Corrosion-resistant impregnated paper and method of making same

Abstract

The present application relates to the technical field of impregnated paper, and particularly relates to a kind of corrosion-resistant impregnated glue film paper and its preparation method.The impregnated glue film paper includes printing paper, the outer surface of the printing paper is provided with protective film layer coated, the protective film layer is prepared by impregnated glue, and the impregnated glue includes the following raw materials by weight: polyurethane emulsion 80-90 parts, epoxy acrylate resin 12-18 parts, PVDF emulsion 5-9 parts, modified nano filler 10-18 parts, silane coupling agent 2-5 parts, hydroxyethyl cellulose 4-7 parts, film forming additive 2-4 parts, defoaming agent 0.1-0.3 parts, and water 20-35 parts.The impregnated glue film paper has better corrosion resistance, water vapor resistance and surface cracking resistance, and has good adhesive strength with artificial board body, and long service life.The preparation method of the corrosion-resistant impregnated glue film paper is simple, easy to control, and convenient for industrial production.

Description

Technical Field

[0001] This invention relates to the field of impregnated paper technology, specifically to a corrosion-resistant impregnated adhesive film paper and its preparation method. Background Technology

[0002] Impregnated paper is made by impregnating base paper, usually printed with text or patterns, into an impregnating adhesive solution. After drying, a protective film forms on the surface of the base paper, protecting it and improving its durability, decorative properties, and adhesion. This makes it suitable for use as a veneer in products such as cabinets, wardrobes, and engineered wood flooring. However, existing impregnated papers often use melamine impregnating solutions. While these papers have excellent performance, they easily release formaldehyde during use, negatively impacting people's lives. Therefore, environmental friendliness and formaldehyde-free impregnated paper have become future development trends. However, existing melamine impregnation methods often suffer from poor corrosion resistance, water vapor resistance, and adhesion, limiting their application. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies of the existing technology, the purpose of this invention is to provide a corrosion-resistant impregnated adhesive film paper and its preparation method. The impregnated adhesive film paper has better corrosion resistance, water vapor resistance and surface crack resistance, long service life and environmental friendliness. The preparation method of the corrosion-resistant impregnated adhesive film paper is simple, easy to operate and convenient for industrial production.

[0004] The objective of this invention is achieved through the following technical solution: a corrosion-resistant impregnated adhesive film paper, comprising printing paper, wherein the outer surface of the printing paper is coated with a protective adhesive film layer, the protective adhesive film layer being prepared by impregnation adhesive, the impregnation adhesive comprising the following raw materials in parts by weight: 80-90 parts of polyurethane emulsion, 12-18 parts of epoxy acrylic resin, 5-9 parts of PVDF emulsion, 10-18 parts of modified nanofiller, 2-5 parts of silane coupling agent, 4-7 parts of hydroxyethyl cellulose, 2-4 parts of film-forming aid, 0.1-0.3 parts of defoamer, and 20-35 parts of water.

[0005] The present invention provides a method for preparing a corrosion-resistant impregnated adhesive film paper, comprising the following steps:

[0006] S1. Take 80-90 parts by weight of polyurethane emulsion, 12-18 parts of epoxy acrylic resin, 5-9 parts of PVDF emulsion, 9-17 parts of modified nanofiller, 2-5 parts of silane coupling agent and 20-35 parts of water, mix and heat and stir continuously to obtain mixture I after reaction.

[0007] S2. Add 4-7 parts of hydroxyethyl cellulose, 2-4 parts of film-forming aid, and 0.1-0.3 parts of defoamer to mixture I, stir evenly, and cool to obtain the impregnation solution;

[0008] S3. The printing paper is impregnated in the impregnation solution and then dried to obtain a corrosion-resistant impregnation solution film paper.

[0009] This invention involves compounding and optimizing the proportions of polyurethane emulsion, epoxy acrylate resin, modified nanofillers, hydroxyethyl cellulose, and silane coupling agents to prepare an impregnating adhesive. The impregnated paper film prepared using this adhesive exhibits excellent corrosion resistance, water vapor resistance, and surface crack resistance, and shows good adhesion to artificial decorative panels.

[0010] Furthermore, in step S1, the silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

[0011] Further, in step S1, the preparation method of the modified nanofiller includes the following steps: 50-70 parts of dimethyl sulfoxide and 5-10 parts of methanol are mixed evenly, then 6-10 parts of nano-kaolin powder and 4-8 parts of nano-zinc oxide are added to form a suspension; the suspension is stirred at 62-70℃ for 2-3 hours, then ultrasonically dispersed for 3-4 hours; finally, the suspension is filtered, dried, and ground to obtain the modified nanofiller. The particle size of the nano-kaolin powder is 60-100 nm, and the particle size of the nano-zinc oxide is 50-80 nm.

[0012] This invention modifies nano-kaolin powder and nano-zinc oxide in advance using the above method, and then mixes them with raw materials such as polyurethane emulsion and PVDF emulsion. This process enhances and toughens the final protective film layer and helps improve its heat resistance.

[0013] Furthermore, in step S1, the reaction temperature is 65-72℃ and the reaction time is 30-60min.

[0014] Furthermore, in step S2, the defoamer is at least one of silicone defoamer, polyether defoamer, and phosphate ester defoamer.

[0015] Furthermore, in step S2, the film-forming aid is at least one of ethylene glycol tert-butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

[0016] Furthermore, in step S2, hydroxyethyl cellulose, film-forming aid and defoamer are added to mixture I, stirred for 20-40 minutes, and cooled to 30-35°C to obtain impregnation solution;

[0017] Furthermore, in step S3, the printing paper is placed in the impregnation solution for complete impregnation, with an impregnation amount of 120-180 g / m². 2Dry at 105-115℃ for 3-5 minutes to obtain corrosion-resistant impregnated paper.

[0018] The beneficial effects of this invention are as follows: This invention prepares an impregnating solution by compounding and optimizing the proportions of raw materials such as polyurethane emulsion, epoxy acrylic resin, modified nanofiller, silane coupling agent, hydroxyethyl cellulose, and silane coupling agent. The impregnated paper prepared using the above-mentioned impregnating solution has excellent corrosion resistance, water vapor resistance, and surface crack resistance, and has good adhesion strength to artificial boards, resulting in a long service life. The preparation method of the corrosion-resistant impregnated paper is simple, easy to operate, and convenient for industrial production. Detailed Implementation

[0019] To facilitate understanding by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1

[0021] In this embodiment, a corrosion-resistant impregnated adhesive film paper includes printing paper. The outer surface of the printing paper is coated with a protective adhesive film layer. This protective adhesive film layer is prepared using an impregnating adhesive, which comprises the following raw materials in parts by weight: 85 parts polyurethane emulsion, 16 parts epoxy acrylate resin, 7 parts PVDF emulsion, 14 parts modified nanofiller, 3 parts silane coupling agent, 5 parts hydroxyethyl cellulose, 3 parts film-forming aid, 0.2 parts defoamer, and 25 parts water. The polyurethane emulsion used is Covestro Dispercoll U XP2643 polyurethane emulsion. The epoxy acrylate resin used is epoxy acrylate resin L-6114. The PVDF emulsion used is Arkema PVDF 2850-00.

[0022] The method for preparing the corrosion-resistant impregnated adhesive film paper in this embodiment includes the following steps:

[0023] S1. Take polyurethane emulsion, epoxy acrylic resin, PVDF emulsion, modified nanofiller, silane coupling agent and water in proportion, mix and heat and stir continuously to obtain mixture I after reaction;

[0024] S2. Add hydroxyethyl cellulose, film-forming aid, and defoamer to mixture I, stir evenly, and cool to obtain impregnation solution;

[0025] S3. The printing paper is impregnated in the impregnation solution and then dried to obtain a corrosion-resistant impregnation solution film paper.

[0026] Furthermore, in step S1, the silane coupling agent is composed of vinyltrimethoxysilane and γ-(methacryloyloxy)propyltrimethoxysilane in a mass ratio of 1:1.

[0027] Further, in step S1, the preparation method of the modified nanofiller includes the following steps: 60 parts of dimethyl sulfoxide and 8 parts of methanol are mixed evenly, then 8 parts of nano-kaolin powder and 6 parts of nano-zinc oxide are added to form a suspension; the suspension is stirred at 67°C for 2.5 hours, then ultrasonically dispersed for 4 hours; after washing with ethanol, the suspension is filtered, dried, and then ground to obtain the modified nanofiller. The particle size of the nano-kaolin powder is 60-100 nm, and the particle size of the nano-zinc oxide is 50-80 nm.

[0028] Furthermore, in step S1, the reaction temperature is 68°C and the reaction time is 40 min.

[0029] Furthermore, in step S2, the defoamer is BYK-1796 silicone defoamer. The film-forming aid is ethylene glycol tert-butyl ether.

[0030] Furthermore, in step S2, hydroxyethyl cellulose, film-forming aid and defoamer are added to mixture I, stirred for 30 minutes, and then cooled to 35°C to obtain impregnation solution;

[0031] Furthermore, in step S3, the printing paper is placed in the impregnation solution for complete impregnation, with an impregnation amount of 160 g / m². 2 The paper is dried at 110℃ for 4 minutes to obtain a corrosion-resistant impregnated adhesive film.

[0032] Example 2

[0033] In this embodiment, a corrosion-resistant impregnated adhesive film paper includes printing paper, the outer surface of which is coated with a protective adhesive film layer. The protective adhesive film layer is prepared by impregnating adhesive, which includes the following raw materials in parts by weight: 80 parts of polyurethane emulsion, 12 parts of epoxy acrylic resin, 5 parts of PVDF emulsion, 11 parts of modified nanofiller, 2 parts of silane coupling agent, 4 parts of hydroxyethyl cellulose, 2 parts of film-forming aid, 0.1 parts of defoamer, and 24 parts of water.

[0034] The method for preparing the corrosion-resistant impregnated adhesive film paper in this embodiment includes the following steps:

[0035] S1. Take polyurethane emulsion, epoxy acrylic resin, PVDF emulsion, modified nanofiller, silane coupling agent and water in proportion, mix and heat and stir continuously to obtain mixture I after reaction;

[0036] S2. Add hydroxyethyl cellulose, film-forming aid, and defoamer to mixture I, stir evenly, and cool to obtain impregnation solution;

[0037] S3. The printing paper is impregnated in the impregnation solution and then dried to obtain a corrosion-resistant impregnation solution film paper.

[0038] Furthermore, in step S1, the silane coupling agent is vinyltriethoxysilane.

[0039] Furthermore, the preparation method of the modified nanofiller includes the following steps: after mixing 50 parts of dimethyl sulfoxide and 6 parts of methanol evenly, 7 parts of nano-kaolin powder and 4 parts of nano-zinc oxide are added to form a suspension; the suspension is stirred at 62°C for 3 hours and then ultrasonically dispersed for 3 hours; after washing with ethanol, the suspension is filtered, dried, and then ground and pulverized to obtain the modified nanofiller.

[0040] Furthermore, in step S1, the reaction temperature is 65°C and the reaction time is 60 min.

[0041] Furthermore, in step S2, the defoamer is the polyether-based aqueous defoamer Rhodoline DF4226. The film-forming aid is dipropylene glycol butyl ether.

[0042] Furthermore, in step S2, hydroxyethyl cellulose, film-forming aid and defoamer are added to mixture I, stirred for 30 minutes, and then cooled to 30°C to obtain impregnation solution;

[0043] Furthermore, in step S3, the printing paper is placed in the impregnation solution for complete impregnation, with an impregnation amount of 120 g / m². 2 Dry at 105℃ for 3 minutes to obtain corrosion-resistant impregnated adhesive film paper.

[0044] The rest of this embodiment is the same as that in Embodiment 1.

[0045] Example 3

[0046] In this embodiment, a corrosion-resistant impregnated adhesive film paper includes printing paper, the outer surface of which is coated with a protective adhesive film layer. The protective adhesive film layer is prepared by impregnating adhesive, which includes the following raw materials in parts by weight: 90 parts of polyurethane emulsion, 18 parts of epoxy acrylic resin, 9 parts of PVDF emulsion, 18 parts of modified nanofiller, 5 parts of silane coupling agent, 7 parts of hydroxyethyl cellulose, 4 parts of film-forming aid, 0.3 parts of defoamer, and 35 parts of water.

[0047] The method for preparing the corrosion-resistant impregnated adhesive film paper in this embodiment includes the following steps:

[0048] S1. Take polyurethane emulsion, epoxy acrylic resin, PVDF emulsion, modified nanofiller, silane coupling agent and water in proportion, mix and heat and stir continuously to obtain mixture I after reaction;

[0049] S2. Add hydroxyethyl cellulose, film-forming aid, and defoamer to mixture I, stir evenly, and cool to obtain impregnation solution;

[0050] S3. The printing paper is impregnated in the impregnation solution and then dried to obtain a corrosion-resistant impregnation solution film paper.

[0051] Furthermore, in step S1, the silane coupling agent is vinyltrimethoxysilane.

[0052] Furthermore, in step S1, the preparation method of the modified nanofiller includes the following steps: 70 parts of dimethyl sulfoxide and 10 parts of methanol are mixed evenly, then 10 parts of nano-kaolin powder and 8 parts of nano-zinc oxide are added to form a suspension; the suspension is stirred at 70°C for 3 hours, then ultrasonically dispersed for 3 hours; then washed with ethanol, filtered, dried, and ground to obtain the modified nanofiller.

[0053] Furthermore, in step S1, the reaction temperature is 72°C and the reaction time is 30 min.

[0054] Furthermore, in step S2, hydroxyethyl cellulose, film-forming aid and defoamer are added to mixture I, stirred for 40 minutes, and then cooled to 30°C to obtain impregnation solution;

[0055] Furthermore, in step S3, the printing paper is placed in the impregnation solution for complete impregnation, with an impregnation amount of 180 g / m². 2 The paper is dried at 115℃ for 4 minutes to obtain a corrosion-resistant impregnated adhesive film.

[0056] The rest of this embodiment is the same as that in Embodiment 1.

[0057] Example 4

[0058] In this embodiment, a corrosion-resistant impregnated adhesive film paper includes printing paper. The outer surface of the printing paper is coated with a protective adhesive film layer. This protective adhesive film layer is prepared using an impregnating adhesive, which comprises the following raw materials in parts by weight: 88 parts polyurethane emulsion, 15 parts epoxy acrylic resin, 6 parts PVDF emulsion, 13 parts modified nanofiller, 4 parts silane coupling agent, 6 parts hydroxyethyl cellulose, 3 parts film-forming aid, 0.2 parts defoamer, and 30 parts water. The remainder of this embodiment is the same as in Embodiment 1.

[0059] Example 5

[0060] In this embodiment, the preparation method of the modified nanofiller in step (1) includes the following steps: 55 parts of dimethyl sulfoxide and 7 parts of methanol are mixed evenly, then 7 parts of nano-kaolin powder and 5 parts of nano-zinc oxide are added to form a suspension; the suspension is stirred at 65°C for 2.5 hours, then ultrasonically dispersed for 3.5 hours; then washed with ethanol, filtered, dried, and ground to obtain the modified nanofiller. The rest of this embodiment is the same as in embodiment 1.

[0061] Comparative Example 1

[0062] The difference between this comparative example and Example 1 is that an equal amount of polyurethane emulsion is used to replace the PVDF emulsion in Example 1.

[0063] Comparative Example 2

[0064] The difference between this comparative example and Example 1 is that an equal amount of unmodified nano-kaolin powder and nano-zinc oxide mixture is used to replace the modified nanofiller in Example 1. The mass ratio of nano-kaolin powder and nano-zinc oxide in this comparative example is the same as the mass ratio of nano-kaolin powder and nano-zinc oxide added during the preparation of the modified nanofiller.

[0065] Application examples

[0066] The impregnated paper from Example 1 and Comparative Examples 1-2 was hot-pressed onto a fiberboard for 2 minutes on one side under a pressure of 5 MPa and a temperature of 165°C. The fiberboard was used as the printing paper, and the printing paper had a basis weight of 70 g / m³. 2 Decorative paper is used to make decorative engineered wood panels, the density of which is 0.7-0.75 g / cm³. 3 The impregnation amount of the impregnated paper in Example 1 and Comparative Examples 1-2 was 160±5 g / m². 3 .

[0067] According to GB / T 28995-2012, the formaldehyde release and glue application amount of the corrosion-resistant impregnated paper were tested, and the appearance quality of the corrosion-resistant impregnated paper was observed. It can be seen that the surface of the corrosion-resistant impregnated paper in Example 1 and Comparative Examples 1-3 is free from damage, stains, gaps, etc., and the appearance quality of the products meets the standard of GB / T 28995-2012. The formaldehyde release of the corrosion-resistant impregnated paper is 0 mg / L.

[0068] The surface bonding strength, surface resistance to staining and corrosion (pattern), surface resistance to water vapor, surface scratch resistance (≥1.5N, no more than 90% of the surface is scratched), surface crack resistance, and surface resistance to thermal cycling of the decorative wood-based panels were determined according to GB / T15102-2017 / GBT17657-2022. The surface resistance to staining and corrosion was determined according to Method 1, Section 4.40 of GB / T17657-2013. The test results are shown in the table below:

[0069]

[0070] As shown in the table above, applying the corrosion-resistant impregnated adhesive film paper prepared by this invention to decorative artificial boards can give the decorative artificial boards better corrosion resistance, surface crack resistance and surface water vapor resistance, high surface bonding strength, long service life, and can reduce formaldehyde release, making them environmentally friendly.

[0071] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A method for preparing a corrosion-resistant impregnated adhesive film paper, characterized in that: Includes the following steps: S1. Take 80-90 parts by weight of polyurethane emulsion, 12-18 parts of epoxy acrylic resin, 5-9 parts of PVDF emulsion, 10-18 parts of modified nanofiller, 2-5 parts of silane coupling agent and 20-35 parts of water, mix and heat and stir continuously, react at a reaction temperature of 65-72℃ for 30-60 minutes, and obtain mixture I after the reaction. S2. Add 4-7 parts of hydroxyethyl cellulose, 2-4 parts of film-forming aid, and 0.1-0.3 parts of defoamer to mixture I, stir evenly, and cool to obtain the impregnation solution; S3. Place the printing paper in the impregnation solution for complete impregnation, with an impregnation amount of 120-180 g / m². 2 Then it is dried to obtain a corrosion-resistant impregnated paper film. In step S1, the preparation method of the modified nanofiller includes the following steps: 50-70 parts of dimethyl sulfoxide and 5-10 parts of methanol are mixed evenly, 6-10 parts of nano-kaolin powder and 4-8 parts of nano-zinc oxide are added to form a suspension, the suspension is stirred at 62-70℃ for 2-3 hours, and then ultrasonically dispersed for 3-4 hours; then filtered, dried, and ground to obtain the modified nanofiller.

2. The method for preparing corrosion-resistant impregnated adhesive film paper according to claim 1, characterized in that: In step S1, the silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

3. The method for preparing corrosion-resistant impregnated adhesive film paper according to claim 1, characterized in that: In step S2, the defoamer is at least one of silicone defoamer, polyether defoamer, and phosphate ester defoamer.

4. The method for preparing corrosion-resistant impregnated adhesive film paper according to claim 1, characterized in that: In step S2, the film-forming aid is at least one of ethylene glycol tert-butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

5. The method for preparing corrosion-resistant impregnated adhesive film paper according to claim 1, characterized in that: In step S2, hydroxyethyl cellulose, film-forming aid and defoamer are added to mixture I, stirred for 20-40 minutes, and then cooled to 30-35℃ to obtain the impregnation solution.

6. The method for preparing corrosion-resistant impregnated adhesive film paper according to claim 1, characterized in that: In step S3, the drying temperature is 105-115℃ and the drying time is 3-5 minutes.

7. A corrosion-resistant impregnated adhesive film paper, characterized in that: The paper includes printing paper, the outer surface of which is covered with a protective adhesive film layer, which is prepared by impregnation with an adhesive solution; The corrosion-resistant impregnated adhesive film paper is prepared by the method described in claim 1.

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