A temperature-sensitive color-changing induction wooden floor

Abstract

The present invention discloses a temperature-sensitive color-changing induction wooden floor, which includes a modified wooden board and a modified base surface. The modified wooden board is impregnated with a modified solvent, polished on the surface, then coated with a polyimide coating and rubbed to form a first groove for alignment, and the first groove is filled with a temperature-sensitive solution; the modified base surface is made of γ-glycidoxypropyltrimethoxysilane-modified silica gel and formed by casting a film. A polyimide coating is coated on the bottom of the modified base surface and rubbed to form a second groove for alignment, and the second groove is filled with a temperature-sensitive solution; the modified base surface is covered on the modified wooden board and formed by vacuum laminating to obtain the wooden floor. In the present invention, the temperature-sensitive solution is filled in two layers between the modified wooden board and the modified base surface. Under the coverage of the modified base surface, the temperature-sensitive solution can block contact with air and reduce the occurrence of oxidation. Moreover, after the temperature-sensitive solution is cured, two temperature-sensitive layers with a phase difference will be formed, which is beneficial to enhancing the level of temperature-sensitive color change. As the temperature rises, the color change of the induction wooden floor gradually deepens.

Description

Technical Field

[0001] The present invention belongs to the technical field of floors, and particularly relates to a temperature-sensitive color-changing induction wooden floor. Background Art

[0002] Wooden floors are mainly divided into six categories: solid wood floors, laminate wood floors, engineered wood floors, multi-layer composite floors, bamboo floors, and cork floors. Due to their strong decorative properties, outstanding resilience, and shock absorption, they are widely loved by the masses and occupy an important position in interior decoration. With the rapid development of real estate, the interior decoration industry closely related to real estate has also developed rapidly, and people have put forward new requirements for the functions of floors.

[0003] Through market research, it is found that temperature-sensitive color-changing induction wooden floors are one of the most anticipated new products by consumers. Currently, this type of product achieves color change at high temperatures by coating a layer of temperature-sensitive paint on the surface of the wooden floor, thereby enhancing the fun of the floor. For example, in the manufacturing process of the temperature-sensitive color-changing floor disclosed in the patent publication number CN114311199A, the temperature-sensitive color-changing paint is coated on the surface of the floor by roll coating to form a temperature-sensitive color-changing pattern, and then a UV adhesion paint is coated on the surface of the temperature-sensitive color-changing pattern; or, for example, in the manufacturing method of the temperature-sensitive color-changing floor disclosed in the patent with the publication number CN101116988A, the floor is manufactured according to the following steps: floor blank → dyeing → primer → topcoat, and the coating liquid is a mixture of a temperature-sensitive color-changing water-based color masterbatch and a water-based primer.

[0004] However, although coating the temperature-sensitive color-changing paint on the surface of the wooden floor can make the floor change color in response to temperature for a certain period of time, the paint will age and fade when directly exposed to air under ultraviolet light irradiation. Therefore, the temperature-sensitive color-changing effect will gradually be lost after a period of time. Considering this factor, the promotion effect of temperature-sensitive color-changing floors is not good. Summary of the Invention

[0005] The purpose of the present invention is to provide a temperature-sensitive color-changing induction wooden floor. After the wooden board is impregnated with a modified solvent, the modified solvent will fill into the cell wall of the wooden board, causing the cell wall to swell, reducing the free hydroxyl groups on the wood molecules, modifying the wooden board, reducing its hygroscopicity, and improving its volume stability. A modified base surface is covered on the modified wooden board, and a temperature-sensitive solution is filled between the modified base surface and the modified wooden board, enabling the induction of the environmental temperature. The modified base surface plays a good barrier role, solving the problems of aging and fading caused by air contact, and being beneficial to extending the service life of temperature-sensitive color change. The above technical objectives of the present invention are achieved through the following technical solutions:

[0006] A temperature-sensitive color-changing induction wooden floor, comprising a modified wooden board and a modified base surface. The modified wooden board is impregnated with a modified solvent for 12 - 72 hours, air-dried, and then the surface is polished. Then, a polyimide coating is applied to the surface of the modified wooden board. After drying, a first groove is evenly rubbed on the polyimide coating for alignment, and the first groove is filled with a temperature-sensitive solution.

[0007] The modified base surface is made of γ-glycidoxytrimethoxysilane-modified silica gel by casting film formation. A polyimide coating is applied to the bottom of the modified base surface. After drying, a second groove is evenly rubbed on the polyimide coating for alignment, and the second groove is filled with a temperature-sensitive solution.

[0008] The modified base surface is covered on the modified wooden board and formed by vacuum laminating to obtain a wooden floor.

[0009] As a preferred solution, the thickness of the modified wooden board is 10 - 50 mm. The greater the thickness, the longer the impregnation time in the modified solvent. The wood used for the modified wooden board can be solid wood board, multi-layer wooden board, fiber board, or particle board.

[0010] As a preferred solution, the modified solvent is used for periodic pressure impregnation of the wooden board. First, the modified wooden board and the modified solvent are placed in a vacuum pressure impregnation device for vacuum treatment for 1 - 2 hours, then the impregnation pressure is increased to 5 MPa - 10 MPa, and the impregnation time is 3 - 5 hours. The operation of vacuum treatment followed by pressure impregnation is repeated 3 - 18 times, which is beneficial to discharging the gas in the wooden board, enabling the modified solvent to fully penetrate into the interior of the wooden board, and facilitating the swelling of the cell wall of the wooden board.

[0011] As a preferred solution, the thickness of the polyimide coating applied to the surface of the modified wooden board is 8 - 10 mm, and a plurality of parallel first grooves are evenly rubbed on the surface of the polyimide coating with a sand rub; the thickness of the polyimide coating applied to the bottom of the modified base surface is 8 - 10 mm, and a plurality of parallel second grooves are evenly rubbed on the surface of the polyimide coating with a sand rub. The first groove and the second groove are both strip-shaped grooves and are arranged at an inclination of 45°. The groove directions of the first groove and the second groove are perpendicular. When the modified base surface is covered on the modified wooden board, the second groove cooperates with the first groove, and the included angle between the two is 90°.

[0012] As a preferred embodiment, the cross-sections of the first groove and the second groove are V-shaped, and the groove depths of the first groove and the second groove are 3-5 mm, the maximum groove width is 5 mm, and the distance between two adjacent grooves does not exceed 2 mm. The temperature-sensitive solution will be aligned along the grooves. Since the modified base surface deviates from the alignment grooves on the surface of the modified wooden board by 90°, the molecules in the temperature-sensitive solution are neatly arranged in a strip shape in the same plane, and the nematic of the molecules will gradually twist by 90° when transitioning from one liquid surface to another liquid surface. That is to say, the phase difference between the modified base surface and the temperature-sensitive solution on the modified wooden board is 90°, which is beneficial to form changes in color depth and enhance the hierarchy of thermochromism.

[0013] As a preferred embodiment, the specific preparation method of the modified solvent is as follows:

[0014] (1) Add 37% formaldehyde to the reaction kettle, adjust the pH value to 8.0-8.5 with triethanolamine, add melamine while stirring, heat up to 70-80 °C, and stir for 1-2 h. The molar ratio of melamine to formaldehyde is 1:4.5-6;

[0015] (2) Add methanol and stir. The molar ratio of methanol to melamine is 5-8:1. Adjust the pH value to 4-7 with acetic acid, keep the reaction at 65 °C for 2-3 h, adjust the pH value to 8.0-8.5 with triethanolamine, and cool to obtain a colorless and transparent dilute mucilage.

[0016] Formaldehyde and melamine will undergo intermolecular polymerization under alkaline conditions to generate a thermosetting resin precondensate. This thermosetting resin precondensate is easy to form hydrogen bonds and is soluble in water. It can be well dispersed into the wooden board structure, swell the wood cell wall, and crosslink and cure with substances such as monosaccharides, tannins, resins, and gums in wood fibers and hemicelluloses. The hardness is increased, and after curing, it can inhibit the shrinkage of the wooden board cell wall and the filling of the cell cavity to make it hydrophobic, reduce the free hydroxyl groups in the molecular structure of the wooden board and thus reduce the hygroscopicity. After the modified solvent penetrates into the wooden board structure and crosslinks and cures, it will generate a very strong structural tensile force, which can prevent the wooden board from deforming and cracking, and can also combine with the surface fibers of the wooden board to more prominently display the texture and grain of the wooden board.

[0017] The preparation method of the modified base surface is as follows:

[0018] Step 1: Weigh silica gel and add it to anhydrous toluene, add γ-glycidoxytrimethoxysilane. The mass ratio of silica gel to γ-glycidoxytrimethoxysilane is 5:1-15, and the concentration of silica gel in anhydrous toluene is 1 g / 10 mL. After evacuating for 30 min under closed conditions, fill with nitrogen, stir under nitrogen protection, react at 100 °C for 24 h. After the reaction, filter by suction. The filter cake is washed with anhydrous toluene and anhydrous methanol respectively, and filtered by suction three times, and then dried in vacuum at 60 °C to obtain reactant 1;

[0019] Step 2: Add reactant 1 and anhydrous methanol into a three-necked flask. The mixing ratio of reactant 1 to anhydrous methanol is 1 g / 10 mL. Add diethanolamine under stirring. The volume ratio of diethanolamine to anhydrous methanol is 1:15 - 20. React at 40 °C for 24 h under nitrogen protection. After the reaction, perform suction filtration. Wash the filter cake with acetone and then dry it in vacuum at 60 °C to obtain reactant 2;

[0020] Step 3: Weigh reactant 2 and add it into anhydrous tetrahydrofuran. After stirring for 1 h, the volume ratio of reactant 2 to anhydrous tetrahydrofuran is 1:10 - 20. Under the condition of an ice bath at 0 °C, add triethylamine and dropwise add bromoisobutyryl bromide. React at 30 °C for 24 h under nitrogen protection. Perform suction filtration and wash repeatedly with tetrahydrofuran, water, and acetone. Dry in vacuum at 60 °C to obtain reactant 3;

[0021] Step 4: Weigh 50 g of reactant 3, 2.2 g of cuprous chloride, 5 g of tris[2-(dimethylamino)ethyl]amine, and 240 g of N-isopropylacrylamide, and add them into a 500 mL mixed solvent of DMF / H₂O (V / V) (50∶50). React for 12 h under nitrogen protection. After the reaction, perform suction filtration and wash repeatedly with water, methanol, and acetone. Dry in vacuum at 60 °C to obtain reactant 4;

[0022] Step 5: Weigh reactant 4 and p-toluenesulfonic acid and add them into deionized water. The mass ratio of reactant 4 to p-toluenesulfonic acid is 6 - 10:1. Stir at 50 - 80 °C for 24 h, perform centrifugal separation. The supernatant is rotary evaporated and then dried in vacuum at 60 °C to obtain reactant 5;

[0023] Step 6: Add reactant 5 and polyurethane resin into an extruder at a mass ratio of 2:5, melt and extrude them. The mixture is sheet-cast onto the surface of a steadily rotating cooling roller. The film is cooled and shaped on the cooling roller, and then formed into a modified base surface after traction and cutting.

[0024] As a preferred solution, the thickness of the modified base surface does not exceed 20 mm. The prepared modified base surface contains reactant 5, which is a thermosensitive substance formed by grafting N-isopropylacrylamide onto silica gel. Energy and electrons can be transferred inside it. The molecule has a capsule structure that has a binding effect on molecules, which is beneficial to the electron transfer in the thermosensitive solution and binds the molecules in the thermosensitive solution, reducing the loss of thermosensitive molecules.

[0025] As a preferred solution, the preparation method of the thermosensitive solution:

[0026] Step 1): Dissolve 1-5 parts by mass of bis-β-naphthospiropyran in 8-15 parts by mass of long-chain alcohol solution, heat and stir in a water bath at 30-50 °C, add 0.5-3 parts by mass of phenolic hydroxyl compound and its derivatives during stirring, and stir at a high speed of 1500-3000 r / min for 1-2 h to form emulsion micelles;

[0027] Step 2): Adjust the rotation speed to 100-500 r / min, add waterborne resin while stirring to obtain a polymer-coated emulsion, and the volume ratio of the emulsion micelles to the waterborne resin is 1:1-1.5;

[0028] Step 3): Disperse 0.5-5 parts by mass of gelatin, 0.5-5 parts by mass of gum arabic, 1-20 parts by mass of polyethylene glycol 200, 1-10 parts by mass of Tween 80, 1-3 parts by mass of acrylic acid, and 1-20 parts by mass of waterborne polyurethane into water, stir well and mix evenly to obtain a mixed solution;

[0029] Step 4): Mix the mixed solution with the polymer-coated emulsion prepared in Step 2) at a volume ratio of 1:1 and stir evenly.

[0030] As a preferred solution, in Step 1), the long-chain alcohol solution selects at least one of the following fatty alcohols: octacosanol, tetracosanol, triacontanol, docosanol, stearyl alcohol, myristyl alcohol, cetyl alcohol; the phenolic hydroxyl compound and its derivatives include at least two of the following: bisphenol A, lauric acid ester, α-naphthol, β-naphthol, phenol, 4-hydroxycoumarin, bisphenol B, benzoate; in Step 2), the waterborne resin selects at least one of the following resins: waterborne acrylic resin, waterborne polyurethane resin, waterborne epoxy resin, waterborne alkyd resin, amino resin.

[0031] As a preferred solution, use an automated special gluing device to coat PUR hot melt adhesive around the wooden floor. After drying, place the wooden floor in silicone waterproofing agent for 10 min, repeat 1-3 times. After drying, coat an adherent waterproof wood wax oil on its decorative upper surface. Finally, use magnetron sputtering method to deposit aluminum oxide wear-resistant particles on the surface of the floor board to construct a hydrophobic wear-resistant layer. The sputtering power is 100 W, the sputtering pressure is 1.5 MPa - 2.5 MPa, and the sputtering time is 60 min - 200 min in an argon atmosphere. Finally, perform freeze-drying to achieve paint-free decoration on the surface of the wooden floor, that is, obtain a temperature-sensitive color-changing induction wooden floor.

[0032] Beneficial effects

[0033] In the induction wooden floor of the present invention, the medium-temperature sensing solution is filled in two layers between the modified wooden board and the modified base surface. The modified base surface has good wear resistance. Under the cover of the modified base surface, the sensing solution can block contact with air and reduce the occurrence of oxidation. Moreover, after the sensing solution solidifies, two temperature-sensing layers with a phase difference will be formed, which is beneficial to enhancing the level of thermochromic color change. As the temperature rises, the color change of the induction wooden floor gradually deepens.

[0034] The polyimide coating has high radiation resistance and heat resistance, which can improve the weather resistance of the temperature-sensing wooden floor. And the polyimide coating has good dielectric properties, which can ensure the electron transfer of the temperature-sensing layer formed by the temperature-sensing solution. The solution mainly contains the chromogenic agent bis-β-naphthospiropyran, the color-developing agent phenolic hydroxyl compound and its derivatives, and the solvent long-chain alcohol solution. The solvent determines the color change temperature. The color change mechanism of bis-β-naphthospiropyran involves the balance between the colorless spiropyran compound and the planar ring-opening compound formed by the cleavage of the spiral carbon and epoxy. Under heating conditions, bis-β-naphthospiropyran opens the ring to form a ring-opening compound and presents color, and returns to the colorless state after cooling and closing the ring.

[0035] Among them, vacuum pumping needs to be carried out on the modified base surface covering the modified wooden board, which can reduce the pores between the modified base surface and the modified wooden board, prevent air bubbles from remaining, and ensure the uniformity of color development. The modified base surface has high thermosensitivity characteristics, which is beneficial to heat transfer and color development, and can also ensure the electron transfer in the temperature-sensing solution and bind the molecules in the temperature-sensing solution, reducing the loss of temperature-sensing molecules.

[0036] The wooden board is modified with a modified solvent, which can alleviate the influence of rapid external temperature changes on the wooden floor, improve its anti-deformation and anti-cracking properties, and enhance its adaptability to the environment. The modified wooden board covers the modified base surface, which can synergistically enhance the temperature response color change effect of the induction wooden floor. Finally, a hydrophobic and wear-resistant layer is deposited on the surface of the wooden floor to realize the floor paint-free technology, improve the surface effect and service performance of the wooden floor, and be more low-carbon and environmentally friendly.

[0037] Of course, it is not necessary for any product implementing the present invention to achieve all the above-mentioned advantages simultaneously. Description of the Drawings

[0038] Figure 1 It is a color rendering diagram of a temperature-sensitive color-changing induction wooden floor at normal temperature in Example 1;

[0039] Figure 2 It is a color rendering diagram of a temperature-sensitive color-changing induction wooden floor at 28 °C in Example 1;

[0040] Figure 3 It is a color rendering diagram of a temperature-sensitive color-changing induction wooden floor at 35 °C in Example 1;

[0041] Figure 4The color rendering diagram of a temperature-sensitive color-changing induction wooden floor in Example 1 at 40 °C. Detailed implementation mode

[0042] The technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0043] Vacuum pressure impregnation equipment: The VPI-500x2500 type fully automatic quick-opening vacuum pressure impregnation equipment provided by Jiangnan Shazhou Chemical Machinery Co., Ltd., Zhangjiagang City is adopted;

[0044] Vacuum film laminating and forming equipment: The TM2480F-2 vacuum skin sucking machine provided by Shandong Yijin Machinery Co., Ltd. is adopted;

[0045] Gluing equipment: The OSD-880 PUR hot melt adhesive machine provided by Suzhou Ostar Hot Melt Adhesive Machinery Co., Ltd. is adopted;

[0046] Mixing machine: The BDH planetary mixer provided by Foshan Bondeshi Machinery Equipment is adopted;

[0047] Modified base surface production: The ND-2400 film production line provided by Quanzhou Nuoda Machinery Co., Ltd. is adopted.

[0048] Example 1

[0049] A temperature-sensitive color-changing induction wooden floor, comprising a modified wooden board and a modified base surface. The modified wooden board is made of willow wood with a thickness of 15 mm. The modified wooden board is subjected to periodic pressure impregnation. First, the modified wooden board and the modified solvent are placed in a vacuum pressure impregnation equipment for vacuum treatment for 1 h, then the impregnation pressure is increased to 8 MPa, and the impregnation time is 3 h. The vacuum treatment and pressure impregnation are repeated 6 times. After impregnation for 24 h, it is air-dried and surface polished. Then, a 10-mm polyimide coating is coated on the surface of the modified wooden board. After drying, the first grooves are evenly rubbed on the polyimide coating for alignment. The groove depth of the first grooves is 3 mm, the maximum groove width is 5 mm, and the distance between adjacent two grooves is 1 mm. The first grooves are filled with a temperature-sensitive solution;

[0050] The specific preparation method of the modified solvent is as follows:

[0051] (1) Add 37% formaldehyde to the reaction kettle, adjust the pH value to 8.3 with triethanolamine, add melamine while stirring, heat up to 80 °C, and stir for 1.2 h. The molar ratio of melamine to formaldehyde is 1:5;

[0052] (2) adding methanol and stirring, with a molar ratio of methanol to melamine of 6:1, adjusting the pH value to 4.5 with acetic acid, maintaining the reaction at 65°C for 2.5 hours, adjusting the pH value to 8.5 with triethanolamine, and cooling to obtain a colorless, transparent, thin viscous liquid;

[0053] Preparation method of the temperature-sensitive solution:

[0054] Step 1): dissolving 5 parts by weight of di-β-naphthospiropyran in 15 parts by weight of myristyl alcohol solution, heating and stirring in a 45°C water bath, adding 2 parts by weight of bisphenol A and 1 part by weight of phenol during stirring, and stirring at a high speed of 2000 rpm for 1.5 hours to form emulsified micelles;

[0055] Step 2): adjusting the rotation speed to 200 rpm, adding aqueous acrylic resin while stirring to obtain a polymer-coated emulsion, wherein the volume ratio of the emulsified micelles to the aqueous acrylic resin is 1:1.2;

[0056] Step 3): Disperse 3 parts by mass of gelatin, 2 parts by mass of gum arabic, 15 parts by mass of polyethylene glycol 200, 8 parts by mass of Tween 80, 3 parts by mass of acrylic acid, and 12 parts by mass of aqueous polyurethane into water, stir thoroughly, and mix uniformly to obtain a mixed solution;

[0057] Step 4): mixing the mixed solution with the polymer coating emulsion prepared in step 2) at a volume ratio of 1:1 and stirring evenly;

[0058] The preparation method of the modified base surface is:

[0059] Step 1: Weigh silica gel and add it to anhydrous toluene, add γ-glycidoxytrimethoxysilane, the mass ratio of silica gel to γ-glycidoxytrimethoxysilane is 5:7, and the concentration of silica gel in anhydrous toluene is 1 g / 10 mL. Vacuum under closed conditions for 30 min and then fill with nitrogen. Stir under nitrogen protection and react at 100°C for 24 h. After the reaction is completed, filter and wash the filter cake with anhydrous toluene and anhydrous methanol, respectively. Filter three times and then dry in vacuo at 60°C to obtain reactant 1;

[0060] Step 2: Add reactant 1 and anhydrous methanol to a three-necked flask at a mixing ratio of 1 g / 10 mL. Add diethanolamine with stirring at a volume ratio of 1:15. React at 40°C under nitrogen for 24 h. After the reaction, filter and wash the filter cake with acetone and vacuum dry at 60°C to obtain reactant 2.

[0061] Step 3: Weigh reactant 2 and add it to anhydrous tetrahydrofuran. After stirring for 1 h, the volume ratio of reactant 2 to anhydrous tetrahydrofuran is 1:10. Under the condition of ice bath at 0 °C, add triethylamine. The mass ratio of triethylamine to reactant 2 is 6:1. Dropwise add bromoisobutyryl bromide. The added volume of bromoisobutyryl bromide is 1 / 10 of the volume of anhydrous tetrahydrofuran. React at 30 °C for 24 h under nitrogen protection. Filter by suction, wash repeatedly with tetrahydrofuran, water, and acetone, and dry in vacuum at 60 °C to obtain reactant 3;

[0062] Step 4: Weigh 50 g of reactant 3, 2.2 g of copper chloride, 5 g of tris[2-(dimethylamino)ethyl]amine, and 240 g of N-isopropylacrylamide, and add them to 500 mL of a mixed solvent of DMF / H₂O (V / V) (50∶50). React under nitrogen protection for 12 h. After the reaction is completed, filter by suction, wash repeatedly with water, methanol, and acetone, and dry in vacuum at 60 °C to obtain reactant 4;

[0063] Step 5: Weigh reactant 4 and p-toluenesulfonic acid and add them to deionized water. The mass ratio of reactant 4 to p-toluenesulfonic acid is 8:1. Stir at 70 °C for 24 h, perform centrifugal separation, and vacuum dry the supernatant after rotary evaporation at 60 °C to obtain reactant 5;

[0064] Step 6: Add reactant 5 and polyurethane resin to the extruder at a mass ratio of 2:5, melt and extrude, and cast in a sheet shape onto the roller surface of a steadily rotating cooling roller. The film is cooled, temperature-controlled, shaped on the cooling roller, and then formed into a modified base surface with a thickness of 15 mm after traction and cutting;

[0065] Coat a polyimide coating with a thickness of 10 mm on the bottom of the modified base surface. After drying, uniformly rub the second grooves on the polyimide coating for alignment, and fill the second grooves with a temperature-sensitive solution;

[0066] Cover the modified base surface on the modified wood board. The second grooves on the modified base surface are matched with the first grooves, and the included angle between the two is 90°. Use a vacuum laminating molding device to perform vacuum laminating molding to obtain a wooden floor;

[0067] Use a gluing device to coat PUR hot melt adhesive around the wooden floor. After drying, place the wooden floor in silicone waterproofing agent FS-150 for 10 min, repeat 2 times. After drying, coat a layer of adherent waterproof wood wax oil on its decorative upper surface. Finally, deposit aluminum trioxide wear-resistant particles on the surface of the floor board by magnetron sputtering to construct a hydrophobic wear-resistant layer. The sputtering power is 100 W, the sputtering gas pressure is 2 MPa, and the sputtering time is 120 min in an argon atmosphere. Finally, perform freeze-drying to achieve paint-free decoration on the surface of the wooden floor, that is, obtain the temperature-sensitive color-changing induction wooden floor.

[0068] Figures 1-44 are color rendering diagrams of the temperature-sensitive color-changing induction wooden floor of this embodiment at room temperature, 28°C, 35°C and 40°C. It can be seen from the four figures that the color of the temperature-sensitive wooden floor of this embodiment gradually changes with the increase of temperature.

[0069] Example 2

[0070] A temperature-sensitive color-changing inductive wood floor comprises a modified wood board and a modified base surface. The modified wood board is made of three-layer birch boards with a thickness of 14 mm. The modified wood board is subjected to periodic pressure impregnation. The modified wood board and a modified solvent are first placed in a vacuum pressure impregnation device for vacuum treatment for 1.5 hours. The impregnation pressure is then increased to 10 MPa for 4.5 hours. The pressure impregnation operation after vacuum treatment is repeated 8 times. After impregnation for 48 hours, the surface is air-dried and polished. An 8 mm polyimide coating is then applied to the surface of the modified wood board. After drying, a first groove is evenly rubbed on the polyimide coating for alignment. The first groove has a groove depth of 2 mm and a maximum groove width of 4 mm. The spacing between adjacent grooves is 1 mm. The first groove is filled with a temperature-sensitive solution.

[0071] The specific preparation method of the modified solvent is:

[0072] (1) Add 37% formaldehyde to a reactor, add triethanolamine to adjust the pH to 8.5, add melamine while stirring, raise the temperature to 77°C, and stir for 1.6 hours. The molar ratio of melamine to formaldehyde is 1:4.5;

[0073] (2) adding methanol and stirring, with a molar ratio of methanol to melamine of 5.5:1, adjusting the pH to 4 with acetic acid, maintaining the reaction at 65°C for 2 hours, adjusting the pH to 8.2 with triethanolamine, and cooling to obtain a colorless, transparent, thin viscous liquid;

[0074] Preparation method of the temperature-sensitive solution:

[0075] Step 1): dissolving 3 parts by mass of di-β-naphthospiropyran in a mixture of 8 parts by mass of myristyl alcohol and 6 parts by mass of cetyl alcohol, heating and stirring in a 50°C water bath, adding 2 parts by mass of α-naphthol and 1 part by mass of lauryl ester during stirring, and stirring at a high speed of 2200 r / min for 1.2 hours to form emulsified micelles;

[0076] Step 2): adjusting the rotation speed to 300 rpm, adding water-based acrylic resin while stirring to obtain a polymer-coated emulsion, wherein the volume ratio of the emulsified micelles to the water-based polyurethane resin is 1:1.3;

[0077] Step 3): Disperse 1 part by mass of gelatin, 4 parts by mass of gum arabic, 18 parts by mass of polyethylene glycol 200, 10 parts by mass of Tween 80, 2 parts by mass of acrylic acid, and 15 parts by mass of aqueous polyurethane in water, stir thoroughly, and mix uniformly to obtain a mixed solution;

[0078] Step 4): Mix the mixed solution and the polymer-coated emulsion prepared in Step 2) at a volume ratio of 1:1, and stir evenly.

[0079] The preparation method of the modified base surface is as follows:

[0080] Step 1: Weigh silica gel and add it to anhydrous toluene, then add γ-glycidoxytrimethoxysilane. The mass ratio of silica gel to γ-glycidoxytrimethoxysilane is 5:10, and the concentration of silica gel in anhydrous toluene is 1 g / 10 mL. After evacuating the air for 30 min under closed conditions, nitrogen is filled in, and stirring is carried out under nitrogen protection. React at 100 °C for 24 h. After the reaction is completed, filter by suction. The filter cake is washed with anhydrous toluene and anhydrous methanol respectively, and after suction filtration three times, it is dried in vacuum at 60 °C to obtain Reactant 1.

[0081] Step 2: Add Reactant 1 and anhydrous methanol to a three-necked flask. The mixing ratio of Reactant 1 to anhydrous methanol is 1 g / 10 mL. Under stirring, add diethanolamine. The volume ratio of diethanolamine to anhydrous methanol is 1:18. React at 40 °C for 24 h under nitrogen protection. After the reaction is completed, filter by suction. The filter cake is washed with acetone and then dried in vacuum at 60 °C to obtain Reactant 2.

[0082] Step 3: Weigh Reactant 2 and add it to anhydrous tetrahydrofuran. After stirring for 1 h, the volume ratio of Reactant 2 to anhydrous tetrahydrofuran is 1:14. Under the condition of an ice bath at 0 °C, add triethylamine. The mass ratio of triethylamine to the reactant is 4:1. Dropwise add bromoisobutyryl bromide. The added volume of bromoisobutyryl bromide is 1 / 10 of anhydrous tetrahydrofuran. React at 30 °C for 24 h under nitrogen protection, filter by suction, and wash repeatedly with tetrahydrofuran, water, and acetone, and then dry in vacuum at 60 °C to obtain Reactant 3.

[0083] Step 4: Weigh 50 g of Reactant 3, 2.2 g of copper chloride, 5 g of tris[2-(dimethylamino)ethyl]amine, and 240 g of N-isopropylacrylamide, and add them to a 500 mL mixed solvent of DMF / H₂O (V / V) (50:50). React for 12 h under nitrogen protection. After the reaction is completed, filter by suction, and wash repeatedly with water, methanol, and acetone, and then dry in vacuum at 60 °C to obtain Reactant 4.

[0084] Step 5: Weigh Reactant 4 and p-toluenesulfonic acid and add them to deionized water. The mass ratio of Reactant 4 to p-toluenesulfonic acid is 9:1. Stir at 78 °C for 24 h, then carry out centrifugal separation. The supernatant is vacuum dried at 60 °C after rotary evaporation to obtain Reactant 5.

[0085] Step 6: Reactant 5 and polyurethane resin are added to an extruder at a mass ratio of 2:5, melted and then extruded. They are cast in a sheet form onto the surface of a steadily rotating cooling roller. The film is cooled and shaped on the cooling roller, and then formed into a modified base surface with a thickness of 12 mm after being drawn and cut.

[0086] A polyimide coating with a thickness of 10 mm is coated on the bottom of the modified base surface. After drying, second grooves are evenly rubbed on the polyimide coating for alignment, and the second grooves are filled with a temperature-sensitive solution.

[0087] The modified base surface is covered on the modified wooden board. The second grooves on the modified base surface covered on the modified wooden board cooperate with the first grooves, and the included angle between the two is 90°. Vacuum laminating and forming are carried out using a vacuum laminating and forming device to obtain a wooden floor.

[0088] A PUR hot melt adhesive is coated around the wooden floor using a coating device. After drying, the wooden floor is placed in an organosilicon waterproofing agent FS-150 for 10 min and repeated 3 times. After drying, an adherent waterproof wood wax oil is coated on its decorative upper surface. Finally, aluminum oxide wear-resistant particles are deposited on the surface of the floor board by magnetron sputtering to construct a hydrophobic wear-resistant layer. The sputtering power is 100 W, the sputtering gas pressure is 2.5 MPa, and the sputtering time is 180 min in an argon atmosphere. Finally, freeze-drying is carried out to achieve paint-free decoration on the surface of the wooden floor, that is, a temperature-sensitive color-changing induction wooden floor is obtained.

[0089] Example 3

[0090] A temperature-sensitive color-changing induction wooden floor includes a modified wooden board and a modified base surface. The modified wooden board is made of a particle board with a thickness of 20 mm. The modified wooden board is subjected to periodic pressure impregnation. First, the modified wooden board and the modified solvent are placed in a vacuum pressure impregnation device for vacuum treatment for 1 h, and then the impregnation pressure is increased to 5 MPa, and the impregnation time is 5 h. The operation of vacuum treatment followed by pressure impregnation is repeated 10 times. After impregnation for 60 h, it is air-dried and surface-polished. Then, a 9-mm-thick polyimide coating is coated on the surface of the modified wooden board. After drying, first grooves are evenly rubbed on the polyimide coating for alignment. The groove depth of the first grooves is 4 mm, the maximum groove width is 4 mm, and the distance between adjacent grooves is 1 mm. The first grooves are filled with a temperature-sensitive solution.

[0091] The specific preparation method of the modified solvent is as follows:

[0092] (1) 37% formaldehyde is added to a reaction kettle, and triethanolamine is added to adjust the pH value to 8.5. Melamine is added while stirring, and the temperature is raised to 76 °C, and stirring is carried out for 2 h. The molar ratio of melamine to formaldehyde is 1:4.5.

[0093] (2) Add methanol and stir. The molar ratio of methanol to melamine is 7:1. Adjust the pH value to 5.6 with acetic acid, maintain the reaction at 65 °C for 3 h, adjust the pH value to 8.0 with triethanolamine, and cool to obtain a colorless transparent dilute mucilage.

[0094] The preparation method of the temperature-sensitive solution is as follows:

[0095] Step 1: Dissolve 3 parts by mass of bis-β-naphthospiropyran in 13 parts by mass of docosanol solution, heat and stir in a water bath at 35 °C. During the stirring process, add 2 parts by mass of bisphenol B and 1 part by mass of 4-hydroxycoumarin, and stir at a high speed of 2500 r / min for 1 h to form emulsified micelles.

[0096] Step 2: Adjust the rotation speed to 250 r / min, add waterborne acrylic resin while stirring to obtain a polymer-coated emulsion. The volume ratio of the emulsified micelles to the waterborne acrylic resin is 1:1.5.

[0097] Step 3: Disperse 5 parts by mass of gelatin, 5 parts by mass of gum arabic, 20 parts by mass of polyethylene glycol 200, 10 parts by mass of Tween 80, 2 parts by mass of acrylic acid, and 17 parts by mass of waterborne polyurethane into water, stir well, and mix evenly to obtain a mixed solution.

[0098] Step 4: Mix the mixed solution with the polymer-coated emulsion prepared in Step 2 at a volume ratio of 1:1, and stir evenly.

[0099] The preparation method of the modified base surface is as follows:

[0100] Step 1: Weigh silica gel and add it to anhydrous toluene, add γ-glycidoxytrimethoxysilane. The mass ratio of silica gel to γ-glycidoxytrimethoxysilane is 5:10. The concentration of silica gel in anhydrous toluene is 1 g / 10 mL. After evacuating for 30 min under closed conditions, fill with nitrogen, stir under nitrogen protection, and react at 100 °C for 24 h. After the reaction, filter by suction. Wash the filter cake with anhydrous toluene and anhydrous methanol respectively, filter by suction three times, and then dry in vacuo at 60 °C to obtain Reactant 1.

[0101] Step 2: Add Reactant 1 and anhydrous methanol to a three-necked flask. The mixing ratio of Reactant 1 to anhydrous methanol is 1 g / 10 mL. Add diethanolamine while stirring. The volume ratio of diethanolamine to anhydrous methanol is 1:20. React at 40 °C for 24 h under nitrogen protection. After the reaction, filter by suction. Wash the filter cake with acetone and then dry in vacuo at 60 °C to obtain Reactant 2.

[0102] Step 3: Weigh reactant 2 and add it to anhydrous tetrahydrofuran. After stirring for 1 h, the volume ratio of reactant 2 to anhydrous tetrahydrofuran is 1:20. Under the condition of an ice bath at 0 °C, add triethylamine. The mass ratio of triethylamine to reactant 2 is 8:1. Dropwise add bromoisobutyryl bromide. The added volume of bromoisobutyryl bromide is 1 / 10 of the volume of anhydrous tetrahydrofuran. React at 30 °C for 24 h under nitrogen protection. Filter by suction, wash repeatedly with tetrahydrofuran, water, and acetone, and dry in vacuo at 60 °C to obtain reactant 3;

[0103] Step 4: Weigh 50 g of reactant 3, 2.2 g of cuprous chloride, 5 g of tris[2-(dimethylamino)ethyl]amine, and 240 g of N-isopropylacrylamide, and add them to 500 mL of a mixed solvent of DMF / H₂O (V / V) (50∶50). React under nitrogen protection for 12 h. After the reaction is completed, filter by suction, wash repeatedly with water, methanol, and acetone, and dry in vacuo at 60 °C to obtain reactant 4;

[0104] Step 5: Weigh reactant 4 and p-toluenesulfonic acid and add them to deionized water. The mass ratio of reactant 4 to p-toluenesulfonic acid is 10:1. Stir at 72 °C for 24 h, perform centrifugal separation. The supernatant is rotary evaporated and then dried in vacuo at 60 °C to obtain reactant 5;

[0105] Step 6: Add reactant 5 and polyurethane resin in a mass ratio of 2:5 and extrude them after melting in an extruder. Cast them into a sheet and flow it onto the surface of a steadily rotating cooling roller. The film is cooled and shaped on the cooling roller, and then formed into a modified base surface with a thickness of 10 mm after traction and cutting;

[0106] Coat a polyimide coating with a thickness of 10 mm on the bottom of the modified base surface. After drying, uniformly rub the second grooves on the polyimide coating for alignment, and fill the second grooves with a temperature-sensitive solution;

[0107] Cover the modified base surface on the modified wooden board. The second grooves on the modified base surface are matched with the first grooves, and the included angle between the two is 90°. Use a vacuum laminating molding device to perform vacuum laminating molding to obtain a wooden floor;

[0108] Use a gluing device to coat PUR hot melt adhesive around the wooden floor. After drying, place the wooden floor in an organosilicon waterproofing agent FS-150 for 10 min, repeat 3 times. After drying, coat a layer of adherent waterproof wood wax oil on its decorative upper surface. Finally, deposit aluminum oxide wear-resistant particles on the surface of the floor board by magnetron sputtering to construct a hydrophobic wear-resistant layer. The sputtering power is 100 W, the sputtering pressure is 1.5 MPa, and the sputtering time is 200 min in an argon atmosphere. Finally, perform freeze-drying to achieve paint-free decoration on the surface of the wooden floor, that is, obtain a temperature-sensitive color-changing induction wooden floor.

[0109] Comparative Example 1

[0110] A temperature-sensitive color-changing induction wooden floor, which is different from that of Example 1 in that it does not have a polyimide coating, a first groove, and a second groove. The temperature-sensitive solution is coated on the upper surface of the modified wooden board, and the modified base surface is covered on the modified wooden board, and then vacuum film-forming is carried out to obtain the wooden floor.

[0111] The preparation method of the above temperature-sensitive color-changing induction wooden floor is the same as that of Example 1, and the component contents are replaced accordingly.

[0112] Comparative Example 2

[0113] A temperature-sensitive color-changing induction wooden floor, which is different from that of Example 1 in that it does not have a modified base surface, and the rest of the technical features are the same as those of Example 1.

[0114] Temperature-sensitive test

[0115] Test method: The temperature-sensitive wooden floors are prepared according to the preparation methods of Examples 1-3 and Comparative Examples 1-2, and are successively labeled as Products 1-5. Heating wires are laid at the bottoms of Products 1-5 respectively, and the temperatures of Products 1-5 are controlled through the heating wires. The color difference values, color change times, and color change effects of Products 1-5 during the temperature changes of 15-20 °C (T0), 20-28 °C (T1), 28-35 °C (T2), and 35-40 °C (T3) are recorded respectively. Then, Products 1-5 are respectively sawn into specimens of 100×100 mm, and then tested with an abrasion tester, and the worn mass is weighed.

[0116] Test instruments: YS3060 spectrophotometer colorimeter, Taber 5135 abrasion tester.

[0117] Test results: Refer to Table 1.

[0118] Table 1 shows the colorimetric results of Products 1-5 at corresponding temperatures

[0119]

[0120]

[0121] It can be obtained from Table 1 that for the temperature-sensitive color-changing induction wooden floor of the present application, the wear amount does not change significantly with the temperature change. However, for the wooden floors of Products 4 and 5, the wear amount increases with the increase of temperature. In terms of the color-changing performance, the color-changing range of Products 1-3 is large, and the color-changing effect becomes more obvious with the increase of temperature. For Products 4 and 5, there is no obvious color change at 15-20 °C and 35-40 °C. It can be speculated that when the temperature is too low or too high, the temperature-sensitive color-changing effect of Products 4 and 5 is not obvious.

[0122] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications, supplements, or use similar methods of substitution to the described specific embodiments. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claims, they shall fall within the protection scope of the present invention.

Claims

1. A temperature-sensitive color-changing induction wooden floor, characterized in that It includes a modified wood board and a modified base surface. The modified wood board is impregnated with a modified solvent for 12 - 72 h, air-dried and then surface-polished. Then, a polyimide coating is applied on the surface of the modified wood board. After drying, first grooves are evenly rubbed on the polyimide coating for alignment, and the first grooves are filled with a temperature-sensitive solution. The modified base surface is made by modifying silica gel with γ-glycidoxytrimethoxysilane and combining it with polyurethane resin through casting film formation. A polyimide coating is applied on the bottom of the modified base surface. After drying, second grooves are evenly rubbed on the polyimide coating for alignment, and the second grooves are filled with a temperature-sensitive solution. The modified base surface is covered on the modified wood board and formed by vacuum laminating to obtain a wooden floor. The preparation method of the modified base surface is as follows: Step 1: Weigh silica gel and add it to anhydrous toluene, then add γ-glycidoxytrimethoxysilane. The mass ratio of silica gel to γ-glycidoxytrimethoxysilane is 5:1 - 15. After evacuating the air for 30 min under a closed condition, nitrogen is filled in, and stirring is carried out under nitrogen protection. The reaction is carried out at 100 °C for 24 h. After the reaction is completed, filtration is carried out. The filter cake is washed with anhydrous toluene and anhydrous methanol respectively, and filtered three times and then vacuum-dried at 60 °C to obtain Reactant 1. Step 2: Add Reactant 1 and anhydrous methanol to a three-necked flask. The mixing ratio of Reactant 1 to anhydrous methanol is 1 g / 10 mL. Diethanolamine is added under stirring. The volume ratio of diethanolamine to anhydrous methanol is 1:15 - 20. The reaction is carried out at 40 °C for 24 h under nitrogen protection. After the reaction is completed, filtration is carried out. The filter cake is washed with acetone and then vacuum-dried at 60 °C to obtain Reactant 2. Step 3: Weigh Reactant 2 and add it to anhydrous tetrahydrofuran. After stirring for 1 h, the volume ratio of Reactant 2 to anhydrous tetrahydrofuran is 1:10 - 20. Under the condition of ice bath at 0 °C, triethylamine is added, and bromoisobutyryl bromide is added drop by drop. The reaction is carried out at 30 °C for 24 h under nitrogen protection. Filtration is carried out, and it is repeatedly washed with tetrahydrofuran, water, and acetone, and vacuum-dried at 60 °C to obtain Reactant 3. Step ④: Weigh 50 g of Reactant 3, 2.2 g of copper chloride, 5 g of tris[2-(dimethylamino)ethyl]amine, and 240 g of N-isopropylacrylamide, and add them to 500 mL of a mixed solvent of DMF / H₂O (V / V) (50∶50). Under nitrogen protection, the reaction is carried out for 12 h. After the reaction is completed, filtration is carried out, and it is repeatedly washed with water, methanol, and acetone, and vacuum-dried at 60 °C to obtain Reactant 4. Step ⑤: Weigh Reactant 4 and p-toluenesulfonic acid and add them to deionized water. The mass ratio of Reactant 4 to p-toluenesulfonic acid is 6 - 10:

1. Stir at 50 - 80 °C for 24 h, carry out centrifugal separation, and the upper clear liquid is rotary-evaporated and then vacuum-dried at 60 °C to obtain Reactant 5. Step ⑥: Reactant 5 and polyurethane resin are added to an extruder in a mass ratio of 2:5, melted and extruded, and cast into a sheet on the surface of a steadily rotating cooling roller. The film is cooled and shaped on the cooling roller, and then formed into a modified base surface after traction and cutting.

2. The temperature-sensitive color-changing induction wooden floor according to claim 1, characterized in that, The specific preparation method of the modified solvent is as follows: (1) Add 37% formaldehyde to a reactor, add triethanolamine to adjust the pH to 8.0-8.5, add melamine while stirring, raise the temperature to 70-80°C, and stir for 1-2 hours. The molar ratio of melamine to formaldehyde is 1:4.5-6; (2) Methanol was added and stirred, with a molar ratio of methanol to melamine of 5-8:1, and the pH value was adjusted to 4-7 with acetic acid. The reaction was maintained at 65°C for 2-3 hours, and the pH value was adjusted to 8.0-8.5 with triethanolamine. The mixture was cooled to obtain a colorless, transparent, thin viscous liquid.

3. A temperature-sensitive color-changing induction wooden floor according to claim 1, characterized in that, When the modified wood board is impregnated with the modified solvent, the modified wood board and the modified solvent are first placed in a vacuum pressure impregnation device for vacuum treatment for 1-2 hours, and then the impregnation pressure is increased to 5MPa-10MPa, the impregnation time is 3h-5h, and the operation is repeated 3-18 times.

4. The temperature-sensitive color-changing induction wooden floor according to claim 1, characterized in that, The wooden floor is immersed in a silicone waterproofing agent for 10 minutes, repeated 1-3 times, and after drying, a layer of adhesive waterproof wood wax oil is coated on the decorative surface. Finally, a magnetron sputtering method is used to deposit aluminum oxide wear-resistant particles on the surface of the floor board to construct a hydrophobic wear-resistant layer. Finally, it is freeze-dried to obtain a temperature-sensitive color-changing induction wooden floor.

5. The temperature-sensitive color-changing induction wooden floor according to claim 4, characterized in that, The specific conditions of the magnetron sputtering method are: sputtering power of 100W, sputtering pressure of 1.5MPa-2.5MPa, and sputtering time of 60min-200min in an argon atmosphere.

6. The temperature-sensitive color-changing induction wooden floor according to claim 1, wherein The preparation method of the temperature-sensitive solution comprises the following steps: step 1): dissolving 1-5 parts by mass of di-β-naphthylspiropyran in 8-15 parts by mass of a long-chain alcohol solution, heating and stirring in a water bath at 30-50° C., adding 0.5-3 parts by mass of a phenolic hydroxyl compound and its derivatives during the stirring process, and stirring at a high speed of 1500-3000 r / min for 1-2 hours to form emulsified micelles; Step 2): adjusting the rotation speed to 100-500 r / min, adding an aqueous resin while stirring to obtain a polymer-coated emulsion, wherein the volume ratio of the emulsified micelles to the aqueous resin is 1:1-1.5; Step 3): dispersing 0.5-5 parts by weight of gelatin, 0.5-5 parts by weight of gum arabic, 1-20 parts by weight of polyethylene glycol 200, 1-10 parts by weight of polysorbate 80, 1-3 parts by weight of acrylic acid, and 1-20 parts by weight of aqueous polyurethane into water, stirring thoroughly, and mixing uniformly to obtain a mixed solution; Step 4): The mixed solution and the polymer coating emulsion prepared in step 2) are mixed in a volume ratio of 1:1 and stirred evenly.

7. The temperature-sensitive color-changing induction wooden floor according to claim 6, characterized in that, In step 1), the long-chain alcohol solution is selected from at least one of the following fatty alcohols: octacosanol, tetracosanol, triacontanol, behenyl alcohol, stearyl alcohol, myristyl alcohol, and cetyl alcohol.

8. The temperature-sensitive color-changing induction wooden floor according to claim 1, characterized in that The first groove and the second groove are both strip-shaped grooves, and the angle between the second groove and the first groove when they are matched is 90°.

9. A temperature-sensitive color-changing induction wooden floor according to claim 1, characterized in that, The cross-sections of the first groove and the second groove are V-shaped, and the groove depths of the first groove and the second groove are 3-5 mm, the maximum groove width is 5 mm, and the spacing between two adjacent grooves does not exceed 2 mm.

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