Multifunctional composite fiber reinforced decorative base paper and preparation method thereof

Abstract

The invention provides multifunctional composite fiber reinforced decorative base paper and a preparation method thereof. The decorative base paper is prepared from the following raw materials in parts by weight: 30-60 phr of wood pulp fibers, 15-35 phr of bamboo fibers, 1-10 phr of polyester fibers, 1-10 phr of polyamide fibers, 57-91 phr of an antibacterial reinforcing agent, 3-20 phr of a flame retardant and 1-10 phr of nano cellulose. The antibacterial reinforcing agent is prepared from the following components in parts by weight: 1 to 5 phr of silver nitrate, 3 to 10 phr of tetrabutyl titanate, 2 to 8 phr of sulfydryl modified chitosan, 50 to 70 phr of absolute ethyl alcohol and 2 to 6 phr of plant essential oil; the flame retardant is a composition of ammonium polyphosphate and aluminum hydroxide wrapped by chitosan. According to the invention, the composite fiber prepared by compounding four fibers is used, and the antibacterial agent, the flame retardant and the nano cellulose are added to supplement functionality, so that the multifunctional composite fiber reinforced decorative base paper with high strength, excellent wear resistance and excellent antibacterial performance is obtained, and the fireproof performance of the multifunctional composite fiber reinforced decorative base paper reaches the national B1-level fireproof standard.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite materials, in particular to a multifunctional composite fiber reinforced decorative base paper. BACKGROUND

[0002] With the improvement of people's living standards, the aesthetic and functional requirements of home decoration and building decoration materials are increasing. As an important raw material for producing decorative paper, artificial board and other decorative materials, the market demand for decorative base paper continues to rise. Traditional decorative base paper has certain limitations in strength, wear resistance, fire resistance, antibacterial and other functions, and it is difficult to meet the demand of high-end market for multifunctional and high-performance decorative materials. For example, in public places and high-end residential decoration, the fire resistance and antibacterial performance of decorative materials are strictly required; in commercial space, high wear-resistant decorative materials are more popular. Therefore, the development of multifunctional composite fiber reinforced decorative base paper can effectively expand the application field of decorative base paper, meet the market demand of continuous segmentation, and has broad market prospect.

[0003] Currently, the decorative base paper industry is facing fierce market competition, and technological innovation has become the key to improving the competitiveness of enterprises. The production technology of traditional decorative base paper is relatively mature, and the products are highly homogenized. In order to stand out in the market, enterprises need to increase research and development investment, introduce advanced technology, and develop new products with differentiated competitive advantage. At the same time, with the deepening of environmental protection concept, consumers also put forward higher requirements on the environmental performance of decorative materials. The development of multifunctional composite fiber reinforced decorative base paper uses environmentally friendly raw materials and production process, which meets the trend of green development of the industry and helps to promote the technological upgrading of the decorative base paper industry.

[0004] The state has introduced a series of policies to encourage the development of high-tech industries, providing a good policy environment for the technological innovation of the decorative base paper industry. For example, the fiscal subsidies and tax incentives for new material research and development reduce the research and development costs of enterprises and improve the enthusiasm of enterprises to carry out technological innovation. Under such policy background, the development of multifunctional composite fiber reinforced decorative base paper development project can make full use of policy resources, accelerate the pace of technological innovation of enterprises, and improve the core competitiveness of enterprises.

[0005] Patent document CN120118457A discloses a bacteriostatic bamboo fiber composite material with good bacteriostatic performance, but the wear resistance, mechanical strength and flame retardance are insufficient; patent document CN119798973A discloses a modified glass fiber reinforced polyamide composite material with good flame retardance and mechanical strength, but the bacteriostatic performance is insufficient. In summary, the performance of the current composite fiber is more or less lacking, so it is very important to study a multifunctional composite fiber reinforced decorative base paper. SUMMARY

[0006] The present application aims to solve the problems of insufficient strength and low wear resistance of the composite fiber base paper, and provides a composite fiber prepared by mixing wood pulp fiber, bamboo fiber, polyester fiber and polyamide fiber, and adding nano-cellulose and nano-zinc oxide, so that the composite fiber has the characteristics of relative environmental protection, high strength and high wear resistance by optimizing the fiber ratio and adding nano-cellulose.

[0007] Another object of the present application is to solve the problem of insufficient antibacterial performance of the composite fiber base paper, and to obtain a composite antibacterial fiber by adding an antibacterial reinforcing agent to the composite fiber, so as to obtain a decorative base paper with good antibacterial effect.

[0008] The present application also aims to solve the problem of low fireproof performance of the composite fiber base paper, and to add flame retardant ammonium polyphosphate and aluminum hydroxide, so that the flame retardant can protect the paper when a fire occurs, thereby improving the fireproof performance of the paper.

[0009] The present application also aims to provide a preparation method of a multifunctional composite fiber reinforced base paper, which uses nano technology, microcapsule technology and chemical coating method to prepare a multifunctional composite fiber reinforced base paper.

[0010] In order to achieve the above-mentioned object, the present application discloses a multifunctional composite fiber reinforced base paper, which comprises the following raw materials by weight: wood pulp fiber 30-60 phr, bamboo fiber 15-35 phr, polyester fiber 1-10 phr, polyamide fiber 1-10 phr, antibacterial reinforcing agent 55-95 phr, flame retardant 1-20 phr, and nano-cellulose 1-10 phr. The wood pulp fiber, bamboo fiber, polyester fiber and polyamide fiber are mixed to prepare a fiber matrix, the wood pulp fiber, bamboo fiber, polyester fiber and polyamide fiber contain a large number of hydroxyl groups, ester groups in the polyester fiber and amide groups in the polyamide fiber, which form an interfacial bond through hydrogen bonding and condensation reaction to enhance the bonding strength of the composite fiber matrix; the long bamboo fiber and short polyester fiber form a three-dimensional network structure to improve the overall strength, and the wood pulp fiber contains lignin to fill the matrix pores; the added nano-cellulose and cellulose crystals in the bamboo fiber enhance the interfacial stress; the benzene ring structure of the polyester fiber improves the overall rigidity, and the methylene group in the polyamide fiber improves the flexibility of the fiber; the blending of the two ensures the strength of the fiber matrix and the flexibility of the fiber; the addition of the flame retardant is closely combined with the fiber matrix to improve the overall flame retardant performance; in summary, a multifunctional composite fiber with high strength and high wear resistance is prepared, thereby preparing a multifunctional composite fiber base paper.

[0011] Preferably, the following raw materials are included by weight parts: wood pulp fiber 40-50 phr, bamboo fiber 20-30 phr, polyester fiber 3-8 phr, polyamide fiber 2-7 phr, antibacterial reinforcing agent 60-90 phr, flame retardant 10-20 phr, nanocellulose 5-10 phr.

[0012] Preferably, the following raw materials are also included by weight parts: nanometer zinc oxide 1-10 phr, dispersant 4-6 phr, wet strength agent 5-7 phr. The nanometer zinc oxide has broad-spectrum antibacterial properties, and has a synergistic effect with the antibacterial reinforcing agent and the bamboo fiber, further providing the composite fiber with antibacterial properties. Meanwhile, the nanometer zinc oxide is a rigid filler that forms hydrogen bonds with the hydroxyl groups of cellulose and the amide groups of polyamide, thereby improving the wear resistance of the fiber. The dispersant and the wet strength agent allow the overall performance of the cellulose to be fully utilized.

[0013] Preferably, the antibacterial reinforcing agent is silver nitrate 1-5 phr, tetrabutyl titanate 3-10 phr, thiol-modified chitosan 2-8 phr, anhydrous ethanol 50-80 phr, and plant essential oil 2-6 phr. The antibacterial reinforcing agent allows the nanometer silver-titanium dioxide to adhere to the surface layer of the composite fiber. The high active sites on the surface of the nanometer silver can directly damage the phospholipid bilayer of the cell membrane of microorganisms, thereby destroying the activity of the microorganisms. The nanometer silver can form a conductive path, effectively allowing the composite fiber decorative base paper to have certain antistatic ability. The nanometer titanium dioxide can improve the self-cleaning performance of the product, allowing the surface of the decorative base paper to form a photocatalytic active layer that can reduce organic pollutants and inhibit the photo-oxidative degradation of the fiber matrix, while also improving the overall antioxidant performance. The plant essential oil can destroy the membrane structure of microorganisms and form a consistent biofilm with the nanometer silver oxide.

[0014] Preferably, the flame retardant is a combination of ammonium polyphosphate and aluminum hydroxide, with the ratio of ammonium polyphosphate to aluminum hydroxide being 1:1-5. The combination of ammonium polyphosphate and aluminum hydroxide can have a synergistic effect at different stages of flame retardation. Aluminum hydroxide mainly functions through gas phase and condensed phase flame retardation, while ammonium polyphosphate focuses on condensed phase flame retardation. The combination of the two can provide comprehensive flame retardation. In addition, ammonium polyphosphate and aluminum hydroxide can balance each other, thereby avoiding problems such as poor mechanical properties and poor water resistance of the paper.

[0015] Preferably, the particle size of the nanometer zinc oxide is 30-60 nm.

[0016] The application also provides a preparation method of the multifunctional composite fiber reinforced decorative base paper, which comprises the following steps: S1, pretreat wood pulp, bamboo pulp, polyester fiber, polyamide fiber, and nanocellulose. After treatment, mix them evenly to obtain composite fiber; S2, immerse the composite fiber in an antibacterial reinforcing agent and solidify to obtain composite antibacterial fiber; S3, the composite antibacterial fiber is dispersed and beaten, and an anti-flaming agent is added to obtain a composite anti-flaming and antibacterial fiber; S4, the composite antibacterial fiber, a wet strength agent, nano zinc oxide and a dispersing agent are mixed and dispersed, and after wet papermaking, a plant essential oil-film forming agent is coated to prepare a multifunctional composite fiber reinforced decorative base paper.

[0017] Preferably, in step 1, the pretreatment of the polyester fiber and the polyamide fiber is soaking in a 15% sodium hydroxide solution for 20 minutes, diluting with water and stirring for 20 minutes, and then adding the treated polyester fiber and the polyamide fiber to the wood pulp and the bamboo pulp after being crushed for 30 minutes, and then adding nano cellulose.

[0018] Preferably, in step S2, the soaking time is 15-30 minutes, and the solidification is performed in a freeze dryer at a solidification temperature of-50°C, a vacuum degree of less than 10 pa, and a drying time of 24 hours.

[0019] Preferably, in step S3, the wet papermaking is sheeting, pressing and drying, and in step S4, the microcapsule technology is chitosan wrapping ammonium polyphosphate and polyamide fiber.

[0020] The multifunctional composite fiber reinforced decorative base paper has the advantages that the tensile strength is increased by more than 30% and the tear strength is increased by more than 20% compared with common decorative base paper, the wear resistance is tested according to the national standard, and the wear resistance reaches more than 5000 times, the fireproof performance reaches the national B1 level fireproof standard, and the antibacterial performance reaches more than 95% against common bacteria such as escherichia coli and staphylococcus aureus. DETAILED DESCRIPTION

[0021] The application will be further described in detail below with reference to specific embodiments.

[0022] Total embodiment: The decorative base paper raw materials include wood pulp fiber 30-60 phr, bamboo fiber 15-35 phr, polyester fiber 1-10 phr, polyamide fiber 1-10 phr, antibacterial reinforcing agent 55-95 phr, anti-flaming agent 1-20 phr, nano cellulose 1-10 phr, nano zinc oxide 1-10 phr, dispersing agent 4-6 phr and wet strength agent 5-7 phr. The antibacterial reinforcing agent includes silver nitrate 1-5 phr, tetrabutyl titanate 3-10 phr, thiol-modified chitosan 2-8 phr, anhydrous ethanol 50-80 phr and plant essential oil 2-6 phr.

[0023] Preparation method: S1, pretreatment: polyester fiber, polyamide fiber is soaked with 15% sodium hydroxide solution for 20 minutes, then diluted with water after stirring for 20 minutes, dispersed uniformly; wood pulp fiber, bamboo fiber is put into the hydraulic pulper, disintegrated for 30 minutes, then add dispersed polyester fiber, polyamide fiber, stirring for 20-30 minutes, get composite fiber.

[0024] S2, antibacterial reinforcement: the composite fiber is immersed in the antibacterial reinforcing agent, immersed for 15-30 minutes, transferred to the freeze dryer, solidification temperature-50℃, vacuum degree <10pa, dried for 24 hours to get composite antibacterial fiber.

[0025] S3, flame retardant addition: the composite antibacterial fiber is beaten to 25-40°SR, dispersed in water, then add chitosan wrapped ammonium polyphosphate, aluminum hydroxide, get composite flame retardant antibacterial fiber.

[0026] S4, preparation of base paper: the composite flame retardant antibacterial fiber, wet strength agent, nano zinc oxide, dispersing agent is mixed and dispersed, sheet, press, dry, plant essential oil-chitosan is sprayed on the paper surface, dried to get multifunctional composite fiber reinforced decorative base paper.

[0027] Example 1: Raw materials: wood pulp fiber 50phr, bamboo fiber 30phr, polyester fiber 8phr, polyamide fiber 7phr, silver nitrate 3phr, tetrabutyl titanate 7phr, mercapto modified chitosan 6phr, anhydrous ethanol 65phr, tea tree oil 4phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10phr, nano cellulose 7phr, nano zinc oxide 7phr, dispersing agent 5phr, wet strength agent 6phr.

[0028] Preparation method: S1, pretreatment: polyester fiber, polyamide fiber is soaked with 15% sodium hydroxide solution for 20 minutes, then diluted with water after stirring for 20 minutes, dispersed uniformly; wood pulp fiber, bamboo fiber is put into the hydraulic pulper, disintegrated for 30 minutes, then add dispersed polyester fiber, polyamide fiber, stirring for 25 minutes, get composite fiber.

[0029] S2, antibacterial reinforcement: the composite fiber is immersed in the antibacterial reinforcing agent, immersed for 20 minutes, transferred to the freeze dryer, solidification temperature-50℃, vacuum degree <10pa, dried for 24 hours to get composite antibacterial fiber.

[0030] S3, flame retardant addition: the composite antibacterial fiber is beaten to 35°SR, dispersed in water, then add chitosan wrapped ammonium polyphosphate, aluminum hydroxide, get composite flame retardant antibacterial fiber.

[0031] S4, preparation of base paper: composite flame-retardant antibacterial fiber, wet strength agent, nano zinc oxide, dispersing agent are mixed and dispersed, sheeting, pressing, drying, plant essential oil-chitosan is sprayed on the paper surface, dried to obtain multifunctional composite fiber reinforced decorative base paper.

[0032] Example 2: Raw materials: wood pulp fiber 30 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano cellulose 7 phr, nano zinc oxide 7 phr, dispersing agent 5 phr, wet strength agent 6 phr.

[0033] The preparation method is the same as that of example 1.

[0034] Example 3: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano cellulose 7 phr, nano zinc oxide 7 phr, dispersing agent 5 phr, wet strength agent 6 phr.

[0035] The preparation method is the same as that of example 1.

[0036] Example 4: Raw materials: wood pulp fiber 50 phr, bamboo fiber 15 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano cellulose 7 phr, nano zinc oxide 7 phr, dispersing agent 5 phr, wet strength agent 6 phr.

[0037] The preparation method is the same as that of example 1.

[0038] Example 5: Raw materials: wood pulp fiber 50 phr, bamboo fiber 35 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano cellulose 7 phr, nano zinc oxide 7 phr, dispersing agent 5 phr, wet strength agent 6 phr.

[0039] The preparation method is the same as Example 1.

[0040] Example 6: Raw materials: wood pulp fiber 50 phr, bamboo fiber 30 phr, polyester fiber 1 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0041] The preparation method is the same as Example 1.

[0042] Example 7: Raw materials: wood pulp fiber 50 phr, bamboo fiber 30 phr, polyester fiber 3 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0043] The preparation method is the same as Example 1.

[0044] Example 8: Raw materials: wood pulp fiber 50 phr, bamboo fiber 30 phr, polyester fiber 10 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0045] The preparation method is the same as Example 1.

[0046] Example 9: Raw materials: wood pulp fiber 50 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 1 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0047] The preparation method is the same as Example 1.

[0048] Example 10: Raw materials: wood pulp fiber 50 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 10 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0049] The preparation method is the same as that of Example 1.

[0050] Example 11: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 1 phr, tetrabutyl titanate 3 phr, thiol-modified chitosan 2 phr, anhydrous ethanol 60 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0051] The preparation method is the same as that of Example 1.

[0052] Example 12: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 5 phr, tetrabutyl titanate 10 phr, thiol-modified chitosan 8 phr, anhydrous ethanol 60 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0053] The preparation method is the same as that of Example 1.

[0054] Example 13: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 2 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0055] The preparation method is the same as that of Example 1.

[0056] Example 14: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 6 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano-cellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0057] The preparation method is the same as that of Example 1.

[0058] Example 15: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 3 phr, nano-cellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0059] The preparation method is the same as that of Example 1.

[0060] Example 16: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 20 phr, nano-cellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0061] The preparation method is the same as that of Example 1.

[0062] Example 17: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:1) 10 phr, nano-cellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0063] The preparation method is the same as that of Example 1.

[0064] Example 18: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 15 phr, nano-cellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0065] The preparation method is the same as in Example 1.

[0066] Example 19: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:5) 10 phr, nano-cellulose 7 phr, nano-zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0067] The preparation method is the same as in Example 1.

[0068] Example 20: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano-cellulose 7 phr, nano-zinc oxide 1 phr, dispersant 5 phr, wet strength agent 6 phr.

[0069] The preparation method is the same as in Example 1.

[0070] Example 21: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano-cellulose 7 phr, nano-zinc oxide 10 phr, dispersant 5 phr, wet strength agent 6 phr.

[0071] The preparation method is the same as in Example 1.

[0072] Example 22: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, cinnamon oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0073] The preparation method is the same as that of Example 1.

[0074] Example 23: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, cinnamon oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 1 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0075] The preparation method is the same as that of Example 1.

[0076] Example 24: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, cinnamon oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 10 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0077] The preparation method is the same as that of Example 1.

[0078] Comparative Example 1: Raw materials: polyester fiber 53 phr, polyamide fiber 52 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol-modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0079] This comparative example lacks wood pulp fiber and bamboo fiber, and the antibacterial performance is expected to be reduced, and the lack of wood pulp fiber and bamboo fiber makes the combination of antibacterial agents decrease, which may also cause the antibacterial performance to decrease; the flame retardant performance is expected to be slightly improved; the wear resistance is improved, the wet strength is greatly improved, and the dry strength is almost unchanged.

[0080] Preparation method: S1, pretreatment: polyester fiber, polyamide fiber is soaked with 15% sodium hydroxide solution for 20 minutes, then diluted with water and stirred for 20 minutes, dispersed uniformly to get composite fiber.

[0081] S2, antibacterial reinforcement: the composite fiber is immersed in the antibacterial reinforcing agent for 20 minutes, transferred to the freeze dryer, the solidification temperature is-50℃, the vacuum degree is <10pa, and dried for 24 hours to get the composite antibacterial fiber.

[0082] S3, flame retardant addition: the composite antibacterial fiber is beaten to 35°SR, dispersed in water, then chitosan wrapped ammonium polyphosphate, aluminum hydroxide is added, to get the composite flame retardant antibacterial fiber.

[0083] S4, preparation of base paper: the composite flame retardant antibacterial fiber, wet strength agent, nano zinc oxide, dispersing agent are mixed and dispersed, sheeted, pressed, dried, and the plant essential oil-chitosan is sprayed on the paper surface, dried to get the multifunctional composite fiber reinforced decorative base paper.

[0084] Comparative example 2: Raw materials: wood pulp fiber 65 phr, bamboo fiber 40 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano cellulose 7 phr, nano zinc oxide 7 phr, dispersing agent 5 phr, wet strength agent 6 phr.

[0085] This comparative example lacks polyester fiber, polyamide fiber, and relies solely on wood pulp fiber and bamboo fiber as the fiber matrix, which changes the system structure.

[0086] Preparation method: S1, pretreatment: wood pulp fiber and bamboo fiber are put into a hydraulic pulper, disintegrated for 30 minutes, stirred for 25 minutes, to get composite fiber. Other steps are the same as comparative example 1.

[0087] Comparative example 3: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nano cellulose 7 phr, nano zinc oxide 7 phr, dispersing agent 5 phr, wet strength agent 6 phr.

[0088] This comparative example lacks silver nitrate, tetrabutyl titanate, thiol modified chitosan, and anhydrous ethanol, and relies solely on the antibacterial reinforcement of plant essential oil, and the antibacterial property still decreases.

[0089] Preparation method: remove S2 step of example 3, other steps are the same as example 3.

[0090] Comparative example 4: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0091] This comparative example lacks plant essential oil, and the plant essential oil-nano silver system is destroyed, and the antibacterial performance is expected to decrease.

[0092] Preparation method: S4, the composite antibacterial fiber, wet strength agent, nano zinc oxide, dispersant are mixed and dispersed, and a multifunctional composite fiber reinforced decorative base paper is prepared by wet laying. Other steps are the same as example 3.

[0093] Comparative example 5: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, nanocellulose 7 phr, nano zinc oxide 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0094] This comparative example lacks flame retardant, and the lack of flame retardant is expected to significantly reduce the fireproof performance of the paper.

[0095] Preparation method: remove S3 step of example 3, other steps are the same as example 3.

[0096] Comparative example 6: Raw materials: wood pulp fiber 60 phr, bamboo fiber 30 phr, polyester fiber 8 phr, polyamide fiber 7 phr, silver nitrate 3 phr, tetrabutyl titanate 7 phr, thiol modified chitosan 6 phr, anhydrous ethanol 65 phr, tea tree oil 4 phr, flame retardant (chitosan: ammonium polyphosphate: aluminum hydroxide: 0.1:1:3) 10 phr, nanocellulose 7 phr, dispersant 5 phr, wet strength agent 6 phr.

[0097] Nanometer zinc oxide is missing, and the wear resistance is expected to be slightly missing. The rigid filler is missing, which reduces the strength of the system.

[0098] Preparation method: S4, the composite antibacterial fiber, wet strength agent, dispersing agent are mixed and dispersed, and after wet laying, the multifunctional composite fiber reinforced decorative base paper is prepared by coating plant essential oil-film forming agent. Other steps are the same as example 3.

[0099] The antibacterial performance test, the fire resistance performance test, the wear resistance performance test, and the strength performance test are carried out on the above examples 1-22 and comparative examples 1-6. The antibacterial performance test: Escherichia coli and Staphylococcus aureus are used as test bacteria, the bacteria solution is added on the surface of the sample, a film is covered, and the number of living bacteria is measured after 24 hours of culture at 37°C, and the antibacterial rate is calculated; the fire resistance performance test: according to the national standard GB8624-2012 “Classification of Combustion Performance of Building Materials and Products” and GB50222-2017 “Fireproof Design Specification for Building Interior Decoration”; surface ignition test: requirement: flame tip height ≤ 150 mm within 60 s, no burning drop ignites filter paper phenomenon. The wear resistance performance test: according to the current national standard GB / T 18102-2020 “Impregnated Paper Laminate Wood Flooring”, the surface wear resistance of the decorative base paper after the product is made. The strength test measures the longitudinal dry tensile strength and longitudinal wet tensile strength.

[0100] Table 1 performance test of examples 1-10.

[0101] From the above table, examples 1-5 study the influence of the addition amount of wood pulp fiber and bamboo fiber on the overall properties, and examples 6-10 study the influence of the addition amount of polyester fiber and polyamide fiber on the overall properties. Bamboo fiber has an influence on antibacterial performance, and with the increase of the addition amount of bamboo fiber, the antibacterial performance is better; polyester fiber and polyamide fiber have a greater influence on wear resistance and tensile strength, and too much wood pulp fiber and bamboo fiber will cause the tensile strength to decrease; the antibacterial performance of example 5 is the best, and the wear resistance and tensile strength performance of example 8 is higher.

[0102] Table 2 performance test of examples 11-22.

[0103] Examples 11-24 are about the study of the addition amount of functional supplements on the overall properties; Examples 11-14 are about the study of the antibacterial supplements on the overall antibacterial performance, with the increase of the addition amount of the plant essential oil and the silver, titanium supplements, the antibacterial performance is also improved, the plant essential oil and the nano silver form an antibacterial protection network, play a sterilization and inactivation role, and have a protective effect on the paper, and the nano titanium dioxide is attached to the surface of the paper at the same time, catalyzes the bacterial inactivation; Examples 22 and 3 are about the influence of different plant essential oils on the antibacterial performance, the influence of the two plant essential oils on the antibacterial performance is almost the same, and the two plant essential oils can be used together.

[0104] Examples 15-19 are the study of the flame retardant on the fireproof performance, the fireproof performance of Example 18 is the best, and all the examples all reach the B1 level of the fireproof standard. Examples 3, 20-21 are the study of the nano zinc oxide, the filling effect of the nano zinc oxide can penetrate into the fiber pores and fill the micro defects; the surface hydroxyl group of the zinc oxide forms a network of bonds with the hydroxyl group of the cellulose molecular weight, enhances the bonding strength, and the more the nano zinc oxide is added, the higher the overall wear resistance is. Examples 3, 23 and 24 are the study of the addition of nano cellulose on the overall performance, the nano cellulose enhances the interface stress of the cellulose crystal in the bamboo fiber, and with the increase of the nano cellulose, the system is better combined and the strength is higher.

[0105] Table 3 Comparative Examples 1-6 Performance Test.

[0106] According to Examples 3 and Comparative Examples 1 and 2, it can be known that the comprehensive performance of the composite fiber is better, and the use of wood pulp fiber, bamboo fiber alone, or the use of polyester fiber, polyamide fiber alone will cause the antibacterial performance or mechanical performance to be poor, so the composite fiber prepared from the wood pulp fiber, bamboo fiber, polyester fiber and polyamide fiber disclosed in the application can achieve the multifunctional composite fiber reinforced decorative base paper.

[0107] According to Examples 3 and Comparative Examples 3 and 4, it can be known that in the antibacterial supplement, if the plant essential oil is missing, the antibacterial effect of the bamboo fiber and the nano silver and titanium dioxide synergistic effect is not high enough; if the nano silver and titanium dioxide are missing, the overall antibacterial performance will be greatly reduced, so the comprehensive antibacterial system of the bamboo fiber, the plant essential oil-nano silver and titanium dioxide provided by the application can make the antibacterial rate of the system reach more than 95%.

[0108] According to the embodiment 3 and the comparative example 5, it can be known that the lack of the flame retardant makes the whole become a flammable product, and the microcapsule-encapsulated ammonium polyphosphate and aluminum hydroxide can release a protective layer when encountering flame to protect the product. According to the embodiment 3 and the comparative example 6, it can be known that the lack of the hydrogen bond formed between the nano zinc oxide and the hydroxyl group of cellulose and the amide group of polyamide reduces the wear resistance of the composite fiber.

[0109] It should be noted that the above examples and comparative examples are only used to illustrate the technical solutions of the present application but not limit the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope of the present application, and all of them should be covered in the scope of the present application.

Claims

1. A multifunctional composite fiber-reinforced decorative base paper, characterized in that, By weight, it includes the following raw materials: 30-60 phr wood pulp fiber, 15-35 phr bamboo fiber, 1-10 phr polyester fiber, 1-10 phr polyamide fiber, 57-91 phr antibacterial reinforcing agent, 3-20 phr flame retardant, and 1-10 phr nanocellulose.

2. The multifunctional composite fiber reinforced decorative base paper according to claim 1, characterized in that, By weight, it includes the following raw materials: 40-50 phr wood pulp fiber, 20-30 phr bamboo fiber, 3-8 phr polyester fiber, 2-7 phr polyamide fiber, 60-90 phr antibacterial reinforcing agent, 10-20 phr flame retardant, and 5-10 phr nanocellulose.

3. A multifunctional composite fiber-reinforced decorative base paper according to claim 1 or 2, characterized in that, By weight, it also includes the following raw materials: 1-10 phr of nano zinc oxide, 4-6 phr of dispersant, and 5-7 phr of wet strength agent.

4. A multifunctional composite fiber-reinforced decorative base paper according to claim 1 or 2, characterized in that, The antibacterial reinforcing agent is silver nitrate 1-5 phr, tetrabutyl titanate 3-10 phr, thiol-modified chitosan 2-8 phr, anhydrous ethanol 50-70 phr, and plant essential oil 2-6 phr; the plant essential oil is one of tea tree oil and cinnamon oil.

5. The multifunctional composite fiber reinforced decorative base paper according to claim 3, characterized in that, The flame retardant is a composition of ammonium polyphosphate and aluminum hydroxide, and is encapsulated by chitosan, with the ratio of chitosan, ammonium polyphosphate and aluminum hydroxide being 0.1:1:1-5.

6. The multifunctional composite fiber reinforced decorative base paper according to claim 3, characterized in that, The required particle size of the nano zinc oxide is 30-60 nm.

7. A method for preparing a multifunctional composite fiber-reinforced decorative base paper, characterized in that, The preparation of a multifunctional composite fiber-reinforced decorative base paper according to any one of claims 1-6 includes the following steps: S1. Pre-treat wood pulp, bamboo pulp, polyester fiber, polyamide fiber, and nanocellulose; after treatment, mix them evenly to obtain composite fiber; S2. The composite fiber is immersed in an antibacterial reinforcing agent and cured to obtain the composite antibacterial fiber; S3. Pulp and disperse the composite antibacterial fiber, add flame retardant to obtain composite flame retardant antibacterial fiber; S4. The composite antibacterial fiber, wet strength agent, nano zinc oxide and dispersant are mixed and dispersed, and after wet papermaking, plant essential oil-film forming agent is coated to prepare a multifunctional composite fiber reinforced decorative base paper.

8. The method for preparing a multifunctional composite fiber reinforced decorative base paper according to claim 7, characterized in that, In step 1, the pretreatment involves soaking polyester fibers and polyamide fibers in a 15% sodium hydroxide solution for 20 minutes, diluting them with water and stirring for 20 minutes, crushing wood pulp and bamboo pulp for 30 minutes, adding the treated polyester fibers and polyamide fibers, and then adding nanocellulose and mixing.

9. The method for preparing a multifunctional composite fiber reinforced decorative base paper according to claim 7, characterized in that, The immersion time in step S2 is 15-30 minutes, and the curing is carried out in a freeze dryer at a curing temperature of -50°C and a vacuum degree of <10 Pa for 24 hours.

10. The method for preparing a multifunctional composite fiber reinforced decorative base paper according to claim 7, characterized in that, In step S3, the paper is pulped to 25-40°SR, and in step S4, the wet papermaking process consists of sheet making, pressing, and drying.

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