Paper deplasticization production process based on nano deplasticizing oil

Abstract

The application discloses a paper plastic removal production process based on nano plastic removal oil and belongs to the technical field of functional coating. The process comprises the following steps: first, printing ink is printed on the surface of paper, and then nano plastic removal oil is coated on the surface of the printing ink; second, the paper coated with the nano plastic removal oil is pre-solidified through 395 and 365nm LED UV light sources; third, the pre-solidified coating is irradiated by a 172nm UV lamp to form a matte coating with tiny folds with a thickness of dozens to hundreds of nanometers; fourth, after deep UV mercury lamp photocuring and air cooling, the paper is collected; after the nano plastic removal oil is coated on the surface of the paper by the process, the printed paper can have excellent wear resistance, folding resistance, anti-burst color, waterproofness and antibacterial and mildew resistance.

Description

Technical Field

[0001] This invention relates to the field of functional coating technology, and more specifically to a paper deplasticizing process based on nano-deplasticizing oil. Background Technology

[0002] The existing lamination process involves printing ink on a paper substrate and then laminating it with PET or BOPP film using adhesive. However, because the film is not easily degradable and the paper and plastic film cannot be separated after lamination, the laminated paper cannot be recycled or degraded, resulting in resource waste and a significant environmental burden.

[0003] Plastic-removing varnishes were developed to replace traditional plastic films in printing technology. When applied to paper, they achieve a laminating effect, offering advantages such as good ink adhesion, abrasion resistance, folding resistance, explosion-proof properties, scratch resistance, matte finish, and ink protection. Simultaneously, they are biodegradable and recyclable, thus achieving the environmental goal of replacing plastic. The use of plastic-removing varnishes to replace traditional plastic films in the printing industry promotes sustainable development and is an inevitable trend. Therefore, plastic-removing varnishes have significant commercial and social value, making them a product worthy of serious research and development by major chemical companies and investors.

[0004] Currently, there are two main types of plastic removal coatings on the market: water-based plastic removal oils and transfer coating (transfer film) processes. Water-based plastic removal oils are widely recognized and used by most manufacturers due to their environmental friendliness, but their performance in terms of wear resistance, folding resistance, explosion-proof color, and scratch resistance still needs improvement, and currently they can only be used in a downgraded manner according to customer requirements. The transfer coating plastic removal process involves transferring the UV coating applied to PET or PP film onto the printed sheet using adhesive to achieve the purpose of wear resistance, folding resistance, explosion-proof color, and scratch resistance. This process has better performance than water-based plastic removal oils, but because it still uses plastic film in the production process, it does not achieve the purpose of plastic removal.

[0005] The oligomers used in UV-curable coatings are mostly linear polymers. Their high viscosity makes coating difficult and affects coating performance. Therefore, a large amount of reactive diluent needs to be added. However, the addition of a large amount of reactive diluent will lead to defects such as reduced yellowing resistance, increased coating volume shrinkage, and reduced adhesion. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a paper deplasticizing process based on nano-deplasticizing oil.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A paper deplasticizing process based on nano-plasticizer includes the following steps:

[0009] The first step is to print ink on the paper surface, and then coat the ink surface with nano plastic remover.

[0010] The second step is to pre-cur the paper coated with nano-plastic remover using 395nm and 365nm LED UV light sources.

[0011] The third step involves irradiating the pre-cured coating with a 172nm UV lamp to form a matte coating with tiny wrinkles that are tens to hundreds of nanometers thick.

[0012] The fourth step involves deep curing with a UV mercury lamp, followed by air cooling and paper collection.

[0013] The nano-plastic remover comprises the following raw materials in parts by weight: 35-60 parts modified polyurethane acrylate, 10-30 parts modified polyester acrylate, 15-20 parts active monomer, 2-5 parts photoinitiator, and 1-8 parts additives.

[0014] The nano-plastic remover is prepared by the following steps: mixing the raw materials and stirring evenly at 50°C to obtain the nano-plastic remover.

[0015] The modified polyurethane acrylate is prepared by the following steps:

[0016] Polytetrahydrofuran diol was added to a three-necked flask containing acetone. The mixture was stirred at room temperature for 30 minutes, then nitrogen gas was introduced. The temperature was raised to 50-60°C, and isophorone diisocyanate and dibutyltin dilaurate were added. The mixture was kept at this temperature and stirred at a constant speed for 2 hours to obtain a prepolymer. Pentaerythritol was then added to the reaction system, followed by the addition of functional monomers under a nitrogen atmosphere at 60°C. The system temperature was maintained at 55-60°C, and the reaction was continued for 2 hours. After the reaction was completed, acetone was removed by rotary evaporation. Modified polyurethane acrylate was prepared, wherein the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on polytetrahydrofuran diol was 1.1-1.2:1, the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on pentaerythritol was 4-4.5:1, the amount of dibutyltin dilaurate was 0.1-0.2% of the weight of isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to functional monomers was 1:1.

[0017] Furthermore, the functional unit is manufactured through the following steps:

[0018] Step S1: Add 4-n-dodecylbenzaldehyde and p-aminobenzoylhydrazine to acetonitrile, add glacial acetic acid, heat to 80-85℃ under nitrogen atmosphere, maintain the temperature and react for 24h. After the reaction is completed, filter to obtain crude product, wash three times with isopropanol to obtain intermediate 1. Control the ratio of 4-n-dodecylbenzaldehyde, p-aminobenzoylhydrazine, glacial acetic acid and acetonitrile to be 10-15mmol:10-15mmol:0.02-0.03mL:150mL.

[0019] In step S1, 4-dodecylbenzaldehyde reacts with a primary amine on p-aminobenzoyl hydrazine to prepare intermediate 1. Intermediate 1 has a Schiff base structure with a hydrophobic long chain. When incorporated into the matrix structure, it can endow the matrix with excellent waterproof and antifungal properties.

[0020] Step S2: Add the obtained intermediate 1 and triethylamine to N-methylpyrrolidone, add methacryloyl chloride under a nitrogen atmosphere, heat to 45-50℃, stir at a constant speed and react for 12h. After the reaction is completed, the functional monomer is obtained. The ratio of intermediate 1, methacryloyl chloride, triethylamine and N-methylpyrrolidone is controlled to be 10-12mmol:10-12mmol:1.5-1.8mL:50-75mL.

[0021] In step S2, the remaining primary amino group in intermediate 1 can react with methacryloyl chloride to introduce a carbon-carbon double bond, thus obtaining a functional monomer.

[0022] Furthermore, the modified polyester acrylate is EBECREL 547.

[0023] Furthermore, the active monomer is one or more of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, and acryloylmorpholine mixed in any proportion.

[0024] Furthermore, the photoinitiator is one or more of photoinitiator 184, photoinitiator 1173 and photoinitiator 2959 mixed in any proportion.

[0025] Furthermore, the additive is a mixture of a leveling agent and an adhesion promoter in a 1:1 weight ratio.

[0026] The beneficial effects of this invention are:

[0027] This invention produces a nano-plastic remover. When applied to the surface of paper using this process, the nano-plastic remover provides excellent abrasion resistance, folding resistance, anti-explosion properties, water resistance, and antibacterial and antifungal properties. The nano-plastic remover uses modified polyurethane acrylate and modified polyester acrylate as the matrix. During the preparation process, the modified polyurethane acrylate undergoes chain extension through polyol to form a hyperbranched polyurethane acrylate structure. This prevents the traditional linear acrylate structure from causing difficulties in coating due to its high viscosity, which affects coating performance and necessitates the addition of a large amount of reactive diluent, leading to yellowing and poor adhesion of the coating. Furthermore, this invention introduces functional monomers. Through the Schiff base structure with hydrophobic long chains on the functional monomers, the coating can be endowed with excellent waterproof, antifungal, and antibacterial properties. Detailed Implementation

[0028] 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.

[0029] Example 1: A paper deplasticizing process based on nano-plasticizer, comprising the following steps:

[0030] The first step is to print ink on the paper surface, and then coat the ink surface with nano plastic remover.

[0031] The second step is to pre-cur the paper coated with nano-plastic remover using 395nm and 365nm LED UV light sources.

[0032] The third step involves irradiating the pre-cured coating with a 172nm UV lamp to form a matte coating with tiny wrinkles that are tens to hundreds of nanometers thick.

[0033] Step 4: After deep curing with a UV mercury lamp, the paper is cooled by air and then collected.

[0034] The nano-plastic remover comprises the following raw materials in parts by weight: 35 parts modified polyurethane acrylate, 10 parts modified polyester acrylate, 15 parts active monomer, 2 parts photoinitiator 184 (Wuhan Camick), and 1 part additive.

[0035] The nano-plastic remover is prepared by the following steps: mixing the raw materials and stirring evenly at 50°C to obtain the nano-plastic remover.

[0036] The modified polyurethane acrylate is prepared by the following steps:

[0037] Polytetrahydrofuran diol was added to a three-necked flask containing acetone. After stirring at room temperature for 30 min, nitrogen gas was introduced, and the temperature was raised to 50°C. Isophorone diisocyanate and dibutyltin dilaurate were added, and the mixture was kept at the same temperature and stirred at a constant speed for 2 h to obtain a prepolymer. Pentaerythritol was then added to the reaction system, and the functional monomer was added under a nitrogen atmosphere at 60°C. The system temperature was maintained at 55°C, and the reaction was continued for 2 h. After the reaction was completed, acetone was removed by rotary evaporation to obtain modified polyurethane acrylate. The molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on polytetrahydrofuran diol was 1.1:1, the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on pentaerythritol was 4:1, the amount of dibutyltin dilaurate was 0.1% of the weight of isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to the functional monomer was 1:1.

[0038] The functional unit is manufactured through the following steps:

[0039] Step S1: Add 4-n-dodecylbenzaldehyde and p-aminobenzoylhydrazine to acetonitrile, add glacial acetic acid, heat to 80°C under nitrogen atmosphere, maintain the temperature and react for 24 h. After the reaction is completed, filter to obtain crude product, wash three times with isopropanol to obtain intermediate 1. Control the ratio of 4-n-dodecylbenzaldehyde, p-aminobenzoylhydrazine, glacial acetic acid and acetonitrile to be 10 mmol: 10 mmol: 0.02 mL: 150 mL.

[0040] Step S2: Add the obtained intermediate 1 and triethylamine to N-methylpyrrolidone, add methacryloyl chloride under a nitrogen atmosphere, heat to 45°C, stir at a constant speed and react for 12 h. After the reaction is completed, the functional monomer is obtained. The ratio of intermediate 1, methacryloyl chloride, triethylamine and N-methylpyrrolidone is controlled to be 10 mmol: 10 mmol: 1.5 mL: 50 mL.

[0041] The modified polyester acrylate is EBECREL 547.

[0042] The active monomer is 1,6-hexanediol diacrylate.

[0043] The additive is a mixture of leveling agent BYK358N and adhesion promoter HY-6030 in a weight ratio of 1:1.

[0044] Example 2: A paper deplasticizing process based on nano-plasticizer, comprising the following steps:

[0045] The first step is to print ink on the paper surface, and then coat the ink surface with nano plastic remover.

[0046] The second step is to pre-cur the paper coated with nano-plastic remover using 395nm and 365nm LED UV light sources.

[0047] The third step involves irradiating the pre-cured coating with a 172nm UV lamp to form a matte coating with tiny wrinkles that are tens to hundreds of nanometers thick.

[0048] Step 4: After deep curing with a UV mercury lamp, the paper is cooled by air and then collected.

[0049] The nano-plastic remover comprises the following raw materials in parts by weight: 50 parts modified polyurethane acrylate, 20 parts modified polyester acrylate, 18 parts active monomer, 4 parts photoinitiator 1173 (Henan Wokas), and 5 parts additives.

[0050] The nano-plastic remover is prepared by the following steps: mixing the raw materials and stirring evenly at 50°C to obtain the nano-plastic remover.

[0051] The modified polyurethane acrylate is prepared by the following steps:

[0052] Polytetrahydrofuran diol was added to a three-necked flask containing acetone. After stirring at room temperature for 30 minutes, nitrogen gas was introduced, and the temperature was raised to 55°C. Isophorone diisocyanate and dibutyltin dilaurate were added, and the mixture was kept at the same temperature and stirred at a constant speed for 2 hours to obtain a prepolymer. Pentaerythritol was then added to the reaction system, and the functional monomer was added under a nitrogen atmosphere at 60°C. The system temperature was maintained at 60°C, and the reaction was continued for 2 hours. After the reaction was completed, acetone was removed by rotary evaporation to obtain modified polyurethane acrylate. The molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on polytetrahydrofuran diol was 1.2:1, the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on pentaerythritol was 4:1, the amount of dibutyltin dilaurate was 0.1% of the weight of isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to the functional monomer was 1:1.

[0053] The functional unit is manufactured through the following steps:

[0054] Step S1: Add 4-n-dodecylbenzaldehyde and p-aminobenzoylhydrazine to acetonitrile, add glacial acetic acid, heat to 85°C under nitrogen atmosphere, maintain the temperature and react for 24 h. After the reaction is completed, filter to obtain crude product, wash three times with isopropanol to obtain intermediate 1. Control the ratio of 4-n-dodecylbenzaldehyde, p-aminobenzoylhydrazine, glacial acetic acid and acetonitrile to be 12 mmol: 12 mmol: 0.02 mL: 150 mL.

[0055] Step S2: Add the obtained intermediate 1 and triethylamine to N-methylpyrrolidone, add methacryloyl chloride under a nitrogen atmosphere, heat to 50°C, stir at a constant speed and react for 12 h. After the reaction is completed, the functional monomer is obtained. The ratio of intermediate 1, methacryloyl chloride, triethylamine and N-methylpyrrolidone is controlled to be 12 mmol: 12 mmol: 1.6 mL: 65 mL.

[0056] The modified polyester acrylate is EBECREL 547.

[0057] The active monomer is tripropylene glycol diacrylate.

[0058] The additive is a mixture of leveling agent BYK358N and adhesion promoter HY-6030 in a weight ratio of 1:1.

[0059] Example 3: A paper deplasticizing process based on nano-plasticizer, comprising the following steps:

[0060] The first step is to print ink on the paper surface, and then coat the ink surface with nano plastic remover.

[0061] The second step is to pre-cur the paper coated with nano-plastic remover using 395nm and 365nm LED UV light sources.

[0062] The third step involves irradiating the pre-cured coating with a 172nm UV lamp to form a matte coating with tiny wrinkles that are tens to hundreds of nanometers thick.

[0063] Step 4: After deep curing with a UV mercury lamp, the paper is cooled by air and then collected.

[0064] The nano-plastic remover comprises the following raw materials in parts by weight: 60 parts modified polyurethane acrylate, 30 parts modified polyester acrylate, 20 parts active monomer, 5 parts photoinitiator 2959 (Hubei Qiansheng Biotechnology), and 8 parts additives.

[0065] The nano-plastic remover is prepared by the following steps: mixing the raw materials and stirring evenly at 50°C to obtain the nano-plastic remover.

[0066] The modified polyurethane acrylate is prepared by the following steps:

[0067] Polytetrahydrofuran diol was added to a three-necked flask containing acetone. After stirring at room temperature for 30 min, nitrogen gas was introduced, and the temperature was raised to 60°C. Isophorone diisocyanate and dibutyltin dilaurate were added, and the mixture was kept at the same temperature and stirred at a constant speed for 2 h to obtain a prepolymer. Pentaerythritol was then added to the reaction system, and the functional monomer was added under a nitrogen atmosphere at 60°C. The system temperature was maintained at 60°C, and the reaction was continued for 2 h. After the reaction was completed, acetone was removed by rotary evaporation to obtain modified polyurethane acrylate. The molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on polytetrahydrofuran diol was 1.2:1, the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on pentaerythritol was 4.5:1, the amount of dibutyltin dilaurate was 0.2% of the weight of isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to the functional monomer was 1:1.

[0068] The functional unit is manufactured through the following steps:

[0069] Step S1: Add 4-n-dodecylbenzaldehyde and p-aminobenzoylhydrazine to acetonitrile, add glacial acetic acid, heat to 80-85℃ under nitrogen atmosphere, keep warm and react for 24h, filter after reaction to obtain crude product, wash three times with isopropanol to obtain intermediate 1, control the ratio of 4-n-dodecylbenzaldehyde, p-aminobenzoylhydrazine, glacial acetic acid and acetonitrile to be 15mmol:15mmol:0.03mL:150mL;

[0070] Step S2: Add the obtained intermediate 1 and triethylamine to N-methylpyrrolidone, add methacryloyl chloride under a nitrogen atmosphere, heat to 50°C, stir at a constant speed and react for 12 h. After the reaction is completed, the functional monomer is obtained. The ratio of intermediate 1, methacryloyl chloride, triethylamine and N-methylpyrrolidone is controlled to be 12 mmol: 12 mmol: 1.8 mL: 75 mL.

[0071] The modified polyester acrylate is EBECREL 547.

[0072] The active monomer is acryloylmorpholine.

[0073] The additive is a mixture of leveling agent BYK358N and adhesion promoter HY-6030 in a weight ratio of 1:1.

[0074] Comparative Example 1: Compared with Example 1, this comparative example uses commercially available polyurethane-modified acrylate instead of the modified polyurethane acrylate of this application, and the rest is the same as Example 1.

[0075] Comparative Example 2: Compared with Example 1, this comparative example does not introduce a functional monomer, but is otherwise the same as Example 1.

[0076] The paper coated with nano-plastic remover in Examples 1-4 and Comparative Example 1 was tested, and the results are shown in Table 1 below:

[0077] Table 1

[0078]

[0079] Table 2

[0080]

[0081] As can be seen from Table 1 above, the coatings prepared in Examples 1-3 of the present invention not only have excellent adhesion but also have a large contact angle and a certain degree of hydrophobicity. As can be seen from Table 2, Examples 1-3 of the present invention have good antibacterial effects.

[0082] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A process for the production of paper based on nano-deplastifying oil, characterized in that, Includes the following steps: The first step is to print ink on the paper surface, and then coat the ink surface with nano plastic remover. The second step is to pre-cur the paper coated with nano-plastic remover using 395nm and 365nm LED UV light sources. The third step is to irradiate the pre-cured coating with a 172nm UV lamp to form a matte coating. Step 4: After deep curing with a UV mercury lamp, the paper is cooled by air and then collected. The nano-plastic remover comprises the following raw materials in parts by weight: 35-60 parts modified polyurethane acrylate, 10-30 parts modified polyester acrylate, 15-20 parts active monomer, 2-5 parts photoinitiator, and 1-8 parts additives. The modified polyurethane acrylate is prepared by the following steps: Polytetrahydrofuran diol was added to a three-necked flask containing acetone. After stirring at room temperature for 30 minutes, nitrogen gas was introduced, and the temperature was raised to 50-60°C. Isophorone diisocyanate and dibutyltin dilaurate were added, and the mixture was kept at this temperature with constant stirring for 2 hours to obtain a prepolymer. Pentaerythritol was then added to the reaction system, followed by the addition of functional monomers under a nitrogen atmosphere at 60°C. The system temperature was maintained at 55-60°C, and the reaction was continued for 2 hours. After the reaction was completed, the product was obtained by rotary evaporation. The modified polyurethane acrylate is obtained, wherein the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on polytetrahydrofuran diol is 1.1-1.2:1, the molar ratio of isocyanate groups on isophorone diisocyanate to hydroxyl groups on pentaerythritol is 4-4.5:1, the amount of dibutyltin dilaurate is 0.1-0.2% of the weight of isophorone diisocyanate, and the molar ratio of isophorone diisocyanate to functional monomer is 1:1; The functional unit is manufactured through the following steps: Step S1: Add 4-n-dodecylbenzaldehyde and p-aminobenzoylhydrazine to acetonitrile, add glacial acetic acid, heat to 80-85℃ under nitrogen atmosphere, keep warm and react for 24h, filter after reaction to obtain crude product, wash three times with isopropanol to obtain intermediate 1. Step S2: Add the obtained intermediate 1 and triethylamine to N-methylpyrrolidone, add methacrylamide chloride under nitrogen atmosphere, heat to 45-50℃, stir at a constant speed and react for 12h. After the reaction is completed, the functional monomer is obtained.

2. A paper de-plasticizing production process based on nano-de-plasticizing oil according to claim 1, characterized in that, In step S1, the ratio of 4-dodecylbenzaldehyde, p-aminobenzoyl hydrazine, glacial acetic acid, and acetonitrile is controlled to be 10-15 mmol: 10-15 mmol: 0.02-0.03 mL: 150 mL.

3. The paper deplasticizing process based on nano-deplasticizing oil according to claim 1, characterized in that, In step S2, the ratio of intermediate 1, methacryloyl chloride, triethylamine and N-methylpyrrolidone is controlled to be 10-12 mmol: 10-12 mmol: 1.5-1.8 mL: 50-75 mL.

4. The paper deplasticizing process based on nano-deplasticizing oil according to claim 1, characterized in that, The active monomer is one or more of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, and acryloylmorpholine mixed in any proportion.

5. The paper deplasticizing process based on nano-deplasticizing oil according to claim 1, characterized in that, The photoinitiator is one or more of photoinitiator 184, photoinitiator 1173 and photoinitiator 2959 mixed in any proportion.

6. The paper deplasticizing process based on nano-deplasticizing oil according to claim 1, characterized in that, The additive is a mixture of leveling agent and adhesion promoter in a 1:1 weight ratio.

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