Anti-deformation and waterproof wooden veneer and preparation method thereof

Abstract

The present invention relates to the technical field of decorative panels, specifically to a deformation-resistant and waterproof wooden decorative panel and a preparation method thereof. The present application replaces melamine formaldehyde resin with acrylic emulsion as the impregnating glue, thereby achieving formaldehyde-free and green processing of decorative panels, and the prepared plywood has excellent waterproof performance, is not easy to deform, and has relatively excellent flame retardant properties. The solution also impregnates the wooden substrate in acrylic emulsion, and pretreats the wooden substrate with acrylic emulsion. On the one hand, it can improve the performance of the wooden substrate, thereby ensuring the comprehensive waterproof and flame retardant properties of the decorative panel. On the other hand, since the wooden substrate has been pretreated, the bonding strength between the impregnated paper and the wooden substrate is higher, the waterproof performance is improved, and it is not easy to deform, and the practicality is higher.

Description

Technical Field

[0001] The present invention relates to the technical field of decorative panels, in particular to a deformation-resistant and waterproof wooden decorative panel and a preparation method thereof. Background Art

[0002] Decorative veneer plywood, also known as wood veneer, is a decorative material used for interior decoration or furniture surface, which is made by slicing natural wood or technical wood into thin slices of a certain thickness, adhering them to the surface of plywood, and then hot pressing. Veneer generally has the advantages of beautiful texture, low cost and environmental protection, and is very popular among consumers.

[0003] Melamine formaldehyde resin is one of the most commonly used impregnating resins on the market. In production, melamine formaldehyde resin is generally used to impregnate base paper and then bonded to the surface of a single board to form a decorative panel. However, melamine formaldehyde resin releases a large amount of free formaldehyde during processing and application, which can easily cause indoor pollution. Therefore, how to replace melamine formaldehyde resin with formaldehyde-free glue while ensuring the quality of the decorative panel is one of the technical problems that we urgently need to solve.

[0004] Based on this situation, the present application discloses a deformation-resistant and waterproof wood veneer panel and a preparation method thereof to solve this technical problem. Summary of the Invention

[0005] The object of the present invention is to provide a deformation-resistant and waterproof wood veneer panel and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A method for preparing a deformation-resistant and waterproof wood veneer panel comprises the following steps:

[0008] (1) Octavinyl POSS, DOPO, and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an oil bath at 80-85° C. for 10-12 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain a flame-retardant silicone;

[0009] (2) Dipropylene glycol and vinyl triethoxysilane are mixed, a catalyst is added, and the mixture is stirred evenly under a nitrogen environment. The mixture is reacted at 80-85° C. for 1-1.5 hours, and then the temperature is raised to 120-125° C. and the reaction is continued for 2-3 hours. After the reaction is completed, the catalyst is removed and the product is collected to obtain a toughened silicone;

[0010] (3) compounding the toughening silicone and the flame retardant silicone to obtain a silicone monomer;

[0011] Mix 1 / 2 part by mass of an emulsifier and deionized water, stir evenly, add an acrylate monomer and an organosilicon monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution;

[0012] Mix a buffer, 1 / 2 parts by weight of an emulsifier, and deionized water, heat to 65-70° C., add 1 / 3 parts by weight of a pre-emulsion and 1 / 3 parts by weight of an initiator solution, react for 10-20 minutes, heat to 80-85° C., add 2 / 3 parts by weight of a pre-emulsion and 2 / 3 parts by weight of an initiator solution, continue to react for 1-2 hours, add a crosslinking monomer, continue to react for 2-3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 30-40%;

[0013] (4) cutting the base paper and dipping it in an acrylic emulsion for a first time for 40 to 50 seconds, drying it at 90 to 95° C. for 30 to 40 seconds, and then dipping it in an acrylic emulsion for a second time for 50 to 60 seconds, and drying it at 100 to 105° C. for 1 to 2 minutes to obtain an impregnated paper;

[0014] The impregnated paper is hot-pressed onto the wooden substrate to obtain a decorative panel.

[0015] In this embodiment, in step (3), the acrylate monomer is a compound of methyl methacrylate, butyl acrylate and acrylic acid, and the mass ratio of methyl methacrylate, butyl acrylate and acrylic acid is 3:10:1; the mass ratio of the toughening silicone and the flame retardant silicone is 2:1, and the amount of the silicone monomer is 5-8wt% of the acrylate monomer.

[0016] In this embodiment, the crosslinking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the crosslinking monomer is 4-5wt% of the acrylate monomer.

[0017] In this embodiment, in step (3), the total amount of ammonium persulfate is 1-2 wt% of the acrylate monomer, and the concentration of the initiator solution is 3-4 wt%; the emulsifier is sodium lauryl sulfate, and the total amount is 3-5 wt% of the total amount of the acrylate monomer and the silicone monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the total amount is 0.01-0.05 wt% of the acrylate monomer.

[0018] In this embodiment, in step (1), the molar ratio of the octavinyl POSS to DOPO is 1:(3-3.2); and the amount of azobisisobutyronitrile is 0.05-0.06 wt % of the octavinyl POSS.

[0019] In this embodiment, the preparation steps of octavinyl POSS are as follows: vinyl triethoxysilane, acetone, concentrated hydrochloric acid and deionized water are mixed, stirred evenly, reacted at 40-50° C. for 20-24 hours, precipitated product, washed and dried to obtain octavinyl POSS.

[0020] In this embodiment, in step (2), the molar ratio of dipropylene glycol to vinyltriethoxysilane is (1.6-1.8):1, the catalyst is barium hydroxide, and the amount of the catalyst is 0.05-0.06 wt% of the total mass of dipropylene glycol and vinyltriethoxysilane.

[0021] In this embodiment, in step (4), the hot pressing temperature is 150-160° C., the hot pressing time is 50-60 s, and the hot pressing pressure is 1-2 MPa.

[0022] In this embodiment, the decorative panel is prepared according to any one of the above methods for preparing a deformation-resistant and waterproof wooden decorative panel.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention discloses a method for preparing a deformation-resistant and waterproof wood veneer panel. The solution replaces conventional melamine-formaldehyde resin with acrylic ester emulsion. The application of melamine-formaldehyde resin in impregnated paper is relatively mature. Many enterprises and R&D personnel have improved its performance to reduce formaldehyde emission and achieve low formaldehyde release, but zero formaldehyde emission has never been achieved. Therefore, the present application replaces melamine-formaldehyde resin with acrylic ester emulsion as the impregnating glue, thereby achieving formaldehyde-free and green processing of veneer panels.

[0025] On this basis, since acrylic emulsion is a linear polymer, the acrylic monomer reacts relatively completely in the emulsion polymerization stage. Therefore, when acrylic emulsion is used as an impregnating glue, the bonding strength between the impregnated paper and the wooden substrate will be reduced. Therefore, the acrylic emulsion needs to be modified so that it can also be cross-linked and cured during the subsequent hot pressing bonding with the wooden substrate to improve the bonding strength between the impregnated paper and the wooden substrate. Based on this, this scheme introduces cross-linking monomers and flame-retardant silicone into the acrylic emulsion. The cross-linking monomers are 1,3-butanediol dimethacrylate and hydroxybutyl acrylate. Hydroxybutyl acrylate introduces hydroxyl groups, which can achieve secondary cross-linking during subsequent hot pressing. 1,3-butanediol dimethacrylate and flame-retardant silicone can effectively improve the cross-linking network of the acrylic emulsion, especially the introduction of flame-retardant silicone, which contains multiple vinyl groups, can effectively increase the cross-linking density of acrylate, make the cross-linking network tighter, and the performance of the acrylic emulsion is better and the waterproofness is better.

[0026] When preparing the flame-retardant silicone, octavinyl POSS and DOPO are grafted and reacted, wherein the DOPO raw material is contained. The introduction of this component can achieve flame-retardant modification, thereby improving the flame-retardant properties of the acrylic emulsion and ensuring that the subsequent impregnated paper also has excellent flame-retardant properties.

[0027] However, since the flame-retardant silicone contains a large number of rigid groups, a large amount of introduction will affect the flexibility of the acrylic emulsion, thereby affecting the impregnation effect of the impregnated paper. Therefore, the present application uses dipropylene glycol and vinyltriethoxysilane for reaction grafting to generate a branched polysiloxane containing hydroxyl groups and vinyl groups. The branched polysiloxane has a large number of flexible chain segments, which can effectively toughen the acrylic emulsion and further improve the cross-linking of the acrylic emulsion. The introduction of hydroxyl groups can also achieve high-temperature secondary cross-linking; therefore, after many experiments, it was concluded that when the toughening silicone and the flame-retardant silicone are compounded in a mass ratio of 2:1, the acrylic emulsion obtained at this time is used as an impregnating latex, which can effectively improve the mechanical properties and waterproof properties of the impregnated paper, and ensure that the impregnated paper has excellent flame retardant properties. Therefore, the performance of the resulting decorative panel is also relatively excellent and the practicality is high.

[0028] At the same time, the solution also impregnates the wood substrate in acrylic emulsion. Pre-treating the wood substrate with acrylic emulsion can, on the one hand, improve the performance of the wood substrate, thereby ensuring the comprehensive waterproof and flame retardant properties of the decorative panel. On the other hand, since the wood substrate has been pre-treated, the bonding strength between the impregnated paper and the wood substrate is higher, the waterproof performance is improved, and it is not easy to deform, which makes it more practical. DETAILED DESCRIPTION

[0029] The following describes preferred implementations of the present invention. Obviously, the described embodiments are only a portion of the embodiments of the present invention, not all of them. It will be apparent to those skilled in the art that all other implementations derived without inventive effort, without departing from the principles of the present invention, are within the scope of protection of the present invention.

[0030] In this embodiment, the preparation steps of octavinyl POSS are as follows: 10 mL of vinyltriethoxysilane, 75 mL of acetone, 12.5 mL of concentrated hydrochloric acid and 15 mL of deionized water are mixed, stirred evenly, reacted at 40° C. for 24 h, the product is precipitated, washed and dried to obtain octavinyl POSS.

[0031] Example 1: A method for preparing a deformation-resistant and waterproof wood veneer panel, comprising the following steps:

[0032] (1) Octavinyl POSS, DOPO and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an 80°C oil bath for 12 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain flame retardant silicone; the molar ratio of octavinyl POSS to DOPO was 1:3.2; the amount of azobisisobutyronitrile was 0.05 wt% of the octavinyl POSS.

[0033] (2) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen atmosphere. The mixture was reacted at 80°C for 1.5 hours, and then the temperature was raised to 120°C and the reaction was continued for 3 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0034] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0035] (3) Compounding the toughening silicone and the flame-retardant silicone to obtain a silicone monomer; the mass ratio of the toughening silicone and the flame-retardant silicone is 2:1.

[0036] Mix 1 / 2 parts by mass of emulsifier and deionized water, stir evenly, add acrylate monomer and silicone monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution.

[0037] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 65°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 20 minutes, heat to 80°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 2 hours, add a cross-linking monomer, continue to react for 2 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0038] The acrylate monomer is a compound of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The amount of the organosilicon monomer is 6% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of the emulsifier is 5% by weight of the total amount of the acrylate monomer and organosilicon monomer.

[0039] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0040] (4) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 90°C for 40 seconds, and then immerse it in acrylic emulsion again for 60 seconds, dry it at 100°C for 1.5 minutes to obtain impregnated paper.

[0041] The impregnated paper and the wooden substrate were hot-pressed to obtain a decorative panel; the hot-pressing temperature was 160° C., the hot-pressing time was 60 s, and the hot-pressing pressure was 1 MPa.

[0042] Example 2: A method for preparing a deformation-resistant and waterproof wood veneer panel, comprising the following steps:

[0043] (1) Octavinyl POSS, DOPO and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an 85°C oil bath for 11 hours. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain flame retardant silicone; the molar ratio of octavinyl POSS to DOPO was 1:3.2; the amount of azobisisobutyronitrile was 0.05 wt% of the octavinyl POSS.

[0044] (2) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen atmosphere. The mixture was reacted at 85°C for 1.5 hours, and then the temperature was raised to 125°C and the reaction was continued for 2.5 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0045] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0046] (3) Compounding the toughening silicone and the flame-retardant silicone to obtain a silicone monomer; the mass ratio of the toughening silicone and the flame-retardant silicone is 2:1.

[0047] Mix 1 / 2 parts by mass of emulsifier and deionized water, stir evenly, add acrylate monomer and silicone monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution.

[0048] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 70°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 15 minutes, heat to 85°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 1.5 hours, add a cross-linking monomer, continue to react for 2.5 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0049] The acrylate monomer is a mixture of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The amount of the organosilicon monomer is 7% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of the emulsifier is 5% by weight of the total amount of the acrylate monomer and organosilicon monomer.

[0050] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0051] (4) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 95°C for 35 seconds, and then immerse it in acrylic emulsion again for 60 seconds, dry it at 105°C for 1 minute to obtain impregnated paper.

[0052] The impregnated paper and the wooden substrate were hot-pressed to obtain a decorative panel; the hot-pressing temperature was 160° C., the hot-pressing time was 60 s, and the hot-pressing pressure was 1 MPa.

[0053] Example 3: A method for preparing a deformation-resistant and waterproof wood veneer panel, comprising the following steps:

[0054] (1) Octavinyl POSS, DOPO and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an 85°C oil bath for 10 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain flame retardant silicone; the molar ratio of octavinyl POSS to DOPO was 1:3.2; the amount of azobisisobutyronitrile was 0.05 wt% of the octavinyl POSS.

[0055] (2) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen. The mixture was reacted at 85°C for 1 hour, and then the temperature was raised to 125°C and the reaction was continued for 2 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0056] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0057] (3) Compounding the toughening silicone and the flame-retardant silicone to obtain a silicone monomer; the mass ratio of the toughening silicone and the flame-retardant silicone is 2:1.

[0058] Mix 1 / 2 parts by mass of emulsifier and deionized water, stir evenly, add acrylate monomer and silicone monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution.

[0059] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 70°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 10 minutes, heat to 85°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 1 hour, add a cross-linking monomer, continue to react for 3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0060] The acrylate monomer is a mixture of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The amount of the organosilicon monomer is 8% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of the emulsifier is 5% by weight of the total amount of the acrylate monomer and organosilicon monomer.

[0061] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0062] (4) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 95°C for 30 seconds, and then immerse it in acrylic emulsion again for 60 seconds, dry it at 105°C for 1 minute to obtain impregnated paper.

[0063] The impregnated paper and the wooden substrate were hot-pressed to obtain a decorative panel; the hot-pressing temperature was 160° C., the hot-pressing time was 60 s, and the hot-pressing pressure was 1 MPa.

[0064] Example 4: A method for preparing a deformation-resistant and waterproof wood veneer panel, comprising the following steps:

[0065] (1) Octavinyl POSS, DOPO and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an 85°C oil bath for 10 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain flame retardant silicone; the molar ratio of octavinyl POSS to DOPO was 1:3.2; the amount of azobisisobutyronitrile was 0.05 wt% of the octavinyl POSS.

[0066] (2) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen. The mixture was reacted at 85°C for 1 hour, and then the temperature was raised to 125°C and the reaction was continued for 2 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0067] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0068] (3) Compounding the toughening silicone and the flame-retardant silicone to obtain a silicone monomer; the mass ratio of the toughening silicone and the flame-retardant silicone is 2:1.

[0069] Mix 1 / 2 parts by mass of emulsifier and deionized water, stir evenly, add acrylate monomer and silicone monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution.

[0070] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 70°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 10 minutes, heat to 85°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 1 hour, add a cross-linking monomer, continue to react for 3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0071] The acrylate monomer is a mixture of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The amount of the organosilicon monomer is 8% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of the emulsifier is 5% by weight of the total amount of the acrylate monomer and organosilicon monomer.

[0072] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0073] (4) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 95°C for 30 seconds, and then immerse it in acrylic emulsion again for 60 seconds, dry it at 105°C for 1 minute to obtain impregnated paper.

[0074] The wooden substrate was placed in an acrylic ester emulsion, vacuumed to -0.1 MPa, immersed for 0.5 h, pressurized to 1 MPa, and immersed for 1 h. After being taken out, it was naturally dried for 5 days, dried at 65°C for 10 h, and then heated to 105°C and dried for 10 h to obtain a pretreated substrate;

[0075] The impregnated paper and the pretreated substrate were hot-pressed to obtain a veneer panel. The hot-pressing temperature was 160°C, the hot-pressing time was 60 seconds, and the hot-pressing pressure was 1 MPa.

[0076] Based on Example 4, a control experiment was conducted, specifically Comparative Examples 1 to 3, as described below:

[0077] Comparative Example 1: A method for preparing a deformation-resistant and waterproof wood veneer panel, comprising the following steps:

[0078] (1) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen atmosphere. The mixture was reacted at 85°C for 1 hour, and then the temperature was raised to 125°C and the reaction was continued for 2 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0079] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0080] (2) Mixing 1 / 2 parts by mass of an emulsifier and deionized water, stirring evenly, adding an acrylate monomer and a toughening silicone to obtain a pre-emulsion; mixing ammonium persulfate and deionized water, stirring evenly, to obtain an initiator solution.

[0081] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 70°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 10 minutes, heat to 85°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 1 hour, add a cross-linking monomer, continue to react for 3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0082] The acrylate monomer is a compound of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The toughening silicone is used in an amount of 8% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of emulsifier is 5% by weight of the total amount of the acrylate monomer and toughening silicone.

[0083] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0084] (3) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 95°C for 30 seconds, and then immerse it in acrylic emulsion again for 60 seconds, and dry it at 105°C for 1 minute to obtain impregnated paper.

[0085] The wooden substrate was placed in an acrylic ester emulsion, vacuumed to -0.1 MPa, immersed for 0.5 h, pressurized to 1 MPa, and immersed for 1 h. After being taken out, it was naturally dried for 5 days, dried at 65°C for 10 h, and then heated to 105°C and dried for 10 h to obtain a pretreated substrate;

[0086] The impregnated paper and the pretreated substrate were hot-pressed to obtain a veneer panel. The hot-pressing temperature was 160°C, the hot-pressing time was 60 seconds, and the hot-pressing pressure was 1 MPa.

[0087] Comparative Example 1 is based on Example 4, but without the addition of flame retardant silicone.

[0088] Comparative Example 2: A method for preparing a deformation-resistant and waterproof wood veneer panel, comprising the following steps:

[0089] (1) Octavinyl POSS, DOPO and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an 85°C oil bath for 10 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain flame retardant silicone; the molar ratio of octavinyl POSS to DOPO was 1:3.2; the amount of azobisisobutyronitrile was 0.05 wt% of the octavinyl POSS.

[0090] (2) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen. The mixture was reacted at 85°C for 1 hour, and then the temperature was raised to 125°C and the reaction was continued for 2 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0091] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0092] (3) Compounding the toughening silicone and the flame-retardant silicone to obtain a silicone monomer; the mass ratio of the toughening silicone and the flame-retardant silicone is 2:1.

[0093] 1 / 2 parts by mass of emulsifier and deionized water are mixed and stirred evenly, and acrylate monomer is added to obtain a pre-emulsion; ammonium persulfate and deionized water are mixed and stirred evenly to obtain an initiator solution.

[0094] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 70°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 10 minutes, heat to 85°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 1 hour, add a cross-linking monomer and a silicone monomer, continue to react for 3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0095] The acrylate monomer is a mixture of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The amount of the organosilicon monomer is 8% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of the emulsifier is 5% by weight of the total amount of the acrylate monomer and organosilicon monomer.

[0096] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0097] (4) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 95°C for 30 seconds, and then immerse it in acrylic emulsion again for 60 seconds, dry it at 105°C for 1 minute to obtain impregnated paper.

[0098] The wooden substrate was placed in an acrylic ester emulsion, vacuumed to -0.1 MPa, immersed for 0.5 h, pressurized to 1 MPa, and immersed for 1 h. After being taken out, it was naturally dried for 5 days, dried at 65°C for 10 h, and then heated to 105°C and dried for 10 h to obtain a pretreated substrate;

[0099] The impregnated paper and the pretreated substrate were hot-pressed to obtain a veneer panel. The hot-pressing temperature was 160°C, the hot-pressing time was 60 seconds, and the hot-pressing pressure was 1 MPa.

[0100] Comparative Example 2 is based on Example 4, but the order of adding the organosilicon monomers is adjusted.

[0101] Comparative Example 3: A method for preparing a deformation-resistant and waterproof wooden veneer panel, comprising the following steps:

[0102] (1) Octavinyl POSS, DOPO and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an 85°C oil bath for 10 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain flame retardant silicone; the molar ratio of octavinyl POSS to DOPO was 1:3.2; the amount of azobisisobutyronitrile was 0.05 wt% of the octavinyl POSS.

[0103] (2) Dipropylene glycol and vinyl triethoxysilane were mixed, a catalyst was added, and the mixture was stirred evenly under nitrogen. The mixture was reacted at 85°C for 1 hour, and then the temperature was raised to 125°C and the reaction was continued for 2 hours. After the reaction was completed, the catalyst was removed and the product was collected to obtain toughened silicone.

[0104] The molar ratio of dipropylene glycol to vinyl triethoxysilane is 1.8: 1. The catalyst is barium hydroxide, and the amount used is 0.06 wt% of the total mass of dipropylene glycol and vinyl triethoxysilane.

[0105] (3) Compounding the toughening silicone and the flame-retardant silicone to obtain a silicone monomer; the mass ratio of the toughening silicone and the flame-retardant silicone is 1:1.

[0106] Mix 1 / 2 parts by mass of emulsifier and deionized water, stir evenly, add acrylate monomer and silicone monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution.

[0107] Mix a buffer, 1 / 2 part by mass of an emulsifier and deionized water, heat to 70°C, add 1 / 3 part by mass of a pre-emulsion and 1 / 3 part by mass of an initiator solution, react for 10 minutes, heat to 85°C, add 2 / 3 parts by mass of a pre-emulsion and 2 / 3 parts by mass of an initiator solution, continue to react for 1 hour, add a cross-linking monomer, continue to react for 3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 35%.

[0108] The acrylate monomer is a mixture of methyl methacrylate, butyl acrylate, and acrylic acid, with a mass ratio of methyl methacrylate, butyl acrylate, and acrylic acid of 3:10:1. The amount of the organosilicon monomer is 8% by weight of the acrylate monomer. The total amount of ammonium persulfate is 1.5% by weight of the acrylate monomer, and the concentration of the initiator solution is 3% by weight. The emulsifier is sodium lauryl sulfate, and the total amount of the emulsifier is 5% by weight of the total amount of the acrylate monomer and organosilicon monomer.

[0109] The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate and hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4wt% of the acrylate monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the amount is 0.05wt% of the acrylate monomer.

[0110] (4) Cut the base paper and immerse it in acrylic emulsion once for 50 seconds, dry it at 95°C for 30 seconds, and then immerse it in acrylic emulsion again for 60 seconds, dry it at 105°C for 1 minute to obtain impregnated paper.

[0111] The wooden substrate was placed in an acrylic ester emulsion, vacuumed to -0.1 MPa, immersed for 0.5 h, pressurized to 1 MPa, and immersed for 1 h. After being taken out, it was naturally dried for 5 days, dried at 65°C for 10 h, and then heated to 105°C and dried for 10 h to obtain a pretreated substrate;

[0112] The impregnated paper and the pretreated substrate were hot-pressed to obtain a veneer panel. The hot-pressing temperature was 160°C, the hot-pressing time was 60 seconds, and the hot-pressing pressure was 1 MPa.

[0113] Comparative Example 3 is based on Example 4, and the amounts of flame retardant silicone and toughening silicone are adjusted.

[0114] In the above examples, all raw materials are from the following sources: DOPO: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, commercially available; base paper: wood grain color, basis weight 80 g / m 2 , provided by Jiangsu Rocky Wood Industry Co., Ltd.; wood substrate: particle board, provided by Guangdong Hansen Environmental Protection Materials Technology Co., Ltd.

[0115] Detection experiment 1:

[0116] According to the methods disclosed in Examples 1 to 4 and Comparative Examples 1 to 3, decorative panel samples were prepared and tested according to the following method:

[0117] 1. Pollution resistance: According to step 4.40 of GB / T17657-2013, add red ink to the surface of the sample and record the pollution resistance level of the sample.

[0118] 2. Bonding strength: Test the bonding strength between the impregnated paper and the wood substrate according to step 4.16 of GB / T17657-2013.

[0119] According to the methods disclosed in Examples 1 to 4 and Comparative Examples 1 to 3, impregnated paper samples were prepared and tested as follows:

[0120] 3. Water resistance: Place the impregnated paper in deionized water for 24 hours, take it out and wipe off the surface moisture, weigh it before and after the test, and calculate the water absorption rate.

[0121] 4. Flame retardant: ASTM D2863 standard tests and records the limiting oxygen index of the impregnated paper.

[0122] project Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Water absorption 2.47％ 2.33％ 2.18％ 2.17％ 3.72％ 3.28％ 2.23％ Limiting oxygen index 30 30 31 31 20 27 32 Bonding strength MPa 0.77 0.82 0.85 0.96 0.84 0.87 0.93 Pollution resistance level Level 5 Level 5 Level 5 Level 5 / / /

[0123] Conclusion: This application uses acrylic emulsion to replace melamine formaldehyde resin as the impregnating glue, thereby achieving formaldehyde-free and green processing of decorative panels. The prepared plywood has excellent waterproof resistance, is not easy to deform, and has excellent flame retardant properties.

[0124] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention, but the scope of protection of this application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the spirit and principles of the present invention and within the technical scope disclosed in this application should be included in the scope of protection of this application. The embodiments and features of the embodiments of this application can be combined with each other unless there is a conflict. Therefore, the scope of protection of this application should be based on the scope of protection of the claims.

Claims

1. A method for preparing a deformation-resistant and waterproof wood veneer panel, characterized by: The following steps are involved: (1) Octavinyl POSS, DOPO, and azobisisobutyronitrile were mixed, toluene was added under nitrogen atmosphere, stirred until dissolved, and reacted in an oil bath at 80-85° C. for 10-12 h. After the reaction, the upper liquid was removed, the product was collected, and vacuum dried to obtain a flame-retardant silicone; (2) Dipropylene glycol and vinyl triethoxysilane are mixed, a catalyst is added, and the mixture is stirred evenly under a nitrogen environment. The mixture is reacted at 80-85° C. for 1-1.5 hours, and then the temperature is raised to 120-125° C. and the reaction is continued for 2-3 hours. After the reaction is completed, the catalyst is removed and the product is collected to obtain a toughened silicone; (3) compounding the toughening silicone and the flame retardant silicone to obtain a silicone monomer; Mix 1 / 2 part by mass of an emulsifier and deionized water, stir evenly, add an acrylate monomer and an organosilicon monomer to obtain a pre-emulsion; mix ammonium persulfate and deionized water, stir evenly to obtain an initiator solution; Mix a buffer, 1 / 2 parts by weight of an emulsifier, and deionized water, heat to 65-70° C., add 1 / 3 parts by weight of a pre-emulsion and 1 / 3 parts by weight of an initiator solution, react for 10-20 minutes, heat to 80-85° C., add 2 / 3 parts by weight of a pre-emulsion and 2 / 3 parts by weight of an initiator solution, continue to react for 1-2 hours, add a crosslinking monomer, continue to react for 2-3 hours, cool and filter to obtain an acrylate emulsion with a solid content of 30-40%; (4) cutting the base paper and dipping it in an acrylic emulsion for a first time for 40 to 50 seconds, drying it at 90 to 95° C. for 30 to 40 seconds, and then dipping it in an acrylic emulsion for a second time for 50 to 60 seconds, and drying it at 100 to 105° C. for 1 to 2 minutes to obtain an impregnated paper; hot pressing the impregnated paper and the wooden substrate to obtain a veneer; The mass ratio of the toughening organic silicon to the flame retardant organic silicon is 2:1, and the amount of the organic silicon monomer is 5-8wt% of the acrylate monomer.

2. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: In step (3), the acrylate monomer is a compound of methyl methacrylate, butyl acrylate and acrylic acid, and the mass ratio of methyl methacrylate, butyl acrylate and acrylic acid is 3:10:

1.

3. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: The cross-linking monomer is 1,3-butanediol dimethacrylate and hydroxybutyl acrylate, the mass ratio of 1,3-butanediol dimethacrylate to hydroxybutyl acrylate is 1:1, and the amount of the cross-linking monomer is 4-5wt% of the acrylate monomer.

4. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: In step (3), the total amount of ammonium persulfate is 1-2 wt% of the acrylate monomer, and the concentration of the initiator solution is 3-4 wt%; the emulsifier is sodium lauryl sulfate, and the total amount is 3-5 wt% of the total amount of the acrylate monomer and the silicone monomer; the buffer is disodium hydrogen phosphate dodecahydrate, and the total amount is 0.01-0.05 wt% of the acrylate monomer.

5. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: In step (1), the molar ratio of the octavinyl POSS to DOPO is 1:(3-3.2); and the amount of azobisisobutyronitrile is 0.05-0.06 wt % of the octavinyl POSS.

6. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 5, characterized in that: The preparation steps of octavinyl POSS are as follows: vinyl triethoxysilane, acetone, concentrated hydrochloric acid and deionized water are mixed, stirred evenly, reacted at 40-50° C. for 20-24 hours, precipitated product, washed and dried to obtain octavinyl POSS.

7. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: In step (2), the molar ratio of dipropylene glycol and vinyltriethoxysilane is (1.6-1.8):1, the catalyst is barium hydroxide, and the amount of the catalyst is 0.05-0.06wt% of the total mass of dipropylene glycol and vinyltriethoxysilane.

8. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: Before hot pressing, the wooden substrate is placed in an acrylic emulsion, vacuumed to -0.1 MPa, immersed for 0.5 to 1 hour, pressurized to 0.8 to 1 MPa, and immersed for another 0.5 to 1 hour. After being taken out, it is naturally dried for 5 to 6 days, dried at 60 to 70°C for 10 to 12 hours, and then heated to 105 to 115°C and dried for 8 to 10 hours to obtain a pretreated substrate. The impregnated paper is laminated to the pretreated substrate by hot pressing to obtain a decorative panel.

9. The method for preparing a deformation-resistant and waterproof wood veneer panel according to claim 1, characterized in that: In step (4), the hot pressing temperature is 150-160° C., the hot pressing time is 50-60 s, and the hot pressing pressure is 1-2 MPa.

10. A veneer panel prepared according to the method for preparing a deformation-resistant and waterproof wood veneer panel according to any one of claims 1 to 9.