CN112265098B - Preparation method of chemical color-changing composite floor - Google Patents

Preparation method of chemical color-changing composite floor Download PDF

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Publication number
CN112265098B
CN112265098B CN202011122284.3A CN202011122284A CN112265098B CN 112265098 B CN112265098 B CN 112265098B CN 202011122284 A CN202011122284 A CN 202011122284A CN 112265098 B CN112265098 B CN 112265098B
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color
veneer
parts
changing
wood
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CN112265098A (en
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程明娟
戴维德
詹先旭
谢序勤
陈凯
丁涛
沈怡强
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Dehua TB New Decoration MaterialsCo Ltd
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Dehua TB New Decoration MaterialsCo Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27MWORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
    • B27M3/00Manufacture or reconditioning of specific semi-finished or finished articles
    • B27M3/04Manufacture or reconditioning of specific semi-finished or finished articles of flooring elements, e.g. parqueting blocks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34Organic impregnating agents
    • B27K3/36Aliphatic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34Organic impregnating agents
    • B27K3/50Mixtures of different organic impregnating agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/02Staining or dyeing wood; Bleaching wood
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27KPROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/04Combined bleaching or impregnating and drying of wood
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48Polymers modified by chemical after-treatment

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

A preparation method of a chemical color-changing composite floor comprises the following steps: the method comprises the following steps: carrying out fading treatment on the double-color or color-changing wood veneer, and drying to obtain a veneer A; step two: dipping the veneer A by using a modifier, and drying to obtain a veneer B; step three: coating the veneer B with a color-changing agent, and drying to obtain a veneer C; step four: carrying out pressing treatment on the C veneer; step five: post-treating to obtain the chemical color-changing solid wood floor; the modifier contains modified polyamide polyamine epichlorohydrin resin, and the modified polyamide polyamine epichlorohydrin resin is prepared by embedding diamine into a polyamide main chain and modifying by epichlorohydrin. The processing technology for processing the wood with the defects of double colors or color change, provided by the invention, has the advantages that the prepared composite board has high mechanical strength, good stability and good coloring effect, the quality grade of the wood is greatly improved, the application range is wide, and the application prospect is good.

Description

Preparation method of chemical color-changing composite floor
Technical Field
The invention belongs to the technical field of wood processing, and particularly relates to a preparation method of a chemical color-changing composite floor.
Background
Along with the improvement of living standard and the change of aesthetic concepts, the home consumption aesthetic feeling is more and more valued by consumers. In the household consumption, the wood product is the largest piece of bearing surface, and the aesthetic feeling of the wood product is mainly derived from the color and natural texture of wood. On the other hand, with the decrease of high-quality wood resources, the grade of wood which can be used for the panel is linearly reduced, a large amount of bicolor materials and decay and discolor materials exist, and the beautiful effect of the panel is reduced. In the production, the decoration effect of the board is mainly improved by a surface painting method, and diversified colors are given to the wood, but the texture of the wood is covered to a certain degree, so that the wood loses the sense of reality.
The document with the application number of CN201110163464.0 discloses a processing method of a black oak surface board solid wood composite floor, which is characterized in that the specific processing method is as follows: putting the veneer with a spacer in the middle of the veneer into a vacuum tank, vacuumizing the vacuum tank to-0.6 kg/cm2 to-0.8 kg/cm2, adding the liquid medicine into the tank to enable the liquid medicine to soak the veneer, pressurizing the tank to 1.5 to 2.0kg/cm2 by an air pump, gradually raising the temperature, namely raising the temperature by 5 ℃ per hour until the temperature reaches 70 to 90 ℃, and then keeping the temperature for 12 to 24 hours when the pressure in the tank reaches 1.5 to 2.0kg/cm 2; evacuating the liquid medicine; and then carrying out secondary vacuum pumping, adding medicine, increasing the pressure in the tank for the second time, heating, pumping back the liquid medicine and taking out the plate. The method comprises the steps of blending liquid medicine according to a set formula proportion by utilizing a vacuum dyeing principle, fully soaking the liquid medicine and surface plate wood in a vacuum tank, heating and pressurizing, carrying out chemical color change in a high-temperature and high-pressure environment, wherein different liquid medicine proportions can generate different color changes; the paint spraying and dyeing qualification rate can be improved by 20-30%. But the processing method has small application range and is only suitable for the black oak surface plate; in addition, the method does not consider that the wood board is easy to expand and deform through liquid medicine dipping treatment, and further the mechanical strength of the wood board is reduced.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of a chemical color-changing composite floor, which is used for processing wood with double-color or color-changing defects, so that the prepared composite board has high mechanical strength, good stability and good coloring effect, greatly improves the quality grade of the wood, and has wide application range and good application prospect.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a chemical color-changing composite floor comprises the following steps:
the method comprises the following steps: carrying out fading treatment on the double-color or color-changing wood veneer, and drying to obtain a veneer A;
step two: dipping the veneer A by using a modifier, and drying to obtain a veneer B;
step three: coating the veneer B with a color-changing agent, and drying to obtain a veneer C;
step four: carrying out pressing treatment on the C veneer;
step five: carrying out post-treatment on the laminated board obtained in the step four to obtain a chemical color-changing composite floor board;
the modifier contains modified polyamide polyamine epichlorohydrin resin, and the modified polyamide polyamine epichlorohydrin resin is prepared by embedding diamine into a polyamide main chain and modifying with epichlorohydrin.
Furthermore, the wood veneer is sliced or sawed by the double-color or color-changing wood veneer, each veneer has double-color or color-changing defects formed by the difference of the core wood and the edge wood, and the tree species can be maple, oak, hickory, rubber wood and the like. Aiming at the defect of the wood veneer, firstly, the wood veneer is subjected to fading treatment to reduce the color of the veneer, particularly the color of a heartwood part, and the extract is removed, so that the subsequent permeation of modified resin and a color-changing agent is facilitated, and the effect of modification and color change is improved; then, matching with polyamide polyamine epichlorohydrin resin which is contained in the modifier and is subjected to block modification for modifying and reinforcing the wood veneer: the PAE resin is known to those skilled in the art as a wet strength agent, because the PAE resin contains a large amount of cationic charges in molecules and has the effect of negative charges on fibers and semi-fibers in a wood veneer, a large amount of wet resin is adsorbed on the surfaces of the fibers, the wood veneer is heated after being dried to dehydrate the molecules, and the wet strength resin is subjected to polycondensation, at the moment, the resin is converted into a water-insoluble state and is crosslinked on a fiber interface to form a resin network structure which cannot be completely destroyed by water, so that swelling of the fibers is reduced, the wet strength of the wood veneer is improved, and the dimensional temperature property of the wood veneer is ensured. The invention carries out modification treatment on PAE resin, synthesizes polyamide polyamine epichlorohydrin resin by a block polymerization technology, not only has the advantages of the PAE resin, but also additionally endows the PAE resin with the characteristic of being capable of being used for enhancing the impact strength of a wood veneer, and has the principle that diamine containing longer aliphatic chains is embedded into a polyamide polyamine main chain and is subjected to graft copolymerization with epichlorohydrin, so that epichlorohydrin tertiary amine groups in the obtained modified polyamide polyamine epichlorohydrin resin are increased, and the epichlorohydrin tertiary amine groups are further self-aminated to form azetidinone groups and chlorine anions, so that the activity of the resin is improved, and the enhancement effect of the wet strength and the impact strength of the wood veneer can be improved under the condition of adding a small amount of the epichlorohydrin tertiary amine groups; meanwhile, the introduced diamine can also convert organic chlorine or residual epoxy chloropropane generated in the reaction process into a stable harmless substance, reduce the residue of the organic chlorine and the epoxy chloropropane and ensure that the wood veneer is compounded with a sanitary environment-friendly standard; finally, the compound color-changing agent is adopted to react with the wood veneer to generate color, and the color-changing agent has better coloring effect on the wood veneer due to the treatment of the color-fading agent, so that the natural texture of the wood can be kept; due to the treatment of the modifier, the wood veneer has a closed protection effect on color, and the color stability and light resistance of the wood veneer are improved. And the scheme can eliminate the defects after three times of color fading, modification and color changing treatment are carried out on the double-color or color-changing wood veneer, the obtained veneer presents colors with natural transition and rich layering sense, and the quality grade of the wood is greatly improved.
As a further preferred aspect of the present invention, a fading agent is used in the fading treatment of the first step, the fading agent comprising, in parts by mass: 20-60 parts of 35% (w/w) hydrogen peroxide, 8-15 parts of sodium silicate, 1-3 parts of magnesium sulfate, 5-10 parts of diethylenetriamine pentamethylene phosphonic acid, 0.1-0.5 part of magnesium aluminum silicate, 1-3 parts of sodium hydroxide and 800-1000 parts of water.
In the design of the scheme, hydrogen peroxide is a main component for fading the wood board, the addition of sodium silicate can play roles of assisting fading and improving stability, magnesium silicate is used as a pollution-free additive for providing magnesium ions to protect wood veneer cellulose and hemicellulose, diethylenetriamine pentamethylene phosphonic acid plays roles of a stabilizer and a chelating agent of hydrogen peroxide, magnesium aluminum silicate is used as a pollution-free additive for providing a role of enabling a liquid system to be uniform and stable, and sodium hydroxide is used for adjusting pH to enable the system to be stable.
As a further preferred aspect of the present invention, the color fading treatment comprises: and heating the color fading agent to 50-60 ℃, controlling the pH value to be 9-10, and then immersing the bicolor or discolored wood veneer into the color fading agent for fading for 2-4 hours.
The modifier further preferably comprises 100-150 parts by mass of the modified polyamide polyamine epichlorohydrin resin, 1-5 parts by mass of the surfactant and 1-10 parts by mass of the tannic acid.
In the design of the scheme, the surfactant is prepared from polyethylene glycol laurate and polyethylene glycol monooleate according to a ratio of 1:1, and the two components are the optimal surfactants which are stable in an acid environment; simultaneously, add tannic acid and carry out acid pretreatment to the wood veneer, tannin content in the increase veneer improves tannin and distributes the degree of consistency, can make the oak class itself contain the wooden veneer of tannin's stability and the degree of consistency that discolours and obtain promoting on the one hand, on the other hand can maple, hickory this kind of wooden veneer that does not contain tannin itself also can have the effect of discolouing.
As a further preferable aspect of the present invention, the color-changing agent in step three includes, in parts by mass: 0.05 to 5 parts of metal salt containing ferric ions or ferrous ions, 0.5 to 2 parts of acidic silica sol and 100 to 200 parts of water.
As a further preferred aspect of the present invention, the modified polyamide polyamine epichlorohydrin resin contains the structure:
Figure DEST_PATH_IMAGE001
wherein R1, R2 are selected from the group:
Figure 204388DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
to (3) is provided.
In the design of the scheme, when the modified polyamide polyamine epoxy chloropropane resin with the structure is used as a main component, epichlorohydrin-based tertiary amine groups in the resin are increased, and the epichlorohydrin-based tertiary amine groups are further self-aminated to form azetidinol groups and chlorine anions, so that the activity of the resin is improved, and the enhancement effect on the wet strength and the impact strength of the wood board can be improved under the condition of adding a small amount of the epichlorohydrin-based epoxy chloropropane resin; and the structural component is stable, the preparation is easy, the pollution is small, and the application prospect is wide.
As a further preferred aspect of the present invention, the process for producing a modified polyamide polyamine epichlorohydrin resin comprises: (1) adding adipic acid a into the hexamethylenediamine solution at a constant speed, and reacting for 30-60 min at 70-80 ℃; (2) adding adipic acid b, adjusting the temperature to 55-65 ℃, and then dropwise adding diethylenetriamine at a constant speed; (3) after the dropwise addition is finished, adjusting the temperature to 90-110 ℃, adding a catalyst, adjusting the temperature to 135-145 ℃, and reacting for 40-70 min; (4) adjusting the temperature to 160-180 ℃, and reacting for 180-280 min; (5) stopping heating, adding water with the temperature of 70-100 ℃, and cooling to obtain a prepolymer; (6) mixing the prepolymer with water, controlling the temperature to be 40-45 ℃, and dropwise adding epoxy chloropropane; (7) and after the dropwise addition is finished, carrying out reaction to obtain the modified polyamide polyamine epichlorohydrin resin.
In a further preferred embodiment of the present invention, the mass ratio of adipic acid a to adipic acid b is 2: 3.
As a further preferred aspect of the present invention, the impregnation treatment conditions in the second step include: the vacuum degree is minus 0.08 to minus 0.1MPa, the vacuum time is 30 to 60min, the pressurizing pressure is 0.5 to 1.5MPa, and the pressurizing time is 4 to 6 hours.
As a further preferred aspect of the present invention, the pressing conditions in the fourth step include: the unit pressure is 0.5-1.5 MPa, the time is 3-7 minutes, and the temperature is 110-140 ℃.
Furthermore, the drying process in the scheme is a step-by-step drying process, the moisture content of the veneer is reduced to 18% -28% through a roller dryer, then the veneer enters a vacuum drying kiln to reduce the moisture content to 8% -15%, and finally the veneer enters a curing room to balance the moisture content to 6% -12%. The veneer dried by the process has flat surface, less cracking and high comprehensive drying efficiency.
Furthermore, the invention selects the wire drawing treatment before the fading treatment, increases the specific surface area and has the gain effect on the subsequent fading, impregnation and discoloration.
In conclusion, the invention has the following beneficial effects:
1. the veneer is firstly subjected to fading treatment, the color of the veneer, particularly the color of a heartwood part, is reduced, the extract is removed, the subsequent permeation of modified resin and a color-changing agent is facilitated, and the effect of modifying and changing color is improved.
2. The modified resin adopts the polyamide polyamine epichlorohydrin resin modified by blocks, the epichlorohydrin tertiary amine groups in the resin are increased while the strength of the resin is ensured, and the epichlorohydrin tertiary amine groups are further self-aminated to form the azetidinone groups and the chloride anions, so that the activity of the resin is improved, the impact strength of the treated veneer is improved by about 20%, the water absorption thickness expansion rate is reduced by about 50%, and the strength and the size stability of the faded veneer can be improved. In addition, tannin pretreatment is carried out while the modification is enhanced, the tannin content in the veneer is increased, the tannin distribution uniformity is improved, on one hand, the color change stability and uniformity of the wood veneer containing tannin of oak can be improved, and on the other hand, the wood veneer containing no tannin of maple and hickory can also have the color change effect.
3. The special compound color-changing agent is adopted to react with the wood veneer to generate color, the natural texture of the wood is kept, meanwhile, the addition of the silica sol has a sealing and protecting effect on the color, and the stability and the light resistance are improved.
4. The double-color defects of the veneer after three treatments of color fading, modification and color changing disappear, the panel presents natural transition and rich-layering color, and the quality grade of the wood is greatly improved.
Detailed Description
First, medicine selection
Fading agent (in parts by mass): 20-60 parts of 35% (w/w) hydrogen peroxide, 8-15 parts of sodium silicate, 1-3 parts of magnesium sulfate, 5-10 parts of diethylenetriamine pentamethylene phosphonic acid, 0.1-0.5 part of magnesium aluminum silicate, 1-3 parts of sodium hydroxide and 800-1000 parts of water.
Modifier (calculated by mass portion): 100-150 parts of modified polyamide polyamine epoxy chloropropane resin, 1-5 parts of surfactant (prepared from polyethylene glycol laurate and polyethylene glycol monooleate according to a ratio of 1: 1), and 1-10 parts of tannic acid.
Color-changing agent (in parts by mass): 0.05 to 5 parts of metal salt containing ferric ions or ferrous ions, 0.5 to 2 parts of acidic silica sol and 100 to 200 parts of water.
The preparation process of the modified polyamide polyamine epichlorohydrin resin comprises the following steps:
(1) weighing 100 parts by mass of adipic acid, 75 parts by mass of diethylenetriamine and 70 parts by mass of water, adding 25 parts by mass of hexamethylenediamine and water into a reaction kettle provided with a reflux device, starting stirring, slowly adding 40% of quantitative adipic acid, wherein the adding rate is 0.5 part by mass/second;
(2) adjusting the temperature, reacting for 60min at the temperature of 70-80 ℃, and adding the rest 60% of adipic acid;
(3) after the adipic acid is completely dissolved, reducing the temperature to 60 ℃, and dropwise adding diethylenetriamine into the reaction system at a dropping speed of 0.1 part by mass/second;
(4) after the dropwise addition, heating the reaction system to a temperature of 90-110 ℃, adding 1 part by mass of p-toluenesulfonic acid monohydrate serving as a catalyst, continuously heating, changing a reflux device into a distillation device when the temperature reaches 140 ℃, receiving water serving as a reaction by-product, and reacting at the temperature for 70 min;
(5) the temperature is continuously increased to the range of 160-180 ℃, the reaction is carried out for 280min at the temperature, and no liquid flows out at the moment;
(6) stopping heating, adding 100 parts by mass of 100 ℃ hot water in two steps when the temperature is cooled to be within the range of 100-130 ℃, adding 50% of the total amount of the hot water, stirring for half an hour after adding, then adding the second step, and cooling after adding, thereby obtaining a prepolymer with the solid content of 48-50%;
(7) weighing 35 parts by mass of the prepolymer and 100 parts by mass of water, adding the mixture into a reaction kettle, uniformly stirring, and starting to heat;
(8) keeping the temperature when the temperature is raised to be within the range of 40-45 ℃, dropwise adding 15 parts by mass of epoxy chloropropane into the system, and completing dripping within 30 min;
(9) after the dropwise addition, preserving heat for 10min at the temperature of 40-45 ℃, heating to the temperature of 60-75 ℃, preserving heat for reaction for 60min, adjusting the pH value to be within the range of 3-4 by using acid, cooling to 30 ℃, and discharging.
Second, specific examples
The compositions of the reagents adopted by the invention are shown in the following table:
Figure 952156DEST_PATH_IMAGE004
Figure DEST_PATH_IMAGE005
Figure 138418DEST_PATH_IMAGE006
examples 1 to 7 were set up, the reagent compositions of which are shown in the following table:
Figure 595944DEST_PATH_IMAGE007
example 1
The process flow is as follows: taking a wood veneer with double-color defects as a raw material, firstly carrying out wire drawing treatment, then carrying out color fading treatment, and then drying to obtain a veneer A; b. the veneer is subjected to impregnation treatment by adopting modified resin, and is dried to prepare a veneer B; c. coating the veneer B with a color-changing agent, and drying to obtain a veneer C; d. coating the environment-friendly glue on the upper surface of the substrate, compounding the C single plate on the upper surface of the substrate coated with the environment-friendly glue, and pressing; e. and (3) cutting, sanding and painting the pressed plate blank to obtain the chemical color-changing composite floor. The fading treatment comprises the following steps: heating the color fading agent to 50 ℃, and immersing the wood veneer into the color fading agent, wherein the bath ratio is V: v plate =20:1, maintain pH 9, time 2 h. The impregnation treatment comprises the following steps: vacuum degree of-0.08 MPa, vacuum time of 30min, pressurizing pressure of 0.5MPa, and pressurizing time of 4 h. The drying process is a step-by-step drying process: the method comprises the steps of firstly reducing the water content of a veneer to be within the range of 18-28% through a roller dryer, then reducing the water content of the veneer to be within the range of 8-15% through a vacuum drying kiln, and finally balancing the water content of the veneer to be within the range of 6-12% through a curing house. The parameters of the pressing process are unit pressure of 0.5MPa, time of 3 minutes and temperature of 110 ℃.
The process flow of examples 2-3 is the same as example 1.
Example 4
The process flow is as follows: a. taking a wood veneer with a color change defect as a raw material, firstly carrying out wire drawing treatment, then carrying out color fading treatment, and then drying to obtain a veneer A; b. the veneer is subjected to impregnation treatment by adopting modified resin, and is dried to prepare a veneer B; c. coating the veneer B with a color-changing agent, and drying to obtain a veneer C; d. coating the environment-friendly glue on the upper surface of the substrate, compounding the C single plate on the upper surface of the substrate coated with the environment-friendly glue, and pressing; e. and (3) cutting, sanding and painting the pressed plate blank to obtain the chemical color-changing composite floor. The fading treatment comprises the following steps: heating the color fading agent to 60 ℃, and immersing the wood veneer into the color fading agent at a bath ratio of VLiquid for medical purpose:VBoard=20:1, pH 10 maintained for 4 h. The impregnation treatment comprises the following steps: vacuum degree of-0.1 MPa, vacuum time of 60min, pressurizing pressure of 1.5MPa, and pressurizing time of 6 h. The drying process is a step-by-step drying process: the method comprises the steps of firstly reducing the water content of a veneer to be within the range of 18-28% through a roller dryer, then reducing the water content of the veneer to be within the range of 8-15% through a vacuum drying kiln, and finally balancing the water content of the veneer to be within the range of 6-12% through a curing house. The parameters of the pressing process are unit pressure of 1.5MPa, time of 7 minutes and temperature of 140 ℃.
The process flow of examples 5-7 is the same as example 4.
Comparative example 1 was set up, which differs from example 1 in that pure water was used instead of the color fading agent.
Comparative facility 2, which is different from example 1 in that pure water was used in place of the modifier.
Comparative example 3 was set up which differs from example 1 in that the modified polyamide polyamine epichlorohydrin resin of the present invention was replaced with a commercially available PAE resin.
Comparative example 4 was set up, which differs from example 1 in that pure water was used instead of tannic acid.
The finished products prepared in the embodiments 1 to 7 and the comparative examples 1 to 4 are detected, and the detection data are as follows:
Figure 144737DEST_PATH_IMAGE009
as shown in the table above, the component ratios of examples 1 to 7 were selected within the range specified in the scheme of the present invention, and the performance of the final composite veneer was not affected. Comparative example 1 lacks the treatment of the color fading agent, the mechanical strength of the obtained composite wood board is not obviously reduced, but the appearance of the finished product is obviously reduced, which proves that the color fading agent adopted by the invention has obvious effect on improving the coloring effect; comparative example 2 lacks modifier modification treatment, and the obtained composite wood board has obvious reduction of each mechanical strength and influences the final coloring effect, so the necessity of the modifier added in the invention for improving the mechanical strength is proved; the comparative example 3 selects the conventional PAE resin, and the obtained composite wood board has the mechanical strength values lower than that of the composite wood board prepared by adopting the modified polyamide polyamine epichlorohydrin resin, so that the reinforcing effect of the modified resin adopted by the invention is proved to be better than that of the PAE resin; comparative example 4, which does not use tannic acid and has a large influence on the final coloring effect, demonstrates the necessity of tannic acid addition of the present invention.
In conclusion, the wood processing technology with the double-color or color-changing defect provided by the invention has the advantages that the prepared composite board has high mechanical strength, good stability and good coloring effect, the quality grade of wood is greatly improved, the application range is wide, and the application prospect is good.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments, or alternatives may be employed, by those skilled in the art, without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (8)

1. The preparation method of the chemical color-changing composite floor is characterized by comprising the following steps of:
the method comprises the following steps: carrying out fading treatment on the double-color or color-changing wood veneer, and drying to obtain a veneer A;
step two: dipping the veneer A by using a modifier, and drying to obtain a veneer B;
step three: coating the veneer B with a color-changing agent, and drying to obtain a veneer C;
step four: carrying out pressing treatment on the C veneer;
step five: carrying out post-treatment on the laminated board obtained in the step four to obtain a chemical color-changing composite floor board;
the modifier contains modified polyamide polyamine epichlorohydrin resin, and the modified polyamide polyamine epichlorohydrin resin is prepared by embedding diamine into a polyamide main chain and modifying with epichlorohydrin;
a color fading agent is used in the color fading treatment of the first step, and the color fading agent comprises the following components in parts by mass: 20-60 parts of 35% (w/w) hydrogen peroxide, 8-15 parts of sodium silicate, 1-3 parts of magnesium sulfate, 5-10 parts of diethylenetriamine pentamethylene phosphonic acid, 0.1-0.5 part of magnesium aluminum silicate, 1-3 parts of sodium hydroxide and 800-1000 parts of water;
the modifier in the second step comprises the following components in parts by mass: 100-150 parts of modified polyamide polyamine epoxy chloropropane resin, 1-5 parts of surfactant and 1-10 parts of tannic acid.
2. The method of claim 1, wherein the color fading process comprises: and heating the color fading agent to 50-60 ℃, controlling the pH value to be 9-10, and then immersing the bicolor or discolored wood veneer into the color fading agent for fading for 2-4 hours.
3. The method for preparing the chemical color-changing composite floor board according to claim 1, wherein the color-changing agent in the third step comprises the following components in parts by mass: 0.05 to 5 parts of metal salt containing ferric ions or ferrous ions, 0.5 to 2 parts of acidic silica sol and 100 to 200 parts of water.
4. The method for preparing a chemical discoloration composite floor according to claim 1, wherein said modified polyamide polyamine epichlorohydrin resin has the structure:
Figure DEST_PATH_IMAGE002
wherein R1, R2 are selected from the group:
Figure DEST_PATH_IMAGE004
Figure DEST_PATH_IMAGE006
one kind of (1).
5. The method for preparing a chemical discoloration composite floor board according to claim 4, wherein the method for preparing the modified polyamide polyamine epichlorohydrin resin comprises the following steps: (1) adding adipic acid a into the hexamethylenediamine solution at a constant speed, and reacting for 30-60 min at 70-80 ℃; (2) adding adipic acid b, adjusting the temperature to 55-65 ℃, and then dropwise adding diethylenetriamine at a constant speed; (3) after the dropwise addition is finished, adjusting the temperature to 90-110 ℃, adding a catalyst, adjusting the temperature to 135-145 ℃, and reacting for 40-70 min; (4) adjusting the temperature to 160-180 ℃, and reacting for 180-280 min; (5) stopping heating, adding water with the temperature of 70-100 ℃, and cooling to obtain a prepolymer; (6) mixing the prepolymer with water, controlling the temperature to be 40-45 ℃, and dropwise adding epoxy chloropropane; (7) and after the dropwise addition is finished, carrying out reaction to obtain the modified polyamide polyamine epichlorohydrin resin.
6. The method as claimed in claim 5, wherein the weight ratio of adipic acid a to adipic acid b is 2: 3.
7. The method as claimed in claim 1, wherein the impregnation treatment conditions in the second step include: the vacuum degree is minus 0.08 to minus 0.1MPa, the vacuum time is 30 to 60min, the pressurizing pressure is 0.5 to 1.5MPa, and the pressurizing time is 4 to 6 hours.
8. The method for preparing a chemical color-changing composite floor as claimed in claim 1, wherein the press-fitting conditions in the fourth step include: the unit pressure is 0.5-1.5 MPa, the time is 3-7 minutes, and the temperature is 110-140 ℃.
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