阅读说明：本技术 一种高色牢度环保灰色系重组装饰单板及其制造工艺 (High-color-fastness environment-friendly gray series recombined decorative veneer and manufacturing process thereof ) 是由 程明娟 彭国青 吴云刚 刘元强 吴翔宇 刘瑶文 陈凯 王俊敏 唐小燕 于 2021-09-13 设计创作，主要内容包括：本发明木材加工领域,特别涉及一种高色牢度环保灰色系重组装饰单板及其制造工艺,本发明制备的单板耐光色牢度高。本发明的单板甲醛释放量≤0.025 mg/m??；总挥发性有机化合物(72 h)≤0.50 mg/m～(2)·h；含水率：4.0%～14.0%；耐光色牢度大于等于灰度卡4级。其制造工艺包括以下步骤：S1、将原木通过旋切或者刨切成单板；S2、将所得旋切/刨切单板进行乙酰化协同紫外线吸收剂预处理改性处理；S3、将所得乙酰化改性后的单板进行染色前预处理,然后初步烘干至含水率8-10%；再接着使用木材染色装置进行染色,染液采用水性高耐光色牢度染液；S4、固色耐光处理；S5、将步骤S4中的染色单板通过修补、仿生组坯、无醛胶黏剂涂胶、胶合、养生等工序加工成重组装饰单板/材。(The invention belongs to the field of wood processing, and particularly relates to an environment-friendly gray system recombined decorative veneer with high color fastness and a manufacturing process thereof. The single-plate formaldehyde emission amount is less than or equal to 0.025 mg/m during the high-speed cultivation; total volatile organic compounds (72 h) is less than or equal to 0.50 mg/m 2 H; water content: 4.0% -14.0%; the color fastness to light is more than or equal to 4 levels of the gray card. The manufacturing process comprises the following steps: s1, rotary cutting or slicing the log into veneers; s2, performing acetylation synergistic ultraviolet absorbent pretreatment modification treatment on the rotary-cut/sliced veneer; s3, pretreating the acetylated and modified veneer before dyeing, and then primarily drying the veneer until the water content is 8-10%; then, dyeing by using a wood dyeing device, wherein the dyeing solution is water-based high light fastness dyeing solution; s4, fixing color and light fastness treatment; and S5, processing the dyed veneer in the step S4 into a recombined decorative veneer/material through the procedures of repairing, bionic assembly, gluing without aldehyde adhesive, gluing, curing and the like.)

1. A high-color-fastness environment-friendly gray series recombined decorative veneer is characterized in that:

carrying out high yield and high yield cultivation under high yield and high yield;

total volatile organic compounds (72 h) is less than or equal to 0.50 mg/m²·h；

Water content: 4.0% -14.0%;

the color fastness to light is more than or equal to 4-level gray card (GB/T15104-.

2. A manufacturing process of a high-color-fastness environment-friendly gray series recombined decorative veneer is characterized by comprising the following steps:

s1, rotary cutting or slicing the log into veneers;

s2, performing acetylation and ultraviolet absorbent synergistic pretreatment modification on the rotary-cut/sliced veneer obtained in the step S1;

s3, pretreating the acetylated and modified veneer obtained in the step S2 before dyeing, and then primarily drying the veneer until the water content is 8-10%; then, dyeing by using a wood dyeing device, wherein the dyeing solution is water-based high light fastness dyeing solution;

s4, fixation and light fastness treatment: adopting ultraviolet absorbent and light stabilizer to carry out single-plate light-resistant treatment; specifically, the mass ratio of 1: 3-6 of titanium oxide and phenyl salicylate are uniformly mixed, ethanol with the mass 20-30 times that of the titanium oxide is added and uniformly mixed to obtain a color fixing soaking solution, then the veneer treated in the step S3 is immersed in the color fixing soaking solution for 30-50 minutes, heated to 50-80 ℃ and kept for 15-20 minutes, naturally cooled, and taken out and dried until the water content is 6-8%;

and S5, processing the dyed veneer in the step S4 into a recombined decorative veneer/material through the procedures of repairing, bionic assembly, gluing without aldehyde adhesive, gluing, curing and the like.

3. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 2, is characterized in that: the method for pretreating and modifying the acetylation synergistic ultraviolet absorbent comprises the step S2 of diluting acetic anhydride with acetic acid solvent to obtain 20-30wt% acetic anhydride solution, adding 4-6 wt% UV1130, and soaking at 110-.

4. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 2, is characterized in that: the aldehyde-free adhesive in the step S5 is prepared by a hydroxymethylation lignin and melamine-urea resin blending technology, and the preparation method comprises the following steps:

s11, processing for 40-80min by adopting a ball milling method when the oscillation frequency is 10-50Hz to obtain lignin powder;

s12, performing addition reaction on the lignin powder to form hydroxymethylated lignin;

s13, uniformly mixing the hydroxymethylated lignin with MUF resin according to the proportion of 20-40wt% to prepare the aldehyde-free lignin-melamine urea-formaldehyde resin adhesive.

5. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 4, is characterized in that: and a first mixing system with the weight percentage of 5-8wt% is added during the mixing in the step S13, and the mass ratio of the first mixing system is 1: 2-4, and mixing the polyvinyl acetate emulsion and the mercaptoacetic glyceride mixture.

6. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 2, is characterized in that: the pretreatment before dyeing of step S3 includes

(1) Weighing anhydrous calcium chloride and acrylic acid according to the mass ratio of 1:5-8 to obtain a primary mixture, grinding stone needle powder until the particle size is 0.2-0.5 mm, and mixing the stone needle powder and the primary mixture according to the mass ratio of 1: 1-3, adding water with the mass 8-10 times of that of the primary mixture, stirring, and then sieving to remove filter residues to obtain a filtrate;

(2) placing the filter residue recovered in the step (1) in a hydrochloric acid solution according to the material liquid mass ratio of 1:4-5 for soaking at normal temperature, filtering and washing after soaking to obtain solid particles, drying the solid particles at the temperature of 100-950 ℃ for 1-2 hours, calcining the solid particles at the temperature of 850-950 ℃ for 1-2 hours, naturally cooling and grinding to obtain stone needle powder with a nano particle size;

(3) adding N-acylamino sodium carbonate accounting for 0.1-0.2% of the mass of the filtrate and stone needle powder accounting for 0.06-0.09% of the mass of the filtrate, which is prepared in the step (2), into the filtrate obtained in the step (1) to obtain a first soaking solution, uniformly stirring and dispersing, soaking the acetylated and modified veneer obtained in the step S2 into the first soaking solution for 10-15 minutes, pressurizing, heating, boiling for 20-30 minutes, naturally cooling, taking out the veneer, and drying until the water content is 8-10%, so that the veneer can be dyed by using the aqueous high-light-fastness dyeing solution.

7. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 2, is characterized in that: the water-based dye solution with high light fastness in the step S3 is a gray system of chloro-S-triazine and vinyl sulfone reactive dyes; the reactive dye is also added with a composite regulator, and the composite regulator is prepared from the following components in a mass ratio of 1: 2-5 of tetraethoxysilane and silane coupling agent.

8. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 7, is characterized in that: the silane coupling agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane and vinyl tri (beta-methoxyethoxy) silane.

9. The manufacturing process of the high-color-fastness environment-friendly gray series recombined decorative veneer according to any one of claims 2 to 8, characterized in that: step S3 high color fastness wood dyeing apparatus includes dye vat (1) and can dismantle lid (2) of connection at dye vat (1) top, its characterized in that: the utility model discloses a dye vat, including lid (2), support ring (32), net section of thick bamboo (3), mounting ring (31) fixed mounting is on the top week side of net section of thick bamboo (3), the bottom fixed mounting of lid (2) has a plurality of elastic telescopic rod (4), the bottom fixed mounting of elastic telescopic rod (4) has and presses otter board (5).

10. The manufacturing process of the high-color-fastness environment-friendly gray system recombined decorative veneer according to claim 9, is characterized in that: elasticity telescopic link (4) include sleeve (41) and movable rod (42), sleeve (41) fixed connection is in the bottom of lid (2), movable rod (42) activity cup joints the bottom at sleeve (41), press otter board (5) fixed mounting in the bottom of movable rod (42), still be provided with spring (411) in sleeve (41), just the one end of spring (411) offsets with the interior roof of sleeve (41), and the other end offsets with movable rod (42).

Technical Field

The invention relates to the field of wood processing, in particular to an environment-friendly gray series recombined decorative veneer with high color fastness and a manufacturing process thereof.

Background

The recombined decorative veneer is made of artificial fast growing wood as raw material, and has no damage to the microstructure and inherent properties of wood, and is made up through rotary cutting of log, bleaching of veneer, dyeing, gluing, assembling, die pressing, curing and slicing.

The luxury of artistic expression is one of the current mainstream decorative styles, however, the gray color is a few of natural precious tree species, and the series of recombined decorative veneer products need to be developed to meet the consumption requirements. The recombined decorative veneer is characterized in that rich and colorful colors are obtained by dyeing in the manufacturing process of the recombined decorative veneer, and when the recombined decorative veneer is stored and used, the colors and the luster can be changed to different degrees under the irradiation of sunlight or other light sources, namely, the problem of low light fastness exists, and a gray product is particularly prominent. In addition, the recombined decorative veneer products are mainly applied to surface decoration production of veneers, and in the current national standards, the recombined decorative veneers and the veneers have different light color fastness detection methods, and the exposure time specified by the veneers standards needs to be prolonged by about 5 times, namely the requirement on the color fastness is higher.

The recombined decorative veneer is suitable for furniture, cabinets, bathroom cabinets, floors, curtain walls, door lines, automotive interior trims and the like, and relates to the fields of home decoration, buildings, traffic and the like. In recent years, gray series recombined decorative veneers are more popular with consumers, but are limited to develop due to the problem of low light fastness.

Disclosure of Invention

The invention aims to provide an environment-friendly gray series recombined decorative veneer with high color fastness.

The second purpose of the present invention is to provide a manufacturing process of a gray reconstituted decorative veneer with high color fastness and environmental protection.

The first technical purpose of the invention is realized by the following technical scheme:

an environment-friendly gray series recombined decorative veneer with high color fastness,

carrying out high yield and high yield cultivation under high yield and high yield;

total volatile organic compounds (72 h) is less than or equal to 0.50 mg/m²·h；

Water content: 4.0% -14.0%;

the color fastness to light is more than or equal to 4-level gray card (GB/T15104-.

The second technical purpose of the invention is realized by the following technical scheme:

a manufacturing process of a high-color-fastness environment-friendly gray series recombined decorative veneer comprises the following steps:

s1, rotary cutting or slicing the log into veneers;

s2, performing acetylation synergistic ultraviolet absorbent pretreatment modification treatment on the rotary-cut/sliced veneer obtained in the step S1;

s3, pretreating the acetylated and modified veneer obtained in the step S2 before dyeing, and then primarily drying the veneer until the water content is 8-10%; then, dyeing by using a wood dyeing device, wherein the dyeing solution is water-based high light fastness dyeing solution;

s4, fixation and light fastness treatment: adopting ultraviolet absorbent and light stabilizer to carry out single-plate light-resistant treatment; specifically, the mass ratio of 1: 3-6 of titanium oxide and phenyl salicylate are uniformly mixed, ethanol which accounts for 20-30 times of the mass of the titanium oxide is added and uniformly mixed to obtain a color fixing soaking solution, then the veneer treated in the step S3 is immersed in the color fixing soaking solution for 30-50 minutes, then the veneer is heated to 50-80 ℃ and kept for 15-20 minutes, the temperature is naturally reduced, and the veneer is taken out and dried until the water content is 6-8%;

and S5, processing the dyed veneer in the step S4 into a recombined decorative veneer/material through the procedures of repairing, bionic assembly, gluing without aldehyde adhesive, gluing, curing and the like.

The recombined decorative veneer after pretreatment and high-color-fastness dyeing has the advantages that a guide pipe is permeated with a treatment liquid, the treatment liquid reacts with hydroxyl and sulfonic acid groups in a three-dimensional space net structure to modify the cellulose of the veneer, the dyeing liquid diffuses to an amorphous area inside the fiber from outside to inside to achieve and maintain dynamic balance, the performances such as dye uptake, light resistance and the like are improved, meanwhile, through further color-fixing light-resistant treatment, the hydroxyl of the cellulose fiber is dissociated to form hydroxyl anions, and the hydroxyl anions and the dyeing liquid undergo chemical reactions such as nucleophilic substitution, nucleophilic addition and the like to generate a firm covalent bond between the fiber and the dyeing liquid, so that the excellent performances in terms of tinting strength and tolerance are achieved. The gray series recombined decorative veneer processed by the method has the color tone from light gray to dark gray, and the color after coloring is uniform and natural; the coloring penetration depth can reach 2-4mm, and the color fastness is high.

The light fastness of the invention is detected according to the national standard method of the veneer, and the requirement of high color fastness is met.

Preferably, the acetylation cooperating with the pretreatment modification of the ultraviolet absorber in step S2 comprises diluting acetic anhydride with acetic acid solvent to obtain 20-30wt% acetic anhydride solution, adding 4-6 wt% UV1130, and soaking at 110-130 deg.C for 20-40min to obtain rotary-cut/sliced veneer in step S1. Wherein, 4-6% (weight ratio) refers to the weight ratio of the acetic anhydride solution.

The method combines a wood fading mechanism, and performs acetylation synergistic ultraviolet absorbent pretreatment modification on the wood, so that the stability of the groups can be improved.

Preferably, the adhesive is prepared by a hydroxymethylation lignin and melamine-urea resin blending technology, and the preparation method comprises the following steps:

s11, processing for 40-80min by adopting a ball milling method when the oscillation frequency is 10-50Hz to obtain lignin powder;

s12, performing addition reaction on the lignin powder to form hydroxymethylated lignin;

s13, uniformly mixing the hydroxymethylated lignin with MUF resin according to the proportion of 20-40wt% to prepare the aldehyde-free lignin-melamine urea-formaldehyde resin adhesive.

The adhesive disclosed by the invention is green and environment-friendly, is beneficial to forming a uniform and stable adhesive system, improves the adhesive bonding capability and adhesive bonding stability of the adhesive, and is beneficial to eliminating stress and improving the adhesive bonding performance of the recombined veneer; meanwhile, the color fastness of the recombinant veneer can be further improved through addition reaction.

Preferably, a first mixing system in an amount of 5-8wt% is further added during the mixing in the step S13, and the first mixing system is a mixture of 1: 2-4, and mixing the polyvinyl acetate emulsion and the mercaptoacetic glyceride mixture.

The first mixed system has a synergistic toughening effect, has a good toughening effect on the urea-formaldehyde resin adhesive, overcomes the defects that a cutter is damaged when a product is sliced and the sliced product is easy to crack because the adhesive layer is hard after the cold-set urea-formaldehyde resin is cured, and manufactures a recombined decorative material product with better performance.

Preferably, the pre-dyeing pretreatment comprises

(1) Weighing anhydrous calcium chloride and acrylic acid according to the mass ratio of 1:5-8 to obtain a primary mixture, grinding stone needle powder until the particle size is 0.2-0.5 mm, and mixing the stone needle powder and the primary mixture according to the mass ratio of 1: 1-3, adding water with the mass 8-10 times of that of the primary mixture, stirring, and then sieving to remove filter residues to obtain a filtrate;

(2) placing the filter residue recovered in the step (1) in a hydrochloric acid solution according to the material liquid mass ratio of 1:4-5 for soaking at normal temperature, filtering and washing after soaking to obtain solid particles, drying the solid particles at the temperature of 100-950 ℃ for 1-2 hours, calcining the solid particles at the temperature of 850-950 ℃ for 1-2 hours, naturally cooling and grinding to obtain stone needle powder with a nano particle size;

(3) adding N-acylamino sodium carbonate accounting for 0.1-0.2% of the mass of the filtrate and stone needle powder accounting for 0.06-0.09% of the mass of the filtrate, which is prepared in the step (2), into the filtrate obtained in the step (1) to obtain a first soaking solution, uniformly stirring and dispersing, soaking the acetylated and modified veneer obtained in the step S2 into the first soaking solution for 10-15 minutes, pressurizing, heating, boiling for 20-30 minutes, naturally cooling, taking out the veneer, and drying until the water content is 8-10%, so that the veneer can be dyed by using the aqueous high-light-fastness dyeing solution.

The veneer subjected to acetylation modification obtained in the step S2 is treated and modified, the prepared nano stone needle powder particles with large specific surface area and capable of emitting infrared rays after being heated are added, the generated surface energy efficiency enables the nano stone needle particles to be fully combined with a veneer matrix, the activity of the reaction of hydroxyl in cellulose, hemicellulose and lignin in the veneer and a water-based dye with high light fastness and high color fastness can be improved, the stability after dyeing is also improved, the toughness, the thermal stability and the size stability of the veneer are remarkably improved after pressure cooking treatment, and the problem that the existing dye is poor in veneer dyeing, particularly gray system dyeing, is solved after dyeing.

Preferably, the aqueous dye solution with high light fastness is a gray system of chlorine-s-triazine and vinyl sulfone reactive dyes; the reactive dye is also added with a composite regulator, and the composite regulator is prepared from the following components in a mass ratio of 1: 2-5 of tetraethoxysilane and silane coupling agent.

The composite regulator can improve the connection between the dye and the wood, the wood fiber and the active dye generate chemical reaction to generate ether bond to fix the active dye on the wood, and the composite regulator has extremely large specific surface area and higher specific surface energy, so that an oxide film with a three-dimensional network structure is easily formed on the surface of the wood, the active dye is three-dimensionally fixed in a siloxane matrix by the oxide film, and the effect of improving the dyeing and color fixing rate of the dyed wood is achieved.

More preferably, the silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.

Preferably, step S3 high colour fastness wood dyeing apparatus includes the dye vat and can dismantle the lid of connection at the dye vat top, the internal perisporium fixed mounting of dye vat has the support ring, the inside of support ring is provided with a net section of thick bamboo, the top week side fixed mounting of a net section of thick bamboo has the collar, collar fixed mounting is on the upper surface of support ring, the bottom fixed mounting of lid has a plurality of elasticity telescopic links, the bottom fixed mounting of elasticity telescopic link has the press screen board.

The device adopts the matching among the net cylinder, the cover body, the sleeve, the spring and the movable rod, wood is put into the net cylinder and the cover body is covered, when the pressing screen plate is contacted with the wood, the movable rod can be contracted into the sleeve and presses the spring, and meanwhile, the pressing screen plate can press the wood so that the wood is completely immersed in the dye solution, thereby solving the problem that the wood is difficult to completely color due to the fact that the density of the wood is lower and the wood is generally in a floating state during dyeing.

More preferably, the inner bottom wall of the dye vat is rotatably connected with a stirring shaft, the bottom wall of the dye vat is fixedly provided with a motor, and the top output end of the motor penetrates through the bottom wall of the dye vat and is fixedly connected with the stirring shaft.

More preferably, a plurality of stirring blades are fixedly installed on the peripheral side surface of the stirring shaft, and the stirring blades are distributed in a circumferential array.

More preferably, the inner bottom wall of the dye vat is provided with a sealing bearing, and the stirring shaft is rotatably connected to the inner part of the sealing bearing.

More preferably, a temperature sensor is fixedly arranged on the inner bottom wall of the dye vat.

More preferably, the bottom of the net cylinder is provided with a heating pipe, the outer wall of the dye vat is provided with a controller, the input end of the controller is electrically connected with the output end of the heating pipe, and the output end of the controller is electrically connected with the input end of the temperature sensor.

More preferably, the elasticity telescopic link includes sleeve and movable rod, sleeve fixed connection is in the bottom of lid, the movable rod activity cup joints in telescopic bottom, press otter board fixed mounting in the bottom of movable rod, still be provided with the spring in the sleeve, just the one end of spring offsets with telescopic interior roof, and the other end offsets with the movable rod.

The invention adopts the matching among the net cylinder, the cover body, the sleeve, the spring and the movable rod, the motor drives the stirring blade to rotate through the stirring shaft and stir the dye liquor in the dye vat, and the dye liquor drives the wood to carry out irregular floating motion in the net cylinder, so that all directions of the wood can be soaked by the dye liquor.

In conclusion, the invention has the following beneficial effects:

1. the wood is acetylated and modified by combining a wood fading mechanism, so that the stability of groups is improved; a specific aqueous dye solution with high light fastness is adopted, according to a dye-uptake mechanism, a composite regulator is preferably selected to improve the connection between the dye and the wood, and then color fixation and light fastness treatment is adopted to further improve the light fastness;

2. the high-temperature and high-pressure dyeing process is adopted, so that the dyeing temperature and the dyeing pressure are improved, on one hand, the high-color-fastness dye with poor permeability can be immersed into the veneer, on the other hand, the dyeing time can be obviously shortened, and the efficiency is improved;

3. the recombined decorative veneer after pretreatment and high-color-fastness dyeing has the advantages that a guide pipe is permeated with a treatment liquid, the treatment liquid reacts with hydroxyl and sulfonic acid groups in a three-dimensional space net structure to modify the cellulose of the veneer, the dyeing liquid diffuses to an amorphous area inside the fiber from outside to inside to achieve and maintain dynamic balance, the performances such as dye uptake, light resistance and the like are improved, meanwhile, through further color-fixing light-resistant treatment, the hydroxyl of the cellulose fiber is dissociated to form hydroxyl anions, and the hydroxyl anions and the dyeing liquid undergo chemical reactions such as nucleophilic substitution, nucleophilic addition and the like to generate a firm covalent bond between the fiber and the dyeing liquid, so that the excellent performances in terms of tinting strength and tolerance are achieved. The gray series recombined decorative veneer processed by the method has the color tone from light gray to dark gray, and the color after coloring is uniform and natural; the coloring penetration depth can reach 2-4mm, and the color fastness is high;

4. the water-based high-color-fastness dye solution is used for replacing common dyes, so that the light color fastness grade of the recombined decorative material is more than or equal to the 4-grade gray card, and other indexes meet the standard requirements of GB/T28999-.

Drawings

FIG. 1 is a schematic view of the overall structure of the present invention;

FIG. 2 is a schematic view of the internal structure of the dye vat of the present invention;

FIG. 3 is a schematic view of a connecting structure of a cover and a pressing screen according to the present invention;

fig. 4 is an enlarged view of the invention at a in fig. 2.

In the figure: 1. a dye vat; 2. a cover body; 3. a net drum; 31. a mounting ring; 32. a support ring; 4. an elastic telescopic rod; 41. a sleeve; 411. a spring; 42. a movable rod; 5. pressing the screen plate; 6. a motor; 61. a stirring shaft; 611. sealing the bearing; 62. a stirring blade; 7. a temperature sensor; 71. heating a tube; 72. and a controller.

Detailed Description

Example 1

A manufacturing process of a high-color-fastness environment-friendly gray series recombined decorative veneer comprises the following steps:

s1, rotary cutting or slicing the log into veneers;

s2, performing acetylation synergistic ultraviolet absorbent pretreatment modification on the rotary-cut/sliced veneer obtained in the step S1, wherein the specific method comprises the steps of diluting acetic anhydride by using an acetic acid solvent to obtain an acetic anhydride solution with the concentration of 20wt%, adding 4% (weight ratio) of UV1130, and soaking the mixture at 110 ℃ for 20min to obtain the rotary-cut/sliced veneer obtained in the step S1;

s3, pretreating the acetylated and modified veneer obtained in the step S2 before dyeing, and then primarily drying the veneer until the water content is 8%; then, dyeing by using a high-color-fastness wood dyeing device, wherein the dye solution adopts a water-based high-light-fastness dye solution;

the aqueous dye liquor with high light fastness is a gray system of chloro-s-triazine and vinyl sulfone reactive dyes; the reactive dye is also added with a composite regulator, and the mass ratio of the composite regulator is 1: 2, mixing tetraethoxysilane and silane coupling agent;

the silane coupling agent is vinyl triethoxysilane;

s4, fixation and light fastness treatment: adopting ultraviolet absorbent and light stabilizer to carry out single-plate light-resistant treatment; specifically, the mass ratio of 1: 3, uniformly mixing the titanium oxide and the phenyl salicylate, adding ethanol with the mass being 20 times that of the titanium oxide, uniformly mixing to obtain a color fixing soaking solution, immersing the veneer treated in the step S3 in the color fixing soaking solution for 30 minutes, heating to 50 ℃, keeping for 15 minutes, naturally cooling, taking out the veneer, and drying until the water content is 6%;

s5, processing the dyed veneer in the step S4 into a recombined decorative veneer/material through the procedures of repairing, bionic assembly, gluing without aldehyde adhesive, gluing, health preserving and the like;

the aldehyde-free adhesive is prepared by hydroxymethylation lignin and melamine-urea resin blending technology, and the preparation method comprises the following steps:

s11, processing for 40min by adopting a ball milling method when the oscillation frequency is 10Hz to obtain lignin powder;

s12, performing addition reaction on the lignin powder to form hydroxymethylated lignin;

s13, uniformly mixing the hydroxymethylated lignin with MUF resin according to the proportion of 20wt% to prepare the aldehyde-free lignin-melamine urea-formaldehyde resin adhesive.

Example 2

A manufacturing process of a high-color-fastness environment-friendly gray series recombined decorative veneer comprises the following steps:

s1, rotary cutting or slicing the log into veneers;

s2, performing acetylation synergistic ultraviolet absorbent pretreatment modification on the rotary-cut/sliced veneer obtained in the step S1, wherein the specific method comprises the steps of diluting acetic anhydride by using an acetic acid solvent to obtain an acetic anhydride solution with the concentration of 30wt%, adding 6% (weight ratio) of UV1130, and soaking at 130 ℃ for 40min to obtain the rotary-cut/sliced veneer obtained in the step S1;

s3, pretreating the acetylated and modified veneer obtained in the step S2 before dyeing, and then primarily drying the veneer until the water content is 10%; then, dyeing by using a high-color-fastness wood dyeing device, wherein the dye solution adopts a water-based high-light-fastness dye solution;

the aqueous dye liquor with high light fastness is a gray system of chloro-s-triazine and vinyl sulfone reactive dyes; the reactive dye is also added with a composite regulator, and the mass ratio of the composite regulator is 1:5, mixing tetraethoxysilane and silane coupling agent; the silane coupling agent is vinyltrimethoxysilane.

S4, fixation and light fastness treatment: adopting ultraviolet absorbent and light stabilizer to carry out single-plate light-resistant treatment; specifically, the mass ratio of 1:6, uniformly mixing titanium oxide and phenyl salicylate, adding ethanol with the mass being 30 times that of the titanium oxide, uniformly mixing to obtain a color fixing soaking solution, immersing the veneer treated in the step S3 in the color fixing soaking solution for 50 minutes, heating to 80 ℃, keeping for 20 minutes, naturally cooling, taking out the veneer, and drying until the water content is 8%;

s5, processing the dyed veneer in the step S4 into a recombined decorative veneer/material through the procedures of repairing, bionic assembly, gluing without aldehyde adhesive, gluing, health preserving and the like;

the aldehyde-free adhesive is prepared by hydroxymethylation lignin and melamine-urea resin blending technology, and the preparation method comprises the following steps:

s11, processing for 80min by adopting a ball milling method when the oscillation frequency is 50Hz to obtain lignin powder;

s12, performing addition reaction on the lignin powder to form hydroxymethylated lignin;

s13, uniformly mixing hydroxymethylated lignin with MUF resin according to the proportion of 40wt% to prepare the aldehyde-free lignin-melamine urea-formaldehyde resin adhesive.

Example 3

A manufacturing process of a high-color-fastness environment-friendly gray series recombined decorative veneer comprises the following steps:

s1, rotary cutting or slicing the log into veneers;

s2, performing acetylation synergistic ultraviolet absorbent pretreatment modification on the rotary-cut/sliced veneer obtained in the step S1, wherein the specific method comprises the steps of diluting acetic anhydride by using an acetic acid solvent to obtain an acetic anhydride solution with the concentration of 25wt%, adding 5% (weight ratio) of UV1130, and soaking at 120 ℃ for 30min to obtain the rotary-cut/sliced veneer obtained in the step S1;

s3, pretreating the acetylated and modified veneer obtained in the step S2 before dyeing, and then primarily drying the veneer until the water content is 9%; then, dyeing by using a high-color-fastness wood dyeing device, wherein the dye solution adopts a water-based high-light-fastness dye solution;

the aqueous dye liquor with high light fastness is a gray system of chloro-s-triazine and vinyl sulfone reactive dyes; the reactive dye is also added with a composite regulator, and the mass ratio of the composite regulator is 1:4, mixing tetraethoxysilane and silane coupling agent; the silane coupling agent is vinyl tri (beta-methoxy ethoxy) silane.

S4, fixation and light fastness treatment: adopting ultraviolet absorbent and light stabilizer to carry out single-plate light-resistant treatment; specifically, the mass ratio of 1:5, uniformly mixing titanium oxide and phenyl salicylate, adding ethanol accounting for 25 times of the mass of the titanium oxide, uniformly mixing to obtain a color fixing soaking solution, immersing the veneer treated in the step S3 in the color fixing soaking solution for 40 minutes, heating to 60 ℃, keeping for 18 minutes, naturally cooling, taking out the veneer, and drying until the water content is 7%;

s5, processing the dyed veneer in the step S4 into a recombined decorative veneer/material through the procedures of repairing, bionic assembly, gluing without aldehyde adhesive, gluing, health preserving and the like;

the aldehyde-free adhesive is prepared by hydroxymethylation lignin and melamine-urea resin blending technology, and the preparation method comprises the following steps:

s11, processing for 60min by adopting a ball milling method when the oscillation frequency is 30Hz to obtain lignin powder;

s12, performing addition reaction on the lignin powder to form hydroxymethylated lignin;

s13, uniformly mixing hydroxymethylated lignin with MUF resin according to the proportion of 30wt% to prepare the aldehyde-free lignin-melamine urea-formaldehyde resin adhesive.

Example 4

The same as example 1, except that 6wt% of a first mixing system is added during the mixing in the step S13, and the mass ratio of the first mixing system is 1: 3 mixing the polyvinyl acetate emulsion and the mercaptoacetic glyceride mixture.

Example 5

The same as example 1, except that 5wt% of a first mixing system is added during the mixing in the step S13, and the mass ratio of the first mixing system is 1: 2 mixing the polyvinyl acetate emulsion and the mercaptoacetic glyceride mixture.

Example 6

The same as example 1, except that 8wt% of a first mixing system is added during the mixing in the step S13, and the mass ratio of the first mixing system is 1:4 mixing the polyvinyl acetate emulsion and the mercaptoacetic glyceride mixture.

Example 7

The same as example 4, except that the pretreatment before dyeing in step S3 includes

(1) Weighing anhydrous calcium chloride and acrylic acid according to the mass ratio of 1:5 to obtain a primary mixture, grinding stone needle powder until the particle size is 0.2 mm, and mixing the stone needle powder and the primary mixture according to the mass ratio of 1: 1, uniformly mixing, adding water with the mass being 8 times that of the primary mixture, stirring, and then sieving to remove filter residues to obtain a filtrate;

(2) placing the filter residue recovered in the step (1) in a hydrochloric acid solution according to the feed liquid mass ratio of 1:4 for soaking at normal temperature, filtering and washing after soaking to obtain solid particles, drying the solid particles at the temperature of 100 ℃ for 1 hour, calcining the solid particles at the temperature of 850 ℃ for 1 hour, naturally cooling and grinding to obtain the stone needle powder with the nano particle size;

(3) adding N-acylamino sodium carbonate accounting for 0.1% of the mass of the filtrate and stone needle powder accounting for 0.06% of the mass of the filtrate, which is prepared in the step (2), into the filtrate obtained in the step (1), uniformly stirring and dispersing to obtain a first soaking solution, soaking the acetylated and modified veneer obtained in the step S2 in the first soaking solution for 10 minutes, pressurizing, heating, boiling for 20 minutes, naturally cooling, taking out the veneer, and drying until the water content is 8%, thus dyeing by using the aqueous high light fastness dyeing solution.

Example 8

The same as example 5, except that the pretreatment before dyeing in step S3 includes

(1) Weighing anhydrous calcium chloride and acrylic acid according to the mass ratio of 1:8 to obtain a primary mixture, grinding stone needle powder until the particle size is 0.5 mm, and mixing the stone needle powder and the primary mixture according to the mass ratio of 1: 3, uniformly mixing, adding water with the mass being 10 times that of the primary mixture, stirring, and then sieving to remove filter residues to obtain a filtrate;

(2) placing the filter residue recovered in the step (1) in a hydrochloric acid solution according to the feed liquid mass ratio of 1:5 for soaking at normal temperature, filtering and washing after soaking to obtain solid particles, drying the solid particles at 120 ℃ for 2 hours, calcining the solid particles at 950 ℃ for 2 hours, naturally cooling and grinding to obtain the stone needle powder with the nano particle size;

(3) adding N-acylamino sodium carbonate accounting for 0.2% of the mass of the filtrate and stone needle powder accounting for 0.09% of the mass of the filtrate, which is prepared in the step (2), into the filtrate obtained in the step (1) to obtain a first soaking solution, uniformly stirring and dispersing, soaking the acetylated and modified veneer obtained in the step S2 in the first soaking solution for 15 minutes, pressurizing, heating, boiling for 30 minutes, naturally cooling, taking out the veneer, and drying until the water content is 10%, thus dyeing by using an aqueous high-light fastness dyeing solution.

Example 9

The same as example 6, except that the pretreatment before dyeing in step S3 includes

(1) Weighing anhydrous calcium chloride and acrylic acid according to the mass ratio of 1:6 to obtain a primary mixture, grinding stone needle powder until the particle size is 0.4 mm, and mixing the stone needle powder and the primary mixture according to the mass ratio of 1: 2, uniformly mixing, adding water with the mass being 9 times that of the primary mixture, stirring, and then sieving to remove filter residues to obtain a filtrate;

(2) placing the filter residue recovered in the step (1) in a hydrochloric acid solution according to the feed liquid mass ratio of 1:4.5 for soaking at normal temperature, filtering and washing after soaking to obtain solid particles, drying the solid particles at the temperature of 110 ℃ for 1-2 hours, calcining the solid particles at the temperature of 900 ℃ for 1.5 hours, naturally cooling, and grinding to obtain the stone needle powder with the nano particle size;

(3) adding N-acylamino sodium carbonate accounting for 0.15% of the mass of the filtrate and stone needle powder accounting for 0.08% of the mass of the filtrate, which is obtained in the step (2), into the filtrate obtained in the step (1) to obtain a first soaking solution, uniformly stirring and dispersing, soaking the acetylated and modified veneer obtained in the step S2 in the first soaking solution for 12 minutes, pressurizing, heating, boiling for 25 minutes, naturally cooling, taking out the veneer, and drying until the water content is 9%, thus dyeing by using an aqueous high light fastness dyeing solution.

Example 10

In the same embodiment 7, except that the high color fastness wood dyeing apparatus of step S3 adopts a specific apparatus structure, please refer to fig. 1, a high color fastness wood dyeing apparatus includes a dye vat 1 and a cover body 2 detachably connected to the top of the dye vat 1 by a snap connection, and the cover body 2 can be sealed by a sealing ring, a horizontally arranged support ring 32 is fixedly installed on the inner peripheral wall of the dye vat 1, a net cylinder 3 for accommodating wood is arranged inside the support ring 32, the net cylinder 3 can be a net structure made of metal, so that the dye in the dye vat 1 can dye wood through the net cylinder 3, a mounting ring 31 is fixedly installed on the top peripheral side of the net cylinder 3, the mounting ring 31 is fixedly installed on the upper surface of the support ring 32 to mount the net cylinder 3, a space for the dye to move is formed between the net cylinder 3 and the inner wall of the dye vat 1, a plurality of elastic telescopic rods 4 are fixedly installed at the bottom of the dye vat 2, elastic telescopic rod 4 can contract when receiving the extrusion, and elastic telescopic rod 4's bottom fixed mounting has presses otter board 5, presses otter board 5 to be the network structure that the metal was made equally, when covering lid 2 at the top of dye vat 1, and elastic telescopic rod 4 can press timber with pressing mutually supporting of otter board 5, makes it submerge completely in the dye liquor.

Specifically, please refer to fig. 3, the elastic telescopic rod 4 includes a sleeve 41 and a movable rod 42, the sleeve 41 is fixedly connected to the bottom of the cover body 2, the movable rod 42 is movably sleeved on the bottom of the sleeve 41, the movable rod 42 can slide along the axial direction of the sleeve 41, the screen plate 5 is fixedly installed at the bottom of the movable rod 42, a spring 411 is further disposed in the sleeve 41, one end of the spring 411 abuts against the inner top wall of the sleeve 41, the other end of the spring abuts against the movable rod 42, when the screen plate 5 is pressed to contact with wood, the movable rod 42 can contract into the sleeve 41 and press the spring 411, so that the wood is immersed in the dye solution without damaging the wood.

Referring to fig. 1 and 4, in order to improve color fastness, a temperature sensor 7 capable of heating the dye liquor is further fixedly mounted on the inner bottom wall of the dye vat 1, so that the activity of the dye liquor can be increased to increase the dyeing effect, a heating pipe 71 for detecting the temperature in the dye vat 1 is arranged at the bottom of the mesh cylinder 3, a controller 72 is arranged on the outer wall of the dye vat 1, the input end of the controller 72 is electrically connected with the output end of the heating pipe 71, the output end of the controller 72 is electrically connected with the input end of the temperature sensor 7, the heating pipe 71 can transmit temperature information to the controller 72, and if the temperature of the dye liquor in the dye vat 1 is too low, the controller 72 can start the temperature sensor 7 and heat the dye liquor in the dye vat 1.

Referring to fig. 4, in order to make the wood contacted with the net cylinder 3 and the elastic telescopic rod 4 to be dip-dyed by pigment, the inner bottom wall of the dye vat 1 is rotatably connected with a stirring shaft 61, the bottom wall of the dye vat 1 is fixedly provided with a motor 6 for driving the stirring shaft 61 to rotate, the top output end of the motor 6 penetrates through the bottom wall of the dye vat 1 and is fixedly connected with the stirring shaft 61, the stirring shaft 61 can stir the dye liquor when rotating, and the dye liquor drives the wood to perform random floating motion in the net cylinder 3, so that all directions of the wood can be soaked by the dye liquor, the circumferential side surface of the stirring shaft 61 is fixedly provided with a plurality of stirring blades 62 for enhancing stirring effect, the plurality of stirring blades 62 are distributed in a circumferential array, in order to prevent the dye liquor in the dye vat 1 from leaking from the dye vat 1 to cause waste of the dye liquor and pollution to the ground, the inner bottom wall of the dye vat 1 is provided with a sealing bearing 611, the stirring shaft 61 is rotatably connected to the inside of the sealing bearing 611 to perform a sealing effect.

The working principle is as follows: add sufficient dye liquor in with dye vat 1, and put into a net section of thick bamboo 3 with timber and cover lid 2, press down otter board 5 and when timber contacted, movable rod 42 is collapsible to the inside of sleeve 41 and presses spring 411, press down otter board 5 simultaneously and can press down timber, make its complete submergence in the dye liquor, starter motor 6, make motor 6 drive stirring vane 62 through (mixing) shaft 61 and rotate and stir the dye liquor in dye vat 1, and make the dye liquor drive timber and carry out irregular floating movement in a net section of thick bamboo 3, make timber all directions can receive soaking of dye liquor.

Example 11

The same as example 8, except that the high-fastness wood dyeing apparatus of step S3 was constructed in the same manner as in example 10.

Example 12

The same as example 9, except that the high-fastness wood dyeing apparatus of step S3 was constructed in the same manner as in example 10.

Comparative example 1

The same as example 1, except that step S2 was omitted and the acetylation modification treatment was not performed.

Comparative example 2

The same as example 2, except that the pretreatment before dyeing is not performed in step S3, and the dyeing is performed after the primary drying is directly performed after the acetylation modification.

Comparative example 3

The same as example 3, except that step S4 was omitted and no specific fixation and light fastness treatment was carried out.

Comparative example 4

The same as example 4, except that the color fixing soaking solution in the color fixing and light-resisting treatment of step S4 does not contain titanium oxide, and the aldehyde-free adhesive of the present invention is not used in the gluing of step S5.

Detection experiment: and performing physical and chemical detection according to the light color fastness, formaldehyde release amount, dipping stripping parameters, static bending strength and elastic modulus of GB/T28999-.

The above data show that:

1. the high-color-fastness environment-friendly gray-series recombined decorative veneers prepared in the examples 1 to 12 have high color fastness level, which is superior to the color fastness of the recombined decorative veneers in the comparative examples 1 to 4;

2. the high-color-fastness environment-friendly gray-series recombined decorative veneers prepared in the examples 1 to 12 have small formaldehyde emission, small dipping and stripping length of each edge on each glue layer, and larger static bending strength and elastic modulus, and are superior to the performances of the recombined decorative veneers of the comparative examples 1 to 4;

3. the color fastness grade of the high-color-fastness environment-friendly gray-series recombined decorative veneers prepared in the examples 4-6 is higher than that of the recombined decorative veneers prepared in the examples 1-3; the color fastness grade of the high-color-fastness environment-friendly gray-series recombined decorative veneers prepared in the examples 7 to 9 is superior to that of the recombined decorative veneers in the examples 4 to 6; the color fastness grade of the high-color-fastness environment-friendly gray-series recombined decorative veneers prepared in the examples 10 to 12 is superior to that of the recombined decorative veneers prepared in the examples 7 to 9; the adhesive, the pretreatment before dyeing and the structure of the high-color-fastness wood dyeing device influence the color fastness and also influence the formaldehyde emission amount, the dipping stripping parameter, the static bending strength and the elastic modulus of the veneer.

The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.