Energy-absorbing and anti-seismic melamine-impregnated bond paper as well as preparation method and application of energy-absorbing and anti-seismic melamine-impregnated bond paper

Abstract

The invention provides energy-absorbing anti-seismic melamine impregnated bond paper as well as a preparation method and application thereof, and belongs to the technical field of triamine decorative materials. The impregnated bond paper is sequentially provided with a back coating resin layer, a urea-formaldehyde resin layer, base material paper, a urea-formaldehyde resin layer and a surface coating resin layer, the surface coating resin layer comprises modified triamine resin; the back coating resin layer is prepared from the following raw materials: modified triamine resin, a curing agent, a release agent, a penetrating agent and a maleic anhydride grafted polyolefin elastomer; the modified triamine resin is prepared from the following raw materials: melamine, a formaldehyde solution, caprolactam, diethylene glycol and polyether block polyamide. The traditional amino resin is modified, and the energy-absorbing and anti-seismic material is introduced, so that the problem of plate surface cracking caused by environmental change can be solved.

Description

Technical Field

[0001] This invention belongs to the field of melamine decorative materials technology, specifically relating to an energy-absorbing and shock-resistant melamine-impregnated adhesive film paper, its preparation method, and its application. Background Technology

[0002] Formaldehyde-free melamine board is an environmentally friendly engineered wood product mainly used in furniture manufacturing and interior decoration. It uses formaldehyde-free adhesives (such as MDI adhesive) instead of traditional urea-formaldehyde resin, blocking formaldehyde release at the source. By 2025, leading brands in the industry had upgraded from E0 to ENF grade, with formaldehyde emission standards reduced from ≤0.05mg / m³. 3 Reduced to 0.025 mg / m³ 3 The formaldehyde emission of the boards is extremely low, meeting national environmental protection standards.

[0003] Formaldehyde-free melamine boards are widely used in furniture, decoration, and construction engineering, with their penetration rate continuously increasing, especially in customized furniture and prefabricated buildings. It is projected that environmentally friendly products will account for over 65% of the industry's total output by 2025, and the market size will continue to expand over the next five years. However, formaldehyde-free melamine boards are prone to cracking in dry environments. Traditional melamine-impregnated paper uses amino resin as the main adhesive. To achieve high hardness, high wear resistance, and high scratch resistance, it has a high cross-linking density after curing, resulting in high brittleness and insufficient ductility. Formaldehyde-free melamine boards use MDI adhesive, which has high surface hardness, high brittleness, and lacks sufficient flexibility. The shrinkage rate difference between the two is approximately 0.4%-0.6%. When temperature and humidity change, this difference leads to surface stress concentration, forming cracks. For example, during winter heating in northern regions, the geothermal environment raises the temperature of the boards and lowers humidity, accelerating the release of internal stress and causing cracking.

[0004] Existing technologies involve adding acrylic or polyurethane resins to amino resins to improve the crack resistance of melamine adhesives after curing, leveraging the flexibility of acrylic acid. However, this technology has several drawbacks: Drawback 1: While increasing the flexibility of the melamine adhesive, it reduces the scratch resistance of the cured melamine surface; Drawback 2: The added acrylic acid easily causes color differences in the melamine paper; Drawback 3: The low solids content, low permeability, and low high-temperature fluidity of acrylic acid can cause fine streaks and whitening on the melamine paper during hot pressing. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes an energy-absorbing and shock-resistant melamine-impregnated paper, its preparation method and application, which solves the problem of surface cracking caused by environmental changes by modifying traditional amino resin and introducing energy-absorbing and shock-resistant materials.

[0006] According to a first aspect of the present invention, an impregnated film paper is provided, which is provided in sequence with a back coating resin layer, a urea-formaldehyde resin layer, a substrate paper, a urea-formaldehyde resin layer and a top coating resin layer. The topcoat resin layer includes a modified triamine resin; The back coating resin layer comprises the following raw materials: modified triamine resin, curing agent, release agent, penetrant, dust remover, and maleic anhydride-grafted polyolefin elastomer; The modified melamine resin comprises the following raw materials: melamine, formaldehyde solution, caprolactam, diethylene glycol, and polyether block polyamide.

[0007] Crosslinking modification is a simple and effective method to improve the properties of melamine resin. Compared with the high crosslinking density of unmodified melamine, the internal toughening modification used in this invention involves the participation of polyether block polyamide in the curing reaction of MF resin (melamine-formaldehyde resin), which changes the molecular structure of MF resin, extends the flexible connection between triazine rings, and reduces the crosslinking density to achieve a toughening effect.

[0008] Preferably, the modified melamine resin comprises the following raw materials in parts by weight: 18-22 parts melamine, 30-35 parts formaldehyde solution, 0.5-2 parts caprolactam, 0.5-2 parts diethylene glycol, and 0.5-3.5 parts polyether block polyamide.

[0009] Preferably, the formaldehyde solution has a mass percentage concentration of 35% to 40%; and / or, the polyether block polyamide has a molecular weight of 1000 to 50000. This invention incorporates polyether block polyamide into the synthesis of melamine resin, grafting long molecular chains onto melamine-formaldehyde resin. This reduces the rigidity of the cured melamine without altering other properties.

[0010] More preferably, the polyether block polyamide is composed of polyamide hard segments and polyether soft segments in a ratio of 1:2.

[0011] More preferably, the polyether block polyamide is 1.2 to 2.2 parts by mass.

[0012] Preferably, the back coating resin layer comprises the following components by weight: 100 parts modified triamine resin, 0.2-0.4 parts curing agent, 0.05-0.2 parts release agent, 0.1-0.3 parts penetrant, 0.1-0.3 parts dust remover, and 6-10 parts maleic anhydride grafted polyolefin elastomer.

[0013] Preferably, the curing agent is model 1010, purchased from Shanghai Hongyi International Trade Co., Ltd.; the release agent is model 856, purchased from Shanghai Hongyi International Trade Co., Ltd.; the penetrant is model 14, purchased from Shanghai Hongyi International Trade Co., Ltd.; and the dust remover is model 306, purchased from Shanghai Hongyi International Trade Co., Ltd.

[0014] Preferably, the modified triamine resin is prepared by a method comprising the following steps: (1) Mix melamine with formaldehyde solution and heat. After the melamine is completely dissolved, add caprolactam and diethylene glycol. Adjust the pH to 8.5-10.5 and keep the temperature for reaction. (2) Determine the water solubility ratio. When the reaction solution shows a mist-like insoluble substance in water at a temperature of 0±1℃, add polyether block polyamide to the reaction solution to continue the reaction. (3) When the reaction solution after adding polyether block polyamide appears as a mist of insoluble matter in water at a temperature of 30±1℃, the temperature is lowered to 25~40℃ to obtain the triamine resin.

[0015] More preferably, in step S1, the heating temperature is 75~85℃; and / or, the temperature of the heat preservation reaction is 90~100℃, and the heat preservation reaction time is 0.5~1.5h.

[0016] More preferably, the water-to-solubility ratio is 1:2.5. This water-to-solubility ratio is the mass ratio of the reaction solution to water.

[0017] According to a second aspect of the present invention, a method for preparing impregnated paper as described in the first aspect of the present invention is provided, comprising the following steps: S1: The substrate paper is impregnated with urea-formaldehyde resin and dried to form a urea-formaldehyde resin layer. S2: The top coating is performed using modified melamine resin, and the back coating is performed using a resin composition containing maleic anhydride-grafted polyolefin elastomer and modified melamine resin. After drying, the impregnated film paper is obtained.

[0018] Preferably, the amount of adhesive applied in step S1 is 150±10g / m 2 ; And / or, the amount of adhesive applied to the surface in step S2 is 50±5 g / m². 2 ; And / or, the amount of adhesive applied to the back coating in step S2 is 50±5 g / m 2 .

[0019] It should be noted that the amount of adhesive applied in step S1 refers to the total amount of adhesive applied to both sides of the substrate paper.

[0020] Preferably, the drying in step S1 is a three-stage drying process, with the temperatures set sequentially to 120±3℃, 140±3℃ and 135±3℃; And / or, the drying in step S2 is a four-stage drying process, with the temperatures set sequentially to 150±3℃, 160±3℃, 160±3℃ and 145±3℃.

[0021] Preferably, the basis weight of the substrate paper is 70~100 g / m². 2 .

[0022] Preferably, the volatile matter content of the impregnated film paper is 6.5% ± 0.2%.

[0023] Preferably, the pre-curing degree of the impregnated film paper is 50% ± 4%.

[0024] According to a third aspect of the present invention, an impregnated paper prepared by the method described in the first aspect of the present invention or the preparation method described in the second aspect of the present invention is proposed for use in furniture manufacturing or interior decoration.

[0025] According to one embodiment of the present invention, at least the following beneficial effects are achieved: (1) In the present invention, polyether block polyamide is added during the synthesis of melamine-formaldehyde resin. Long molecular chains are grafted into melamine-formaldehyde resin, which reduces the rigidity of melamine after curing without changing other properties.

[0026] (2) In this invention, maleic anhydride-grafted polyolefin elastomer is added to the back coating resin of melamine paper. The elastomer contains active maleic anhydride groups, which can react chemically with melamine resin to enhance compatibility and interfacial bonding, improve the elasticity of melamine resin, thereby reducing the local stress generated by the formaldehyde-free board and playing a buffering role. Attached Figure Description

[0027] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein: Figure 1 This is a flowchart illustrating the preparation process of the energy-absorbing and shock-resistant melamine-impregnated adhesive film paper of Example 1 of the present invention. Detailed Implementation

[0028] The following will describe the concept and technical effects of the present invention clearly and completely with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention.

[0029] Unless otherwise specified, the raw materials, reagents, or apparatus used in the following examples and comparative examples can be obtained from conventional commercial sources or by existing known methods. The polyether block polyamide is Arkema's PEBAX 4533SA 01 MED, with a polyamide hard segment: polyether soft segment ratio of 1:2; the maleic anhydride grafted polyolefin elastomer is BLOC MPO from Platinum Fiber (Hangzhou) New Materials Co., Ltd.; curing agent 1010, release agent 856, penetrant 14, and dust remover 306 were all purchased from Shanghai Hongyi International Trading Co., Ltd.

[0030] Example 1 This embodiment provides a method for preparing impregnated adhesive film paper, including the following steps: (1) Preparation of crack-resistant triamine resin 20 parts of melamine and 32 parts of 37% formaldehyde solution were added to a reaction vessel, and the temperature was raised to 80℃. After the melamine was completely dissolved, 1 part of caprolactam and 1 part of diethylene glycol were added, and the temperature was raised to 95℃ for a sustained reaction. The pH was adjusted to approximately 9.0, and the reaction was maintained for 1 hour. The water solubility ratio of the resin (1:2.5) was then tested. When the resin showed a mist-like insoluble substance in water at 0℃, 1.5 parts of polyether block polyamide with a molecular weight of 20,000 were added to graft the polyether block polyamide into the melamine resin. When the resin showed a mist-like insoluble substance in water at 25℃, the temperature was lowered to 40℃ to obtain the crack-resistant melamine resin. The test results and physicochemical performance requirements are shown in Table 1 below.

[0031] Table 1. Physical and chemical properties requirements of melamine resin resistant to tortoise shells for energy-absorbing and shock-resistant impregnated paper.

[0032] (2) Introducing energy-absorbing and shock-resistant materials by backing the impregnated paper film. The prepared crack-resistant triamine resin was prepared by mixing a curing agent, a release agent, a penetrant, a dust remover, and a maleic anhydride-grafted polyolefin elastomer into the crack-resistant triamine resin. The components were then mixed thoroughly. The component ratios are as follows: 100 parts of crack-resistant melamine resin 0.3 parts curing agent 0.1 parts release agent 0.2 parts of penetrant 0.1 parts dust collector 8 parts of maleic anhydride-grafted polyolefin elastomer (3) Preparation of energy-absorbing and shock-resistant melamine-impregnated paper Using a weight of 80g / m 2 The printing paper undergoes a single impregnation treatment, impregnating it with 150g / m² of low-formaldehyde urea-formaldehyde resin (U / F=1.15). 2The wet adhesive was pre-treated by drying in a three-stage oven at temperatures of 120℃, 140℃, and 135℃. Then, a 50g / m² layer of crack-resistant melamine adhesive was simultaneously applied to the surface. 2 Wet adhesive amount: 50g / m² of crack-resistant melamine adhesive with maleic anhydride grafted polyolefin elastomer added to the back coating. 2 Wet adhesive amount. Drying was performed in a four-stage oven at temperatures of 150℃, 160℃, 160℃, and 145℃. The final product was an energy-absorbing and shock-resistant melamine-impregnated paper with a volatile content of 6.5% and a pre-curing degree of 50%.

[0033] Comparative Example 1 This comparative example provides a melamine-impregnated film paper, which differs from Example 1 in that the crack-resistant melamine resin formulation does not contain polyether block polyamide, but contains 10 wt% acrylic acid.

[0034] Comparative Example 2 This comparative example provides a melamine-impregnated film paper, which differs from Example 1 in that the amount of polyether block polyamide added during the preparation of the crack-resistant melamine resin is 5 parts.

[0035] Test case The test results and physicochemical properties of the melamine-impregnated films of Examples 1 and Comparative Examples 1-2 are shown in Table 2 below.

[0036] Table 2. Physical and chemical property requirements for energy-absorbing and shock-resistant melamine-impregnated paper.

[0037] It is evident that the melamine-impregnated film paper proposed in this invention has excellent wear resistance, scratch resistance, crack resistance, and resistance to thermal cycling. Comparative Example 1, which uses acrylic acid modification, has relatively low wear resistance and scratch resistance. Furthermore, the addition of excessive polyether block polyamide in Comparative Example 2 also leads to a decrease in scratch resistance.

[0038] The embodiments of the present invention have been described in detail above with reference to the tables. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. An impregnated gummed paper, characterized by, A back-coating resin layer, a urea-formaldehyde resin layer, a base paper, a urea-formaldehyde resin layer and a face-coating resin layer are sequentially arranged; The face-coating resin layer comprises a modified triamine resin; The back-coating resin layer comprises the following raw materials: a modified triamine resin, a curing agent, a release agent, a penetrating agent, a dust removal agent and a maleic anhydride grafted polyolefin elastomer; The modified triamine resin comprises the following raw materials: melamine, formaldehyde solution, caprolactam, diethylene glycol and polyether block polyamide.

2. The impregnated film paper of claim 1, wherein The modified triamine resin comprises the following raw materials by mass fraction: melamine 18-22 parts, formaldehyde solution 30-35 parts, caprolactam 0.5-2 parts, diethylene glycol 0.5-2 parts and polyether block polyamide 0.5-3.5 parts.

3. The impregnated film paper of claim 2, wherein, The mass percentage concentration of the formaldehyde solution is 35%-40%; and / or the molecular weight of the polyether block polyamide is 1000-50000.

4. The impregnated paper of claim 1, wherein The back-coating resin layer comprises the following components by weight fraction: modified triamine resin 100 parts, curing agent 0.2-0.4 parts, release agent 0.05-0.2 parts, penetrating agent 0.1-0.3 parts, dust removal agent 0.1-0.3 parts and maleic anhydride grafted polyolefin elastomer 6-10 parts.

5. The impregnated paper of claim 1, wherein The modified triamine resin is made by a preparation method comprising the following steps: (1) heating melamine and formaldehyde solution, adding caprolactam and diethylene glycol after the melamine is completely dissolved, adjusting pH to 8.5-10.5 and then keeping the reaction; (2) determining the water-soluble ratio, adding polyether block polyamide to the reaction solution when fog-like insoluble substances appear in the reaction solution at a water temperature of 0±1℃, and continuing the reaction; (3) when fog-like insoluble substances appear in the reaction solution after adding polyether block polyamide at a water temperature of 30±1℃, cooling to 25-40℃ to obtain the triamine resin.

6. The impregnated gummed paper of claim 5, wherein, In step S1, the heating temperature is 75-85℃; and / or the temperature of the keeping reaction is 90-100℃, and the time of the keeping reaction is 0.5-1.5h.

7. A process for the production of impregnated film paper as claimed in any one of claims 1 to 6, characterized in that, comprising the following steps: S1: impregnating the base paper with urea-formaldehyde resin, and drying to form a urea-formaldehyde resin layer; S2: face-coating with modified triamine resin, and back-coating with a resin composition containing maleic anhydride grafted polyolefin elastomer and modified triamine resin, and drying to obtain the impregnated film paper.

8. The preparation method according to claim 7, characterized in that, The amount of sizing in step S1 is 150 ± 10 g / m 2 ; And / or, the amount of glue applied in step S2 is 50 ± 5 g / m 2 ; And / or, the amount of the back-coating glue in step S2 is 50±5 g / m 2 .

9. The preparation method according to claim 7, characterized in that, The drying in step S1 is three-stage drying, and the temperatures are sequentially set to 120±3℃, 140±3℃ and 135±3℃; And / or, the drying in step S2 is four-stage drying, and the temperatures are sequentially set to 150±3℃, 160±3℃, 160±3℃ and 145±3℃.

10. Use of the impregnated film paper of any one of claims 1-6 or the impregnated film paper prepared by the preparation method of any one of claims 7-9 in furniture manufacturing or interior decoration.

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