The wallpaper-based paper according to claim 1, wherein the modified polyacrylamide is prepared by water dispersion polymerization technology, and the specific steps are as follows:
    将一定比例量的丙烯酰胺、羧甲基纤维素、甲基丙烯酰氧乙基三甲基氯化铵、亚甲基琥珀酸和甲基丙烯酸二甲氨基乙酯单体，溶解在适量水中，并加入过硫铵引发剂、甲基丙烯磺酸盐转移剂，控制其聚合单体质量分数分别为：18-20％、10-12％、4-5％、3-5％和1-2％，引发剂和转移剂质量分数分别为0.2-0.3％、0.5-0.6％，调节pH至3-4，70-75℃搅拌反应1-2小时，反应结 束后蒸干溶剂，烘干产物，研磨，即可得到改性的聚丙烯酰胺聚合物。Dissolve a certain amount of acrylamide, carboxymethyl cellulose, methacryloyloxyethyl trimethyl ammonium chloride, methylene succinic acid, and dimethylaminoethyl methacrylate monomer in the appropriate amount of water, Add ammonium persulfate initiator and methacrylic acid sulfonate transfer agent to control the mass fraction of its polymerized monomers: 18-20%, 10-12%, 4-5%, 3-5% and 1-2 %, The mass fractions of initiator and transfer agent are 0.2-0.3% and 0.5-0.6% respectively, adjust the pH to 3-4, stir and react at 70-75 ° C for 1-2 hours, after the reaction is over, evaporate the solvent and dry the product, After grinding, the modified polyacrylamide polymer can be obtained.
  4. 如权利要求1所述的壁纸基纸，其特征在于，所述层状复合金属氧化物为至少包括金属镁、铝的氧化物，具体制备步骤如下：The wallpaper-based paper according to claim 1, wherein the layered composite metal oxide is an oxide including at least metal magnesium and aluminum, and specific preparation steps are as follows:
    在1000ml去离子水中，加入1molγ-Al2O3纳米分子筛作为反应载体，并加入1-1.5mol氯化镁粉末、0.5-1mol氯化铝以及任选的硼酸锌0.3-0.5mol，搅拌均匀后，室温下在搅拌条件下缓慢加入质量分数为30-50％的氢氧化钠或氢氧化钾碱性溶液，加入碱液完毕后继续搅拌反应0.5-1小时，随后在聚四氟乙烯内衬的密闭反应釜中80-90℃下晶化处理3-5h，将沉淀过滤，醇洗，真空干燥，研磨，制得所述层状复合金属氧化物。In 1000ml of deionized water, add 1mol γ-Al2O3 nano molecular sieve as the reaction carrier, and add 1-1.5mol magnesium chloride powder, 0.5-1mol aluminum chloride and optional zinc borate 0.3-0.5mol, after stirring evenly, stir at room temperature Under conditions, slowly add an alkaline solution of sodium hydroxide or potassium hydroxide with a mass fraction of 30-50%. After the addition of the alkaline solution, continue to stir the reaction for 0.5-1 hour, and then 80 in a closed reaction kettle lined with polytetrafluoroethylene -Crystallizing treatment at -90 ° C for 3-5 hours, filtering the precipitate, washing with alcohol, vacuum drying, and grinding to prepare the layered composite metal oxide.
  5. 一种权利要求1所述的壁纸基纸的制备方法，包括纤网骨架构建和表面材料贴合步骤，其特征在于，具体包括如下步骤：A method for preparing wallpaper-based paper according to claim 1, comprising the steps of constructing a web skeleton and bonding surface materials, characterized in that it specifically includes the following steps:
    S1：按比例配制基质原料，并分别加入适当量的助剂A、B以得到骨架层和贴合层所需原料，室温下分别混匀，混合均匀后进行真空烘干处理，并于造粒机中加热、造粒；S1: Prepare the matrix raw materials in proportion, and add appropriate amounts of additives A and B respectively to obtain the raw materials needed for the skeleton layer and the bonding layer. Mix them separately at room temperature. After mixing evenly, perform vacuum drying treatment and granulate. Heating and granulating in the machine;
    S2：将两种原料颗粒分别在各自混炼机中加热到170-200℃进行充分混炼，使有机材料和各种助剂与无机矿粉熔融均质；S2: The two raw material particles are heated to 170-200 ° C in their respective mixers to be fully mixed, so that the organic materials and various additives are melted and homogenized with the inorganic ore powder;
    S3：将均质后的材料分别通过管道输送至各自捏合密炼机中加温至210-230℃捏合密炼，使物料进一步混合，形成均匀的熔融物料；S3: Transfer the homogenized materials to the respective kneading mixers through pipelines and heat them to 210-230 ° C to knead and knead them to further mix the materials to form uniform molten materials;
    S4：将密炼机挤出的骨架层熔融物料经管道输送至温度不低于200℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后，再经均压处理形成均压熔融物料；S4: The molten material of the skeleton layer extruded by the internal mixer is transported to the screw extruder whose temperature is not lower than 200 ℃ through the pipeline. After the molten material is extruded by the screw extruder, it is then processed by pressure equalization to form a uniform pressure molten material ;
    S5：均压物料喷丝构建纤网骨架：将均压熔融物料均匀地通过热熔喷丝装置的定向喷丝孔进行纵横喷丝并热熔粘结，从而热铺成网，冷却，形成拟无纺布结构的人工纤维纺丝网，从而得到纤网骨架粗品，控制纤维间隔在50-100微米，并控制纤维直径小于100微米；S5: Spinning the pressure-equalized material to construct the fiber web skeleton: The pressure-equalized molten material is evenly and horizontally sprayed through the directional spinneret of the hot-melt spinning device and hot-melt bonded, so as to be thermally laid into a net, cooled, and formed Artificial fiber spinning net of non-woven fabric structure to obtain coarse web skeleton, control fiber interval between 50-100 microns, and control fiber diameter less than 100 microns;
    S6：将密炼机挤出的贴合层熔融物料经管道输送至温度不低于210℃的螺杆挤出机，熔融物料经螺杆挤出机挤出后输送至压延机辊筒，压延，得到厚度不大于500微米的贴合层纸粗品；S6: The molten material of the laminating layer extruded from the internal mixer is transported to the screw extruder whose temperature is not lower than 210 ° C through the pipeline. After the molten material is extruded by the screw extruder, it is transported to the roller of the calender and calendered to obtain Coarse paper with a thickness not greater than 500 microns;
    S7：加热贴合成型：在贴合机中将得到的贴合层粗品置于拟无纺布结构的骨架纤网上，加热至120-150℃进行热熔粘结，滚压贴合至合适厚度，整平，冷却降温，即得到所述的高分子-无机材料复合壁纸基纸。S7: Heat-bonded synthetic type: Place the obtained coarse layer of bonding layer on the skeleton web of the non-woven fabric structure in the bonding machine, heat to 120-150 ℃ for hot-melt bonding, and roll bonding to the appropriate thickness , Leveling, cooling and cooling, that is to obtain the polymer-inorganic material composite wallpaper base paper.
  6. 如权利要求5所述的制备方法，其特征在于，所述复合壁纸基纸的厚 度为0.02～1.0mm。The preparation method according to claim 5, wherein the thickness of the composite wallpaper base paper is 0.02 to 1.0 mm.
  7. 权利要求1-6所述壁纸基纸用于各类壁纸的用途。The wallpaper base paper described in claims 1-6 is used for various types of wallpaper.
PCT/CN2019/101281 2018-10-16 2019-08-19 Synthesized wallpaper base having improved fire resistance and printability, and preparation method therefor WO2020078096A1 (en)

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CN109112896B (en) * 2018-10-16 2020-12-01 新昌县勤勉生物医药科技有限公司 Synthetic wallpaper base paper capable of improving flame retardance and printability and preparation method thereof
US20220186003A1 (en) * 2019-03-26 2022-06-16 Afi Licensing Llc Surface covering including a polyester-polyolefin-blend core
CN111875984B (en) * 2020-08-26 2021-12-24 湖州菱创科技有限公司 Preparation method of high-temperature-resistant iron oxide yellow pigment
CN115181422B (en) * 2021-04-02 2023-06-27 中国科学院大连化学物理研究所 Flame retardant based on polyimide foam material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005188010A (en) * 2003-12-26 2005-07-14 Mitsui Chemicals Inc Wall paper
KR20070033080A (en) * 2005-09-20 2007-03-26 삼성토탈 주식회사 Frame retardant wallpaper for reducing sick house syndrome
CN102166870A (en) * 2011-01-05 2011-08-31 上海奇葩环境科技有限公司 Method for manufacturing fireproof flame-retardation wallpaper
CN109112896A (en) * 2018-10-16 2019-01-01 求秋平 A kind of synthesis wallpaper base paper and preparation method improving anti-flammability and printability

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060246259A1 (en) * 2005-04-29 2006-11-02 Ching-Tien Chen Wallpaper manufacture method and its wallpaper products
CN103343491B (en) * 2013-07-09 2015-12-09 浙江凯恩特种材料股份有限公司 Mosquito-proof nonwoven wallpaper base stock of a kind of on-line coater type and preparation method thereof
CN106703311A (en) * 2016-12-22 2017-05-24 安徽易有墙纸有限公司 Heat-resisting waterproof wallpaper and production method thereof
CN107299559A (en) * 2017-08-30 2017-10-27 陈雪珍 The production method of environmental protection flame retardant wallpaper
CN108203895A (en) * 2017-12-25 2018-06-26 福建省大投科技有限公司 A kind of wet method prepares the production method of staple fibre paper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005188010A (en) * 2003-12-26 2005-07-14 Mitsui Chemicals Inc Wall paper
KR20070033080A (en) * 2005-09-20 2007-03-26 삼성토탈 주식회사 Frame retardant wallpaper for reducing sick house syndrome
CN102166870A (en) * 2011-01-05 2011-08-31 上海奇葩环境科技有限公司 Method for manufacturing fireproof flame-retardation wallpaper
CN109112896A (en) * 2018-10-16 2019-01-01 求秋平 A kind of synthesis wallpaper base paper and preparation method improving anti-flammability and printability

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