CN109551855B - Photocatalytic high-pressure decorative plate and preparation method thereof - Google Patents

Photocatalytic high-pressure decorative plate and preparation method thereof Download PDF

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Publication number
CN109551855B
CN109551855B CN201811452285.7A CN201811452285A CN109551855B CN 109551855 B CN109551855 B CN 109551855B CN 201811452285 A CN201811452285 A CN 201811452285A CN 109551855 B CN109551855 B CN 109551855B
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photocatalytic
decorative
layer
pressure
resin
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CN109551855A (en
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任太平
徐明华
卢泓楠
刘玉秀
陈佳音
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HENAN YONGWEI SECURITY CO Ltd
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HENAN YONGWEI SECURITY CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/0866—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements composed of several layers, e.g. sandwich panels or layered panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/26—All layers being made of paper or paperboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/12—Paper, e.g. cardboard
    • B32B2317/122—Kraft paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/12—Paper, e.g. cardboard
    • B32B2317/125—Paper, e.g. cardboard impregnated with thermosetting resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2601/00—Upholstery

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a photocatalytic high-pressure decorative board and a preparation method thereof. The photocatalysis high-pressure decorative board is formed by a substrate layer, an adhesive layer and a photocatalysis decorative layer at one time through high temperature and high pressure. The photocatalytic decorative layer comprises a composite photocatalyst plate layer. The photocatalytic high-pressure decorative board has a photocatalytic function, can degrade various harmful substances generated in the decoration process such as indoor formaldehyde, organic pollutants and the like, avoids long-time ventilation of newly-decorated houses, and can also continuously degrade and remove the harmful substances generated by the decoration. Avoids the harm to human body and the influence to environment caused by the continuously generated harmful substances of the decoration material. Has good application prospect.

Description

Photocatalytic high-pressure decorative plate and preparation method thereof
Technical Field
The invention belongs to the technical field of decorative plates. In particular to a photocatalysis high-pressure decorative board and a preparation method thereof.
Background
At present, indoor decoration materials in China mainly comprise paint, coating, soft decoration materials, wallpaper, wall cloth and decorative plates. The paint coating mostly contains volatile organic pollutants such as benzene and toluene and heavy metals such as lead, mercury, chromium and cadmium, and has great potential harm to the health of users or residents and great harm to the surrounding environment; wallpaper, wall cloth and the like have the defects of no water resistance, no moisture resistance, easy falling off and easy mildew when the humidity is high, and the glue used in pasting is mostly benzene solution of rubber adhesives, so that volatile solvents have great harm to human bodies; most of the decorative boards are made of wood or wood derivatives, and are pasted on a base material after being painted. The high-pressure decorative laminated board is produced by impregnating paper with thermosetting resin and then carrying out high-temperature high-pressure production, has various designs (hundreds of designs), has various forms such as high-gloss, matte and embossed surfaces after surface treatment, and has high resin content, high-temperature high-pressure process and compact surface, so that the high-pressure decorative laminated board has good water resistance, dry-heat resistance, corrosion resistance and impact resistance, and does not need coating of paint. Therefore, the high-pressure decorative plate gradually becomes a main material for furniture and interior decoration, and can be widely applied to the interior decoration of families, the decoration and decoration of furniture in office places and public places, carriage plates and partitions of steamships, interior decoration of schools and hospitals, cabinets in the fast food industry, working tables and the like. However, most of the wood, wood derivatives or paper used as the decorative board is treated with formaldehyde to prolong the service life of the decorative board and ensure the stability of the decorative board in use in order to prevent damage by worms. Therefore, the purification of indoor and indoor air after decoration and fitment is a problem of continuous and deep research in the decoration industry.
The indoor air is purified mainly by (1) spraying vinegar, an air freshener and the like, and the purification principle is that the odor of pollutants is shielded by the odor of the indoor air, formaldehyde and benzene series substances are not purified, but the stress reaction of a human respiratory system to the polluted air is weakened, so that more harmful gases are inhaled; (2) plants are planted indoors, the purification principle is that the plants absorb and decompose a small amount of formaldehyde and benzene series substances in vivo, and the plants have purification effect but are trace; (3) activated carbon adsorption cannot decompose formaldehyde and benzene series substances, saturation can be realized after certain pollution amount is adsorbed, and secondary pollution can be caused when the saturated adsorption becomes a pollution source; (4) the formaldehyde catching agent and the formaldehyde scavenging agent are used for neutralizing or oxidizing and decomposing formaldehyde, mainly aiming at formaldehyde, can strongly neutralize or decompose formaldehyde, but have little effect on air pollution of benzene series, TVOC and the like, and have no effect after the reaction of reactants is finished; (5) the photocatalyst has strong decomposition effect on most air pollution by oxidative decomposition, has killing effect on most bacteria and viruses, and can be used as a catalyst for long-term effect as long as the catalyst does not fall off.
The photocatalyst can effectively degrade pollutants such as formaldehyde, benzene, toluene, xylene, ammonia, TVOC and the like, has high-efficiency and wide disinfection performance, and can decompose and harmlessly treat toxins released by bacteria or fungi. The photocatalyst can not change and lose under the conditions of no abrasion and no peeling when in use, can continuously purify pollutants under the irradiation of light, has the characteristics of lasting time and long lasting effect, can be reused after being treated for a certain time when being used for reaching the service life, and can be well recycled.
Disclosure of Invention
The invention aims at the technical problems that: in the prior art, pollution caused by indoor and outdoor decoration plates cannot be efficiently and continuously removed, and pollutants such as formaldehyde, organic pollutants, bacteria, mold and the like carried in the decoration process cannot be effectively and continuously removed; the house needs long-time ventilation before living, but harmful substances such as formaldehyde, organic pollutants and the like still volatilize after living, causing long-term harm to human bodies; the common photocatalyst titanium dioxide can only be used under the condition of specific wavelength, has narrow application range and cannot be well applied to decoration materials.
In order to solve the problems, the invention provides a photocatalytic high-pressure decorative board and a preparation method thereof, the photocatalytic high-pressure decorative board is endowed with a composite photocatalyst, so that the photocatalytic high-pressure decorative board can continuously decompose pollutants such as formaldehyde, benzene, toluene, xylene, ammonia, TVOC and the like in the use process, can decompose and harmlessly treat toxins released by bacteria or fungi, has long catalytic service life, and effectively solves the pollution problem brought by indoor and outdoor decoration processes.
The invention is realized by the following technical scheme
A composite photocatalyst is prepared from the following raw materials: 60-70% of meteorological titanium dioxide with the particle size of 5-10 nm, 30-40% of hydrophilic silicon dioxide with the particle size of 10-20 nm and photosensitizer organic dye accounting for 0.3% of the total mass of the raw materials;
preferably, the photosensitizer organic dye is triarylamine organic dye.
The preparation method of the composite photocatalyst comprises the following steps: mixing meteorological titanium dioxide with the particle size of 5-10 nm and hydrophilic silicon dioxide with the particle size of 10-20 nm according to a required proportion, adding a photosensitizer organic dye accounting for 0.3% of the total mass of the mixture after uniformly mixing to obtain a photosensitizer mixture, then adding a polyvinyl alcohol aqueous solution, uniformly mixing and stirring, and then preparing a composite photocatalyst microcapsule by adopting a molecular coating method;
preferably, the mass percentage concentration of the polyvinyl alcohol aqueous solution is 15%; the mass ratio of the photosensitizer mixture to the polyvinyl alcohol aqueous solution is 1: 5;
preferably, the particle size of the composite photocatalyst microcapsule is 500-800 meshes.
A photocatalysis high-pressure decorative board containing the composite photocatalyst comprises a substrate layer, and an adhesive layer and a photocatalysis decorative layer which are sequentially arranged on two sides of the substrate layer from inside to outside; the photocatalytic decorative layer comprises a photocatalytic decorative plate and melamine formaldehyde resin layers which are coated on the two surfaces of the photocatalytic decorative plate and added with the composite photocatalyst.
The substrate layer is prepared by a plurality of layers of kraft paper impregnated with thermosetting resin; the thickness of the kraft paper is 0.10-0.12 mm; the thickness of the substrate layer is 8-16 mm, the bonding layer is prepared from kraft paper impregnated with thermosetting resin, the thickness of the kraft paper is 0.10-0.12 mm, and the thickness of the bonding layer is 0.2 mm;
preferably, the thermosetting resin is a water-soluble phenolic resin.
The photocatalytic high-pressure decorative board is characterized in that the photocatalytic decorative layer is made of decorative paper impregnated with resin, and the thickness of the photocatalytic decorative layer is 0.1-1.2 mm;
the photocatalytic decorative layer is impregnated with resin by decorative paper in a secondary impregnation mode; the decorative paper is firstly dipped with melamine formaldehyde resin and dried to obtain a photocatalytic decorative board, and the upper surface and the lower surface of the photocatalytic decorative board are coated with the melamine formaldehyde resin added with the composite photocatalyst; the decorative paper can be single-color paper or printing paper;
preferably, the thicknesses of the melamine formaldehyde resin layers coated on the upper surface and the lower surface of the photocatalytic decorative board are both 0.03-0.05 mm.
Preferably, the mass percentage of the composite photocatalyst in the melamine formaldehyde resin added with the composite photocatalyst is 1.2-1.9%.
The photocatalysis high-pressure decorative plate is 0.7-1.2 mm in thickness, 960-1830 mm in width and 2000-3660 mm in length.
The photocatalytic high-pressure decorative board is formed by a base board layer, an adhesive layer and a photocatalytic decorative layer through high-temperature and high-pressure one-step forming at the temperature of 130-135 ℃ and the pressure of 4.8-6.0 MPa.
The preparation method of the photocatalytic high-pressure decorative board comprising the composite photocatalyst comprises the following steps:
(1) preparation of photocatalytic decorative layer
Placing the decorative paper in melamine formaldehyde resin for impregnation, and drying after the impregnation is finished; after drying, coating melamine formaldehyde resin added with the composite photocatalyst on the upper surface and the lower surface of the substrate, drying after coating, and cutting according to the required size after drying to obtain the photocatalytic decorative layer;
(2) preparation of the substrate layer
Placing kraft paper in thermosetting resin for dipping, drying after dipping, cutting according to the required length after drying to obtain the dipped kraft paper, and superposing and bonding a plurality of the dipped kraft paper to obtain a substrate layer; (the number of kraft paper is determined according to actual needs);
(3) preparation of adhesive layer
The kraft paper is placed in thermosetting resin for impregnation, drying is carried out after impregnation, the impregnated kraft paper is obtained by cutting according to the required length after drying, and the adhesive layer can be obtained by superposing and adhering a plurality of impregnated kraft paper; (the number of kraft paper is determined according to actual needs);
(4) preparation of photocatalytic high-pressure decorative board
a: each layer in the intermittent hot press is paved according to the sequence from bottom to top: the heat-conducting and heat-insulating floor mat comprises a base plate, a heat-conducting cushion pad, a template, a photocatalytic decorative layer, an adhesive layer, a substrate layer, a BOPP isolating film, a substrate layer, an adhesive layer and a photocatalytic decorative layer, wherein the template, the photocatalytic decorative layer, the adhesive layer, the substrate layer, the BOPP isolating film, the substrate layer, the adhesive layer and the photocatalytic decorative layer are sequentially paved in sequence, namely … …; after the paving is finished, the mounting machine is finished;
b: c, boosting and heating the hot press paved in the step a, when the temperature reaches 130-135 ℃, the pressure is 4.8-6.0 MPa, and pressing for 30-45 min at high temperature and high pressure under the temperature and pressure condition;
c: and c, maintaining the pressure and reducing the temperature of the decorative plate pressed at high temperature and high pressure in the step b, relieving the pressure when the temperature is reduced to 40 ℃, unloading the decorative plate, and obtaining the photocatalytic high-pressure decorative plate.
The preparation method of the photocatalytic high-pressure decorative board comprises the following steps of (1), dipping the melamine formaldehyde resin, wherein the gluing amount of the resin is 60-80%, and the volatile component is 11.0-13.0%; after the decorative paper is coated with resin and dried, the total gluing amount of the resin is 95-120% (the gluing amount refers to the mass percentage of the resin impregnated on the decorative paper or the printing paper in the decorative paper or the printing paper is 95-120%), the final volatile matter after drying is 7.5-9.5% (the volatile matter refers to the mass percentage of the volatile matter in the drying process in the total mass percentage of the decorative paper or the printing paper after coating the resin is 7.5-9.5%), and the final pre-curing degree is 35-45% (the pre-curing degree refers to the ratio of the cured resin after impregnation and drying in the total gluing amount);
after the melamine formaldehyde resin added with the composite photocatalyst in the step (1) is coated, the temperature of an oven for drying is 110-140 ℃, and the paper advancing speed is 25-35 m/min;
the preparation method of the melamine formaldehyde resin added with the composite photocatalyst comprises the following steps: preparing melamine formaldehyde resin by a conventional method, reducing the temperature of a reaction system to 70 ℃ after the reaction reaches the end point, adding the composite photocatalyst, uniformly mixing, reducing the temperature of the system to 35 ℃ after uniform mixing, and starting discharging;
preferably, the mass percent of the composite photocatalyst in the melamine formaldehyde resin is 1.2-1.9%;
in the preparation method of the photocatalytic high-pressure decorative board, in the step (2) and the step (3), the gluing amount of the kraft paper after resin impregnation is 45-55% (the gluing amount means that the mass of the resin glue on the kraft paper accounts for 45-55% of the mass of the kraft paper), and the volatile components after drying are 7.5-9.5% (the volatile components after drying means that the mass of the volatile components after drying accounts for 7.5-9.5% of the total mass of the kraft paper before drying after gluing);
preferably, the thermosetting resin is a thermosetting water-soluble phenolic resin.
According to the preparation method of the photocatalytic high-pressure decorative board, in the step a, the number of the templates in the hot press is 7, and 14 groups of board blanks are pressed; the time for heating the temperature to 130-135 ℃ in the step b is 15-20 min, and the heating medium adopted during heating is high-pressure steam or superheated water; and c, cooling the temperature from 130-135 ℃ to 40 ℃ for 30-40 min, wherein the cooling medium adopted in the cooling is softened water.
The drying is carried out at a stable temperature of 110-140 ℃ and the paper advancing speed of 25-35 m/min.
The invention combines the self-made high-efficiency composite photocatalyst with the high-pressure decorative plate, so that the decorative plate for indoor and outdoor decoration can remove pollutants such as formaldehyde carried by the decorative plate under the condition of light irradiation, and can also remove indoor or outdoor pollutants, bacteria and the like. Particularly, the air purifier brings great safety and convenience to indoor decoration, does not need to ventilate for a long time to remove aldehyde, and also ensures the safety of indoor air to human bodies.
Compared with the prior art, the invention has the following positive beneficial effects
The composite photocatalyst prepared by the simple and easy-to-operate method can generate a strong catalytic degradation function under the action of ultraviolet light with longer wavelength and partial visible light, can effectively degrade toxic and harmful gases in the air, effectively kill multipurpose bacteria, and can decompose and harmlessly treat toxins released by bacteria or fungi. The composite material has obvious effects of removing formaldehyde, deodorizing, resisting pollution and purifying air; the problem that the photocatalyst titanium dioxide cannot be used for decoration materials is efficiently solved;
the high-pressure decorative plate prepared by the high-efficiency composite photocatalyst has the functions of catalyzing and degrading pollutants, bacteria and fungi, and is waterproof, moistureproof and widely applied. Therefore, when the high-pressure decorative plate is used as a decoration material, particularly as an indoor decoration material, the high-pressure decorative plate can efficiently remove pollutants such as formaldehyde, bacteria and fungi reserved in the plate, and simultaneously has the effect of degrading and removing the pollutants such as the indoor formaldehyde, so that the problem that long-time ventilation is needed in indoor decoration is completely solved, and the safety of indoor air can be ensured. Under the action of the composite photocatalyst, indoor air, particularly formaldehyde and other substances can be continuously purified, the harm of newly decorated houses to human bodies is avoided, and the composite photocatalyst has a good application prospect.
Drawings
FIG. 1 is a schematic sectional view of a photocatalytic high-pressure decorative sheet;
FIG. 2 is a schematic cross-sectional view of a photocatalytic decorative layer;
the drawing symbols indicate the following meanings: 1 denotes a substrate layer, 2 denotes an adhesive layer, 3 denotes a photocatalytic decorative layer, 301 denotes a photocatalytic decorative sheet, and 302 denotes a melamine-formaldehyde resin layer to which a composite photocatalyst is added.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments, but the present invention is not limited to the embodiments.
The materials and preparation process of the thermosetting melamine formaldehyde resin described in the following examples are as follows:
the reaction molar ratio is melamine: formaldehyde 1: 2.3 to 3.0;
catalyst: an aqueous sodium hydroxide solution containing 30% by mass of sodium hydroxide;
the diluent is water, and the mass of the diluent added is 70 percent of that of the melamine (the diluent is added in two times, 35 percent of the total amount of the water added in the first time and 65 percent of the total amount of the water added in the second time);
the reaction process is as follows:
(1) adding formaldehyde and water (for the first time), adjusting the pH value to be between 9.3 and 9.5 by using 30 percent sodium hydroxide, and slowly heating;
(2) when the temperature is raised to 60 ℃, adding melamine, and slowly raising the temperature;
(3) when the temperature is raised to 80 ℃, the mixture is completely dissolved, and the temperature is raised after 20 minutes of heat preservation;
(4) when the temperature is raised to 94 ℃, keeping the temperature between 94 and 96 ℃, and measuring the water solubility times of the resin and water after reacting for about 60 min; (5) when the water solubility is 1: and (3) reaching the reaction end point 1.8-2.2, adding water (for the second time), cooling, and discharging when the temperature is reduced to 45 ℃.
The preparation of the melamine formaldehyde resin added with the composite photocatalyst comprises the following steps: when the melamine formaldehyde resin is prepared, the water solubility times are 1: and (3) when the reaction end point is reached at 1.8-2.2, cooling the temperature of the reaction system to 70 ℃, then adding the composite photocatalyst, uniformly mixing, adding water (for the second time), cooling the temperature of the system to 35 ℃, and starting discharging. (curing agent which accounts for 0.23 to 0.26 percent of the total mass of the resin is added before use, and then coating is carried out for use).
The materials and preparation process of the thermosetting water-soluble phenolic resin in the following examples are as follows:
the reaction molar ratio is phenol: formaldehyde 1: 1.7-1.9, urea: the adding amount is 17 percent of the mass of the phenol;
catalyst: solid sodium hydroxide with the mass of 3 percent of the added phenol;
the diluent is water, and the mass of the diluent added is 90 percent of that of phenol (the diluent is added in two times, 35 percent of the total amount of water added in the first time and 65 percent of the total amount of water added in the second time);
the reaction process is as follows:
(1) adding formaldehyde, water (for the first time), phenol and sodium hydroxide, heating, and reacting for 60 minutes at 65-68 ℃;
(2) stopping heating when the temperature rises to 75 ℃, and slowly rising to 96 ℃; reacting at 96-98 deg.c, adding water and urea at 80-85 deg.c when dynamic viscosity reaches 14-16 Pa.s;
(3) carrying out heat preservation reaction at the temperature of 80-85 ℃, and rapidly cooling when the dynamic viscosity is measured and the viscosity reaches 18-23 Pa.s; discharging when the temperature is reduced to 45 ℃.
Said trimeric indenyl triarylamine organic dyes (from SURTECO Pte Ltd)
Example 1
The composite photocatalyst is prepared from the following raw materials in parts by weight: 60 percent of meteorological titanium dioxide with the particle size of 5-10 nm, 40 percent of hydrophilic silicon dioxide with the particle size of 10-20 nm and trimeric indenyl triarylamine organic dye accounting for 0.3 percent of the total mass of the raw materials;
the preparation method of the composite photocatalyst comprises the following steps: mixing meteorological titanium dioxide with the particle size of 5-10 nm and hydrophilic silicon dioxide with the particle size of 10-20 nm according to the mass ratio of 60: 40, adding trimeric indenyl triarylamine organic dye accounting for 0.3 percent of the total mass of the mixture after uniformly mixing, uniformly mixing to obtain a photosensitizer mixture, adding a polyvinyl alcohol aqueous solution with the mass percentage concentration of 15 percent into the photosensitizer mixture, uniformly mixing and stirring (the mass of the polyethylene energy-producing aqueous solution is 5 times of that of the photosensitizer mixture), and preparing the composite photocatalyst microcapsule with the particle size of 500-800 meshes by adopting a molecular coating method.
Example 2
The composite photocatalyst is prepared from the following raw materials in parts by weight: 65 percent of meteorological titanium dioxide with the particle size of 5-10 nm, 35 percent of hydrophilic silicon dioxide with the particle size of 10-20 nm and trimeric indenyl triarylamine organic dye accounting for 0.3 percent of the total mass of the raw materials;
the preparation method of the composite photocatalyst is the same as that of the embodiment 1.
Example 3
The composite photocatalyst is prepared from the following raw materials in parts by weight: 70 percent of meteorological titanium dioxide with the particle size of 5-10 nm, 30 percent of hydrophilic silicon dioxide with the particle size of 10-20 nm and trimeric indenyl triarylamine organic dye accounting for 0.3 percent of the total mass of the raw materials;
the preparation method of the composite photocatalyst is the same as that of the embodiment 1.
Example 4
The utility model provides a contain photocatalysis high pressure decorative board of compound photocatalyst of embodiment 1~ 3, this decorative board includes base plate layer 1, base plate layer 1 upper and lower two surfaces from inside to outside set gradually adhesive linkage 2 and photocatalysis decorative layer 3, photocatalysis decorative layer 3 including the melamine formaldehyde resin layer 302 that adds compound photocatalyst of two surface coating about photocatalysis decorative board 301 and the photocatalysis decorative board.
The substrate layer 1 is prepared by a plurality of layers of kraft paper impregnated with thermosetting resin; the thickness of the kraft paper is 0.10-0.12 mm, and the thickness of the substrate layer is 8-16 mm; the adhesive layer 2 is prepared from kraft paper impregnated with thermosetting resin, the thickness of the kraft paper is 0.10-0.12 mm, and the thickness of the adhesive layer is 0.2 mm;
the photocatalytic decorative layer is prepared from decorative paper impregnated with resin, and the thickness of the photocatalytic decorative layer is 0.1-1.2 mm; the photocatalytic decorative layer is impregnated with resin by decorative paper in a secondary impregnation mode; the decorative paper is firstly impregnated with melamine formaldehyde resin and dried to obtain a photocatalytic decorative board 301, the upper surface and the lower surface of the photocatalytic decorative board are coated with melamine formaldehyde resin layers 302 added with composite photocatalyst, and the thickness of the melamine formaldehyde resin layers 302 on the upper surface and the lower surface is 0.03-0.05 mm.
Further, the thermosetting resin is thermosetting water-soluble phenolic resin.
Furthermore, the decorative paper can be single-color paper or printing paper.
Further, the mass percentage of the composite catalyst in the melamine formaldehyde resin added with the composite photocatalyst is 1.2-1.9%.
Furthermore, the photocatalytic high-pressure decorative board is formed by the substrate layer, the bonding layer and the photocatalytic decorative layer through high-temperature and high-pressure one-step forming at the temperature of 130-135 ℃ and the pressure of 4.8-6.0 MPa.
Example 5
A photocatalytic high-pressure decorative board containing the composite photocatalyst described in embodiments 1-3 comprises a substrate layer 1, wherein an adhesive layer 2 and a photocatalytic decorative layer 3 are sequentially arranged on the upper surface and the lower surface of the substrate layer from inside to outside, and the photocatalytic decorative layer 3 comprises a photocatalytic decorative board 301 and a melamine formaldehyde resin layer 302 which is coated on the two surfaces of the photocatalytic decorative board and is added with the composite photocatalyst;
the substrate layer is prepared by a plurality of layers of kraft paper impregnated with thermosetting resin; the thickness of the kraft paper is 0.11mm, and the thickness of the substrate layer is 11 mm; the adhesive layer is prepared from kraft paper impregnated with thermosetting resin, the thickness of the kraft paper is 0.10mm, and the thickness of the adhesive layer is 0.2 mm; the sizing amount of the kraft paper impregnated with the resin is 45-55%, and the volatile components after drying are 7.5-9.5%;
the photocatalytic decorative layer is prepared from decorative paper impregnated with resin, and the thickness of the photocatalytic decorative layer is 1.2 mm; the photocatalytic decorative layer is impregnated with resin by decorative paper in a secondary impregnation mode; the decorative paper is firstly dipped with melamine formaldehyde resin, dried to obtain the photocatalysis decorative board, then the upper surface and the lower surface of the photocatalysis decorative board are coated with the melamine formaldehyde resin layers added with the composite photocatalyst, the thickness of the melamine formaldehyde resin layers on the upper surface and the lower surface of the photocatalysis decorative board is 0.05mm,
wherein after the melamine formaldehyde resin is impregnated and dried, the gluing amount of the resin is 60-80%, and the volatile component is 11.0-13.0%; the total gluing amount of the resin after the decorative paper is impregnated and coated with the resin and dried is 95-120%, the volatile matter is 7.5-9.5%, and the pre-curing degree is 35-45%.
Further, the thermosetting resin is water-soluble phenolic resin.
Further, the mass percentage of the composite catalyst in the melamine formaldehyde resin added with the composite photocatalyst is 1.9%.
Furthermore, the decorative paper can be single-color paper or printing paper.
The photocatalytic high-pressure decorative board is obtained by performing high-temperature and high-pressure one-step molding on a substrate layer, an adhesive layer and a photocatalytic decorative layer.
Example 6
One preparation method of a photocatalytic high-pressure decorative board comprising a composite photocatalyst comprises the following steps: (1) preparation of photocatalytic decorative layer
Placing the decorative paper in melamine formaldehyde resin for impregnation, and drying after the impregnation is finished; after drying, coating melamine formaldehyde resin layers added with composite photocatalyst on the upper surface and the lower surface of the melamine formaldehyde resin (the mass percentage of the composite photocatalyst in the melamine formaldehyde resin is 1.2 percent), drying after coating, and cutting according to the required size after drying to obtain the photocatalytic decorative layer;
wherein the dipping melamine formaldehyde resin has 60 to 80 percent of gluing amount and 11.0 to 13.0 percent of volatile component; after the decorative paper is coated with resin and dried, the total gluing amount of the resin in two times is 95-120%, the volatile matter is 7.5-9.5%, and the pre-curing degree is 35-45%; the thickness of the melamine formaldehyde resin layer added with the composite photocatalyst is 0.03 mm;
(2) preparation of the substrate layer
Soaking kraft paper with the thickness of 0.11mm in thermosetting water-soluble phenolic resin, drying after soaking, cutting according to the required length after drying to obtain the soaked kraft paper, soaking and cutting 100 pieces of kraft paper according to the same method, and then overlapping and bonding the kraft paper and the soaked kraft paper together to obtain a substrate layer;
the sizing amount of the kraft paper after resin impregnation is 45-55%, and the volatile component after drying is 7.5-9.5%;
(3) preparation of adhesive layer
Putting kraft paper with the thickness of 0.1mm into thermosetting water-soluble phenolic resin for impregnation, drying after impregnation, cutting according to the required length after drying to obtain impregnated kraft paper, taking 2 pieces of kraft paper for impregnation and cutting according to the same method, and superposing and bonding the 2 pieces of impregnated kraft paper to obtain a bonding layer;
the sizing amount of the kraft paper impregnated with the resin is 45-55%, and the volatile component after drying is 7.5-9.5%.
(4) Preparation of photocatalytic high-pressure decorative board
a: each layer in the intermittent hot press is paved according to the sequence from bottom to top: the composite material comprises a base plate, a heat-conducting cushion pad, a template, a photocatalytic decorative layer, an adhesive layer, a substrate layer, a BOPP isolating film, a substrate layer, an adhesive layer and a photocatalytic decorative layer, wherein the template, the photocatalytic decorative layer, the adhesive layer, the substrate layer, the BOPP isolating film, the substrate layer, the adhesive layer and the photocatalytic decorative layer are sequentially paved into 14 plate blanks according to the sequence, and the total number of the 7 templates is … …; after the paving is finished, the mounting machine is finished;
b: step a, boosting and heating the hot press paved in the step a, adopting high-pressure steam or superheated water as a heating medium, enabling the temperature to reach 130-135 ℃ within 15-20 min, enabling the pressure to be 4.8-6.0 MPa, and pressing at the temperature and the pressure for 30-45 min at high temperature and high pressure;
c: and c, maintaining the pressure and reducing the temperature of the decorative plate pressed at high temperature and high pressure in the step b by using softened water as a cooling medium, reducing the temperature from 130-135 ℃ to 40 ℃ within 30-40 min, then releasing the pressure, unloading and discharging the decorative plate, thus obtaining the photocatalytic high-pressure decorative plate.
The thickness of the photocatalytic high-pressure decorative plate is 0.7mm, the width of the photocatalytic high-pressure decorative plate is 960mm, and the length of the photocatalytic high-pressure decorative plate is 2000 mm; in the above preparation process, the impregnated paper is cut according to the size.
Example 7
A second preparation method of a photocatalytic high-pressure decorative board comprising a composite photocatalyst, which comprises the following steps: (1) preparation of photocatalytic decorative layer
Placing the decorative paper in melamine formaldehyde resin for impregnation, and drying after the impregnation is finished; after drying, coating melamine formaldehyde resin added with the composite photocatalyst on the upper surface and the lower surface (the mass percentage of the composite photocatalyst in the melamine formaldehyde resin is 1.9 percent), drying after coating, and cutting according to the required size after drying to obtain the photocatalytic decorative layer;
wherein the dipping melamine formaldehyde resin has 60 to 80 percent of gluing amount and 11.0 to 13.0 percent of volatile component; after the decorative paper is coated with resin and dried, the total gluing amount of the resin is 95-120%, the volatile matter is 7.5-9.5%, and the pre-curing degree is 35-45%; the thickness of the melamine formaldehyde resin layer added with the composite photocatalyst is 0.05 mm;
(2) preparation of the substrate layer
Soaking kraft paper with the thickness of 0.11mm in thermosetting water-soluble phenolic resin, drying after soaking, cutting according to the required length after drying to obtain the soaked kraft paper, soaking and cutting 120 pieces of kraft paper according to the same method, and then stacking and bonding together to obtain a substrate layer;
the sizing amount of the kraft paper after resin impregnation is 45-55%, and the volatile component after drying is 7.5-9.5%;
(3) preparation of adhesive layer
Putting kraft paper with the thickness of 0.1mm into thermosetting water-soluble phenolic resin for impregnation, drying after impregnation, cutting according to the required length after drying to obtain impregnated kraft paper, taking 2 pieces of kraft paper for impregnation and cutting according to the same method, and superposing and bonding the 2 pieces of impregnated kraft paper to obtain a bonding layer;
the sizing amount of the kraft paper impregnated with the resin is 45-55%, and the volatile component after drying is 7.5-9.5%.
(4) Preparation of photocatalytic high-pressure decorative board
a: each layer in the intermittent hot press is paved according to the sequence from bottom to top: the composite material comprises a base plate, a heat-conducting cushion pad, a template, a photocatalytic decorative layer, an adhesive layer, a substrate layer, a BOPP isolating film, a substrate layer, an adhesive layer and a photocatalytic decorative layer, wherein the template, the photocatalytic decorative layer, the adhesive layer, the substrate layer, the BOPP isolating film, the substrate layer, the adhesive layer and the photocatalytic decorative layer are sequentially paved into 14 plate blanks according to the sequence, and the total number of the 7 templates is … …; after the paving is finished, the mounting machine is finished;
b: step a, boosting and heating the hot press paved in the step a, adopting high-pressure steam or superheated water as a heating medium, enabling the temperature to reach 130-135 ℃ within 15-20 min, enabling the pressure to be 4.8-6.0 MPa, and pressing at the temperature and the pressure for 30-45 min at high temperature and high pressure;
c: and c, maintaining the pressure and reducing the temperature of the decorative plate pressed at high temperature and high pressure in the step b by using softened water as a cooling medium, reducing the temperature from 130-135 ℃ to 40 ℃ within 30-40 min, then releasing the pressure, unloading and discharging the decorative plate, thus obtaining the photocatalytic high-pressure decorative plate.
The thickness of the photocatalytic high-pressure decorative plate is 1.2mm, the width of the photocatalytic high-pressure decorative plate is 1830mm, and the length of the photocatalytic high-pressure decorative plate is 3660 mm; in the above preparation process, the impregnated paper is cut according to the size.
The initial performance test of the product prepared by the invention is carried out, and the results are shown in the following table 1:
table 1 test results of the photocatalytic high-pressure decorative sheet according to the present invention
Figure BDA0001886900710000111
Therefore, the photocatalytic high-pressure decorative board prepared by the method has the performances of water resistance, moisture resistance, wear resistance, aging resistance and the like; and harmful substances such as formaldehyde in the air can be removed by illumination, and the air can be effectively degraded by bacteria and the harmful substances released by the bacteria. Particularly for newly decorated houses, the method can efficiently remove and degrade the harmful gas in the house, and completely avoid the condition of long-time ventilation (the long-time ventilation can not efficiently remove harmful substances such as the harmful gas brought by decoration); the photocatalytic decorative board can effectively remove and degrade harmful substances such as formaldehyde brought by other furniture and the like. Has good application prospect.

Claims (9)

1. The composite photocatalyst is characterized by being prepared from the following raw materials: 60-70% of gas-phase titanium dioxide with the particle size of 5-10 nm, 30-40% of hydrophilic silicon dioxide with the particle size of 10-20 nm and photosensitizer organic dye accounting for 0.3% of the total mass of the raw materials; the photosensitizer organic dye is triarylamine organic dye;
the preparation method of the composite photocatalyst comprises the following steps: mixing 5-10 nm of gas-phase titanium dioxide and 10-20 nm of hydrophilic silicon dioxide according to a required proportion, adding a photosensitizer organic dye accounting for 0.3% of the total mass of the mixture after uniformly mixing to obtain a photosensitizer mixture, then adding a 15% polyvinyl alcohol aqueous solution by mass percentage, uniformly mixing and stirring, and then preparing the composite photocatalyst microcapsule with the particle size of 500-800 meshes by adopting a molecular coating method; the mass ratio of the photosensitizer mixture to the polyvinyl alcohol aqueous solution is 1: 5.
2. a photocatalytic high-pressure decorative sheet containing the composite photocatalyst of claim 1, which is characterized by comprising a substrate layer, and an adhesive layer and a photocatalytic decorative layer which are sequentially arranged from inside to outside on two sides of the substrate layer; the photocatalytic decorative layer comprises a photocatalytic decorative plate and melamine formaldehyde resin layers which are coated on two sides of the photocatalytic decorative plate and added with composite photocatalyst.
3. The photocatalytic high-pressure decorative sheet according to claim 2, wherein the substrate layer is prepared from a plurality of layers of kraft paper impregnated with thermosetting resin; the thickness of the kraft paper is 0.10-0.12 mm; the thickness of the substrate layer is 8-16 mm, the bonding layer is prepared from kraft paper impregnated with thermosetting resin, the thickness of the kraft paper is 0.10-0.12 mm, and the thickness of the bonding layer is 0.2 mm; the thermosetting resin is thermosetting water-soluble phenolic resin.
4. The photocatalytic high-pressure decorative board according to claim 2, wherein the photocatalytic decorative layer is prepared by resin-impregnated decorative paper, and the thickness of the photocatalytic decorative layer is 0.1-1.2 mm;
the photocatalytic decorative layer is impregnated with resin by decorative paper in a secondary impregnation mode; firstly dipping melamine formaldehyde resin in the decorative paper, drying to obtain a photocatalytic decorative board, and coating melamine formaldehyde resin layers added with composite photocatalyst on the upper surface and the lower surface of the photocatalytic decorative board; the thickness of the melamine formaldehyde resin layers coated on the upper surface and the lower surface of the photocatalytic decorative board is 0.03-0.05 mm;
the mass percentage of the composite photocatalyst in the melamine formaldehyde resin added with the composite photocatalyst is 1.2-1.9%.
5. The photocatalytic high-pressure decorative sheet according to claim 2, wherein the photocatalytic high-pressure decorative sheet has a thickness of 0.7 to 1.2mm, a width of 960 to 1830mm, and a length of 2000 to 3660 mm.
6. A method of making a photocatalytic high pressure decorative sheet comprising a composite photocatalyst as claimed in claim 2, comprising the steps of:
(1) preparation of photocatalytic decorative layer
Placing the decorative paper in melamine formaldehyde resin for impregnation, and drying after the impregnation is finished; after drying, coating melamine formaldehyde resin added with the composite photocatalyst on the upper surface and the lower surface of the substrate, drying after coating, and cutting according to the required size after drying to obtain the photocatalytic decorative layer;
(2) preparation of the substrate layer
Placing kraft paper in thermosetting resin for dipping, drying after dipping, cutting according to the required length after drying to obtain dipped kraft paper, and superposing and bonding the dipped kraft paper to obtain a substrate layer;
(3) preparation of adhesive layer
The kraft paper is placed in thermosetting resin for impregnation, drying is carried out after impregnation, the impregnated kraft paper is obtained by cutting according to the required length after drying, and the impregnated kraft paper is superposed and bonded to obtain a bonding layer;
(4) preparation of photocatalytic high-pressure decorative board
a: each layer in the intermittent hot press is paved according to the sequence from bottom to top: the heat-conducting and heat-insulating base plate comprises a base plate, a heat-conducting cushion pad, a template, a photocatalytic decorative layer, an adhesive layer, a base plate layer, a BOPP isolating film, a base plate layer, an adhesive layer and a photocatalytic decorative layer, wherein the template, the photocatalytic decorative layer, the adhesive layer, the base plate layer, the BOPP isolating film, the base plate layer, the adhesive layer and the photocatalytic decorative layer are sequentially paved in the sequence; after the paving is finished, the mounting machine is finished;
b: c, boosting and heating the hot press paved in the step a, when the temperature reaches 130-135 ℃, the pressure is 4.8-6.0 MPa, and pressing for 30-45 min at high temperature and high pressure under the temperature and pressure condition;
c: and c, maintaining the pressure and reducing the temperature of the decorative plate pressed at high temperature and high pressure in the step b, relieving the pressure when the temperature is reduced to 40 ℃, unloading the decorative plate, and obtaining the photocatalytic high-pressure decorative plate.
7. The preparation method of the photocatalytic high-pressure decorative board according to claim 6, wherein in the step (1), the decorative paper is impregnated with melamine formaldehyde resin, the gluing amount of the resin is 60-80%, and the volatile matter is 11.0-13.0%; coating resin on the decorative paper and drying to obtain resin with a total gluing amount of 95-120%; the final volatile matter after drying is 7.5-9.5%; the final pre-curing degree is 35-45%; after the melamine formaldehyde resin added with the composite photocatalyst in the step (1) is coated, the temperature of an oven for drying is 110-140 ℃, and the paper advancing speed is 25-35 m/min;
the preparation method of the melamine formaldehyde resin added with the composite photocatalyst comprises the following steps: preparing melamine formaldehyde resin by a conventional method, reducing the temperature of a reaction system to 70 ℃ after the reaction reaches the end point, adding the composite photocatalyst, uniformly mixing, reducing the temperature of the system to 35 ℃ after uniform mixing, and starting discharging;
the mass percentage of the composite photocatalyst in the melamine formaldehyde resin is 1.2-1.9%.
8. The preparation method of the photocatalytic high-pressure decorative board according to claim 6, wherein in the step (2) and the step (3), the kraft paper is impregnated with the thermosetting resin, the sizing amount is 45-55%, and the volatile components after drying are 7.5-9.5%; the thermosetting resin is thermosetting water-soluble phenolic resin.
9. The preparation method of the photocatalytic high-pressure decorative board according to claim 6, wherein the template in the hot press in the step a is 7 sheets and 14 groups of slabs are pressed; the time for heating the temperature to 130-135 ℃ in the step b is 15-20 min, and the heating medium adopted during heating is high-pressure steam or superheated water; and c, cooling the temperature from 130-135 ℃ to 40 ℃ for 30-40 min, wherein the cooling medium adopted in the cooling is softened water.
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