Preparation method of four-color water transfer printing paper

Abstract

The present invention discloses a preparation method of a four-color water transfer printing paper. In the present invention, softwood and hardwood are used to make the base paper. First, a soluble resin solution is coated to form a gel film, then the pattern is restored by printing with yellow, magenta, cyan, and black as the primary colors, and finally a waterproof film-forming resin is coated to shape and protect the pattern, thereby obtaining the four-color water transfer printing paper.

Description

Technical Field

[0001] The present invention relates to the field of printing technology, and more specifically to a method for preparing a four-color water transfer printing paper. Background Art

[0002] With the development of social economy and the continuous improvement of people's living standards, traditional printing technologies can no longer meet the needs of people's daily life. To meet the needs of surface packaging from daily necessities to office supplies, and even home decoration and the automotive industry, etc., adopting the new industrial technology of water transfer printing is the best choice.

[0003] Transfer printing technology is a revolutionary transfer printing technology developed to address problems such as difficulty in printing on objects with complex shapes, overweight, oversized, or fragile objects in general traditional printing, and the presence of printing dead corners on objects. It can be transferred onto any flat, curved, or irregularly shaped object. It is widely used in fields such as telecommunications products, daily necessities, handicrafts, sports equipment, and the automotive industry, greatly meeting people's personalized needs in daily life.

[0004] However, at the current stage, there are still problems with the carrier water transfer printing paper of this technology in one application aspect. For example, the upper pigment pattern generally has a long demolding reaction time and low transfer efficiency during the transfer decal process, and it is prone to deformation and rupture of the pigment pattern caused by external force pulling during the demolding process, resulting in the scrapping of the water transfer printing paper. And because the objects to be transferred may have uniqueness, such as being used at high temperatures or the size may change during use, etc., which may lead to damage to the pattern. Therefore, providing a water transfer printing paper that is easy to demold, heat-resistant, and has high toughness is exactly the goal of the present invention. Summary of the Invention

[0005] 1. To solve the above technical problems, the technical solution provided by the present invention includes the following steps:

[0006] (1) Mix 90 parts of softwood and 10 parts of hardwood in a total of 100 parts, and make a pulp with a beating degree of 32°SR as the standard;

[0007] (2) Sequentially add 0.8 - 1.2 parts of AKD, 4 - 6 parts of heavy calcium carbonate, 0.5 - 1.1 parts of cationic starch, and 0.5 - 1.5 parts of strong wetting agent to the pulp, and mix evenly to obtain mixture A;

[0008] (3) Sheet mixture A on a square sheet former at 140 g / m 2 Dry it at 95°C after sheeting;

[0009] (4) After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at a temperature of 23°C and a humidity of 50% for moisture balance to obtain the base paper;

[0010] (5) Mix 100 - 150 parts of a water - soluble resin solution at 60°C with 10 - 16 parts of an antifoaming agent, and then coat it on one side of the base paper at a sizing amount of 0.8 - 1.2 g / m 2 by spreading sizing, and let it cool naturally until the water - soluble resin gels to form a film;

[0011] (6) Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four - color printing to restore the pattern on the water - soluble resin layer;

[0012] (7) After the pattern is formed, mix 100 - 150 parts of a waterproof film - forming resin with 10 - 16 parts of an antifoaming agent and coat it at a sizing amount of 0.6 - 1.0 g / m 2 by spreading sizing, and spray triglycidyl isocyanurate to cure the waterproof film - forming resin into a film, then the four - color water transfer printing paper is obtained.

[0013] 2. Further, the preparation method of the water - soluble resin solution is as follows:

[0014] (1) Weigh 90 - 110 parts of N,N,N',N'-tetraglycidyl - 4,4'-diaminodiphenylmethane and 50 - 60 parts of 2-(hydroxymethylamino)ethanol;

[0015] (2) Place N,N,N',N'-tetraglycidyl - 4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir it at 60°C until it is completely dissolved;

[0016] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved in ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl - 4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time;

[0017] (4) Keep the coolant in the reactor in a condensing reflux cycle, then heat the mixture to 80°C and continuously stir for the first reaction for 2 h;

[0018] (5) After the first reaction is completed, cool down to 60°C, add glacial acetic acid dropwise in the reactor to adjust the pH to neutral. After dropping, heat back to 80°C for the second reaction for 30 min;

[0019] (6) After the second reaction is completed, place the product in a vacuum oven at 60°C to remove the solvent ethanol, and then the water - soluble resin can be obtained;

[0020] (7) Add 1200 - 1400 parts of distilled water and heat it to 60°C to prepare a solution, and then the water - soluble resin solution is obtained.

[0021] 3. Further, the composition of the waterproof film - forming resin is 70 - 80% octadecyl polymethacrylate, and the rest is tetra - n - butylammonium phosphate.

[0022] 4. Further, the defoaming agent is composed of 2,5,8,11 - tetramethyl - 6 - dodecyn - 5,8 - diol polyoxyethylene ether.

[0023] The beneficial effects of the present invention are as follows:

[0024] 1) The water transfer printing paper uses a water - soluble resin to adsorb on the surface of the base paper and dissolves in water during use to form a micelle adhesive, realizing the separation of the pattern from the base paper and making the film adsorb on the carrier. In the present invention, N,N,N',N' - tetra - glycidyl - 4,4' - diaminodiphenylmethane is selected as the original resin, and 2 - (hydroxymethylamino) ethanol is used for modification to destroy part of the epoxy groups and adjust its water - soluble rate.

[0025] 2) The modified N,N,N',N' - tetra - glycidyl - 4,4' - diaminodiphenylmethane resin has excellent adhesion performance and film - forming performance, meeting the requirements of the water - soluble resin layer. Compared with other water - soluble resins, this resin has excellent mechanical and heat - resistant properties, which can greatly expand the application range of the printing paper, and avoid the deformation of the adhesion layer and the detachment or deformation of the pattern caused by high temperature or external force in applications such as ceramics and metal processing.

[0026] 3) The modified N,N,N',N' - tetra - glycidyl - 4,4' - diaminodiphenylmethane resin has a three - dimensional cross - linked structure, which can increase the contact area with the carrier, strengthen the color - fixing effect, improve the lifespan of the pattern, and also reduce the shrinkage rate of the carrier, reducing the possibility of pattern deformation, and facilitating the optimization of the transfer effect of larger and more complex patterns.

[0027] 4) The water - proof film - forming resin requires dimensional stability, water - proofness, and chemical inertness. Usually, polyester, polyunsaturated hydrocarbons and derivatives, and melamine - formaldehyde resin are selected. After the printing paper absorbs water, the pattern can adhere to the water - proof film - forming resin layer to maintain the integrity of the pattern and form a tough film. In the present invention, octadecyl methacrylate is selected, which has a long alkyl chain with eighteen carbons and excellent hydrophobicity. The long - chain polymeric fiber endows it with excellent physical properties. Through modification with tetra - n - butylammonium phosphate, the water - proof film - forming resin has excellent heat - resistant properties and is suitable for use in various scenarios, expanding the application range of the printing paper.

[0028] 5) The combination of octadecyl methacrylate and tetra - n - butylammonium phosphate makes the liquid resin change from a sparse layered part to a closely packed hexagonal structure, making the resin have appropriate hardness to protect the printing pattern from external damage. At the same time, the co - existence of the sparse layered and closely packed hexagonal structures enables the resin to undergo a phase change after heating, effectively improving the heat - resistant property of the system and protecting the integrity of the pattern at high temperature.

[0029] 6) Resin coating is usually in liquid form. In the present invention, the resin selected to maintain excellent bonding effect has a relatively high viscosity, which leads to a large amount of air bubbles being contained, easily affecting the characterization of the properties after the resin film is formed, damaging the original resin structure, making the patterns of the printed paper rough and the stability worse. Therefore, an antifoaming agent is supplemented to assist in removing the air bubbles in the liquid resin. 2,5,8,11-Tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether is a non-ionic antifoaming agent that can effectively remove the air bubbles in the organic resin.

[0030] 7) 2,5,8,11-Tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether is an excellent antifoaming agent. At the same time, its long carbon chain forms a bondage in the resin, facilitating the maintenance of the original size and the stable pattern ratio after being water-soluble. Moreover, the rich ethoxy groups can effectively reduce the surface tension, stabilize the resin system, and enhance the adhesion of the pattern, avoiding the damage of the pattern during the water-soluble process. Detailed implementation mode

[0031] The present invention will be further described in detail below with reference to the embodiments.

[0032] In the embodiments of the present invention, raw materials and chemical reagents are obtained through conventional commercial channels without special instructions.

[0033] Embodiment 1

[0034] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0035] (1) Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol;

[0036] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C to completely dissolve it;

[0037] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved with ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time;

[0038] (4) Keep the coolant circulation of the reactor for condensation reflux, then heat the mixture to 80 °C, and continuously stir for the first reaction for 2 h;

[0039] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise in the reactor to adjust the PH to neutral. After the dropping is completed, heat back to 80 °C for the second reaction for 30 min;

[0040] After the second reaction is completed, the product is placed in a vacuum oven at 60 °C to remove the solvent ethanol, and a water-soluble resin can be obtained.

[0041] (7)Add 1300 parts of distilled water and heat it to 60 °C to prepare a solution, and a water-soluble resin solution is obtained.

[0042] 2. The composition of the waterproof film-forming resin is 75% octadecyl polymethacrylate, and the rest is tetrabutylammonium phosphate.

[0043] 3. Mix 9 parts of softwood and 1 part of hardwood, a total of 100 parts, and make a pulp with a beating degree of 32 °SR as the standard.

[0044] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5 w% PPE solution to the pulp in sequence, and mix evenly to obtain a mixture A.

[0045] 5. Spread the mixture A on a square sheet former at 140 g / m 2 Make a sheet, and dry it at 95 °C after making the sheet.

[0046] 6. After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at 23 °C and 50% humidity for moisture balance to obtain the base paper.

[0047] 7. Mix 125 parts of the water-soluble resin solution at 60 °C with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat and size it on one side of the base paper at a sizing amount of 1 g / m 2 Let it cool naturally until the water-soluble resin gels and forms a film.

[0048] 8. Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the sample pattern on the water-soluble resin layer.

[0049] 9. After the pattern is formed, mix 125 parts of the waterproof film-forming resin with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, coat and size it at a sizing amount of 0.8 g / m 2 Spray isocyanuric acid triglycidyl ester to cure and form a film of the waterproof film-forming resin, and a four-color water transfer printing paper is obtained.

[0050] Example 2

[0051] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0052] (1)Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol.

[0053] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C until it is completely dissolved;

[0054] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved in ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time;

[0055] (4) Keep the coolant of the reactor in a condensing reflux cycle, then heat the mixture to 80 °C and continuously stir for the first reaction for 2 h;

[0056] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise to the reactor to adjust the pH to neutral. After the addition is complete, heat back up to 80 °C for the second reaction for 30 min;

[0057] (6) After the second reaction is completed, place the product in a vacuum oven at 60 °C to remove the solvent ethanol, and then a water-soluble resin can be obtained;

[0058] (7) Add 1300 parts of distilled water and heat to 60 °C to prepare a solution, and then a water-soluble resin solution is obtained.

[0059] 2. The composition of the waterproof film-forming resin is 70% octadecyl polymethacrylate, and the rest is tetrabutylammonium phosphate;

[0060] 3. Mix 90 parts of softwood and 10 parts of hardwood, a total of 100 parts, and make pulp according to the beating degree of 32°SR;

[0061] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5 w% PPE solution to the pulp in sequence, and mix evenly to obtain the mixture A;

[0062] 5. Sheet the mixture A on a square sheet former at 140 g / m 2 and dry it at 95 °C after sheeting;

[0063] 6. After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at 23 °C and 50% humidity for moisture balance to obtain the base paper;

[0064] 7. Mix 100 parts of the 60 °C water-soluble resin solution with 10 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat and size on one side of the base paper at a sizing amount of 0.8 g / m 2 and let it cool naturally until the water-soluble resin gels and forms a film;

[0065] 8. Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the pattern on the water-soluble resin layer;

[0066] 9. After the pattern is formed, 150 parts of waterproof film-forming resin are mixed with 16 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and sized at a sizing amount of 1.0 g / m 2 Apply sizing, spray triglycidyl isocyanurate to cure the waterproof film-forming resin into a film, and then the four-color water transfer printing paper is obtained.

[0067] Example 3

[0068] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0069] (1) Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol;

[0070] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C until it is completely dissolved;

[0071] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved with ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3-5 parts each time;

[0072] (4) Keep the coolant circulation of the reactor for condensation reflux, then heat the mixture to 80 °C, and continuously stir for the first reaction for 2 h;

[0073] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise to the reactor to adjust the PH to neutral. After the dropping is completed, heat back to 80 °C for the second reaction for 30 min;

[0074] (6) After the second reaction is completed, place the product in a vacuum oven at 60 °C to remove the solvent ethanol, and then the water-soluble resin can be obtained;

[0075] (7) Add 1300 parts of distilled water and heat to 60 °C to prepare a solution, and then the water-soluble resin solution is obtained.

[0076] 2. Configure the waterproof film-forming resin with a composition of 80% octadecyl polymethacrylate and the rest being tetrabutylammonium phosphate;

[0077] 3. Mix 100 parts of softwood and hardwood in a ratio of 9:1, and make a pulp with a beating degree of 32 °SR as the standard;

[0078] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5w% PPE solution to the slurry in sequence, and mix evenly to obtain mixture A;

[0079] 5. Sheet the mixture A on a square sheet former at 140 g / m 2 and dry it at 95 °C after sheeting;

[0080] 6. After drying, calender it with a calender, and then place it in a constant temperature and humidity chamber at 23 °C and 50% humidity for moisture balance to obtain the base paper;

[0081] 7. Mix 150 parts of a water-soluble resin solution at 60 °C with 16 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat it on one side of the base paper at a sizing amount of 1.2 g / m 2 and let it cool naturally until the water-soluble resin gels to form a film;

[0082] 8. Decompose the required printing sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the pattern on the water-soluble resin layer;

[0083] 9. After the pattern is formed, mix 100 parts of a waterproof film-forming resin with 10 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat it at a sizing amount of 0.6 g / m 2 and spray isocyanuric acid triglycidyl ester to cure the waterproof film-forming resin to form a film, then the four-color water transfer printing paper is obtained.

[0084] Comparative Example 1

[0085] The difference between this comparative example and Example 1 is that bisphenol A diglycidyl ether is used instead of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in step 1, and the rest of the implementation methods are the same as those in Example 1.

[0086] Comparative Example 2

[0087] The difference between this comparative example and Example 1 is that diisopropanolamine is used instead of 2-(hydroxymethylamino)ethanol in step 1, and the rest of the implementation methods are the same as those in Example 1.

[0088] Comparative Example 3

[0089] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0090] (1) Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol;

[0091] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C until it is completely dissolved;

[0092] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved in ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time;

[0093] (4) Keep the coolant of the reactor in condensing reflux circulation, then heat the mixture to 80 °C and continuously stir for the first reaction for 2 h;

[0094] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise to the reactor to adjust the pH to neutral. After the dropping is completed, heat back up to 80 °C for the second reaction for 30 min;

[0095] (6) After the second reaction is completed, place the product in a vacuum oven at 60 °C to remove the solvent ethanol, and then a water-soluble resin can be obtained;

[0096] (7) Add 1300 parts of distilled water and heat up to 60 °C to prepare a solution, thus obtaining a water-soluble resin solution.

[0097] 2. The composition of the waterproof film-forming resin is 75% octadecyl polymethacrylate, and the rest is tetrabutylammonium phosphate;

[0098] 3. Mix 100 parts of softwood and hardwood in a ratio of 9:1, and make pulp with a beating degree of 32°SR as the standard;

[0099] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5 w% PPE solution to the pulp in sequence, and mix evenly to obtain mixture A;

[0100] 5. Sheet mixture A on a square sheet former at 140 g / m 2 and dry it at 95 °C after sheeting;

[0101] 6. After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at a temperature of 23 °C and a humidity of 50% for moisture balance to obtain the base paper;

[0102] 7. Mix 50 parts of the 60 °C water-soluble resin solution with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat and size on one side of the base paper at a sizing amount of 1 g / m 2 and let it cool naturally until the water-soluble resin gels and forms a film;

[0103] 8. Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the pattern on the water-soluble resin layer;

[0104] 9. After the pattern is formed, 125 parts of waterproof film-forming resin are mixed with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and sized at a sizing amount of 0.8 g / m 2 Apply sizing, spray triglycidyl isocyanurate to cure the waterproof film-forming resin into a film, and then the four-color water transfer printing paper is obtained.

[0105] Comparative Example 4

[0106] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0107] (1) Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol;

[0108] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C until it is completely dissolved;

[0109] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved in ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3-5 parts each time;

[0110] (4) Keep the coolant in the reactor circulating for condensation reflux, then heat the mixture to 80 °C, and continuously stir for the first reaction for 2 h;

[0111] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise to the reactor to adjust the pH to neutral. After the addition is complete, heat back to 80 °C for the second reaction for 30 min;

[0112] (6) After the second reaction is completed, place the product in a vacuum oven at 60 °C to remove the solvent ethanol, and then the water-soluble resin can be obtained;

[0113] (7) Add 1300 parts of distilled water and heat to 60 °C to prepare a solution, and then the water-soluble resin solution is obtained.

[0114] 2. Configure the waterproof film-forming resin with a composition of 75% octadecyl polymethacrylate and the rest being tetrabutylammonium phosphate;

[0115] 3. Mix 100 parts of softwood and hardwood in a ratio of 9:1, and make a pulp with a beating degree of 32 °SR as the standard;

[0116] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5w% PPE solution to the slurry in sequence, and mix evenly to obtain mixture A;

[0117] 5. Sheet mixture A on a square sheet former at 140 g / m 2 and dry it at 95 °C after sheeting;

[0118] 6. After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at 23 °C and 50% humidity for moisture balance to obtain base paper;

[0119] 7. Mix 200 parts of water-soluble resin solution at 60 °C with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat and size on one side of the base paper at a sizing amount of 1 g / m 2 and let it cool naturally until the water-soluble resin gels and forms a film;

[0120] 8. Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the sample pattern on the water-soluble resin layer;

[0121] 9. After the pattern is formed, mix 125 parts of waterproof film-forming resin with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, coat and size at a sizing amount of 0.8 g / m 2 and spray isocyanuric acid triglycidyl ester to cure and form a film of the waterproof film-forming resin, then the four-color water transfer printing paper is obtained.

[0122] Comparative Example 5

[0123] The difference between this comparative example and Example 1 is that the octadecyl polymethacrylate in step 2 is melamine formaldehyde, and the other implementation manners are the same as those in Example 1.

[0124] Comparative Example 6

[0125] The difference between this comparative example and Example 1 is that the tetrabutylammonium phosphate in step 2 is ammonium polyphosphate, and the other implementation manners are the same as those in Example 1.

[0126] Comparative Example 7

[0127] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0128] (1) Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol;

[0129] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C until it is completely dissolved;

[0130] (3) After completely dissolving 2-(hydroxymethylamino)ethanol in ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time;

[0131] (4) Keep the coolant of the reactor in condensing reflux circulation, then heat the mixture to 80 °C and continuously stir for the first reaction for 2 h;

[0132] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise in the reactor to adjust the pH to neutral. After the dropping is completed, heat back to 80 °C for the second reaction for 30 min;

[0133] (6) After the second reaction is completed, place the product in a vacuum oven at 60 °C to remove the solvent ethanol, and then a water-soluble resin can be obtained;

[0134] (7) Add 1300 parts of distilled water and heat to 60 °C to prepare a solution, and then a water-soluble resin solution is obtained.

[0135] 2. The composition of the waterproof film-forming resin is 75% octadecyl polymethacrylate, and the rest is tetrabutylammonium phosphate;

[0136] 3. Mix 100 parts of softwood and hardwood in a ratio of 9:1, and make pulp with a beating degree of 32°SR as the standard;

[0137] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5 w% PPE solution to the pulp in sequence, and mix evenly to obtain mixture A;

[0138] 5. Sheet mixture A on a square sheet former at 140 g / m 2 Dry it at 95 °C after sheeting;

[0139] 6. After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at 23 °C and 50% humidity for moisture balance to obtain the base paper;

[0140] 7. After mixing 125 parts of the 60 °C water-soluble resin solution with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, apply sizing on one side of the base paper at a sizing amount of 1 g / m 2 and let it cool naturally until the water-soluble resin gels to form a film;

[0141] 8. Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the pattern on the water-soluble resin layer;

[0142] 9. After the pattern is formed, 50 parts of waterproof film-forming resin are mixed with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and sized at a sizing amount of 0.8 g / m 2 Apply sizing, spray triglycidyl isocyanurate to cure the waterproof film-forming resin into a film, and then the four-color water transfer printing paper is obtained.

[0143] Comparative Example 8

[0144] 1. Prepare a water-soluble resin solution, and the steps are as follows:

[0145] (1) Weigh 100 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 55 parts of 2-(hydroxymethylamino)ethanol;

[0146] (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60 °C to completely dissolve it;

[0147] (3) After 2-(hydroxymethylamino)ethanol is completely dissolved in ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time;

[0148] (4) Keep the coolant circulation of the reactor for condensation reflux, then heat the mixture to 80 °C and continuously stir for the first reaction for 2 h;

[0149] (5) After the first reaction is completed, cool down to 60 °C, add glacial acetic acid dropwise to the reactor to adjust the pH to neutral. After the addition is completed, heat back to 80 °C for the second reaction for 30 min;

[0150] (6) After the second reaction is completed, place the product in a 60 °C vacuum oven to remove the solvent ethanol, and then the water-soluble resin can be obtained;

[0151] (7) Add 1300 parts of distilled water and heat to 60 °C to prepare a solution, and then the water-soluble resin solution is obtained.

[0152] 2. Configure the waterproof film-forming resin with a composition of 75% octadecyl polymethacrylate and the rest being tetrabutylammonium phosphate;

[0153] 3. Mix 100 parts of softwood and hardwood in a ratio of 9:1, and make a pulp with a beating degree of 32 °SR as the standard;

[0154] 4. Add 1 part of AKD, 5 parts of heavy calcium carbonate, 0.8 part of cationic starch, and 1 part of 12.5w% PPE solution to the slurry in sequence, and mix evenly to obtain mixture A;

[0155] 5. Sheet the mixture A at 140 g / m 2 on a square sheet former, and dry it at 95 °C after sheeting;

[0156] 6. After drying, carry out calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at 23 °C and 50% humidity for moisture balance to obtain the base paper;

[0157] 7. Mix 125 parts of water-soluble resin solution at 60 °C with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat and size on one side of the base paper at a sizing amount of 1 g / m 2 naturally cool and wait for the water-soluble resin to gel and form a film;

[0158] 8. Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then carry out four-color printing to restore the sample pattern on the water-soluble resin layer;

[0159] 9. After the pattern is formed, mix 200 parts of waterproof film-forming resin with 13 parts of 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether, and coat and size at a sizing amount of 0.8 g / m 2 Spray isocyanuric acid triglycidyl ester to cure and form a film of the waterproof film-forming resin, and then the four-color water transfer printing paper is obtained.

[0160] Comparative Example 9

[0161] The difference between this comparative example and Example 1 is that the 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether in Steps 7 and 9 is 2,5,8,11-tetramethyl-5-decyn-4,7-diol, and the rest of the implementation manners are the same as those in Example 1.

[0162] Product determination:

[0163] Prepare four-color water transfer printing paper samples according to Examples 1-3 and Comparative Examples 1-9 respectively;

[0164] 1. Measure the cobb value, and use a paper surface absorption weight measuring instrument to measure each paper sample at room temperature. The obtained data are shown in Table 1.

[0165] 2. Demoulding property test: Immerse the inkjet water transfer printing paper printed with the pattern in water, and the film carrying the image can be separated from the base paper. It is required that the film carrying the image can be smoothly separated from the base paper within 60 seconds (it can slide with a little force instead of being torn), and record the time required for demoulding. The results are shown in Table 1.

[0166] 3. Adhesion performance test. The transfer effect was measured by the cross-cut method. Transfer a 10-mm 2 pattern to the surface of a metal sheet and use a blade to divide the pattern into 100 small grids of 1 mm * 1 mm each. The scoring must reach the bottom of the ink layer. Clean the surface debris, stick the tested small grid with 3M 600 adhesive tape, heat the back of the metal sheet to 300 °C, wipe the tape with an eraser, hold one end of the tape by hand, and quickly tear off the tape at a 90° angle. The test was completed at least at three different positions, and the average percentage of the pattern peeling area was recorded. The results are shown in Table 1.

[0167] 4. Anti-friction performance test. Manual detection method was adopted: Use a 500-g cube iron block with a white test paper attached to its bottom. Hold the iron block with the white test paper attached by a pushing rod by hand, electrically heat the iron block to 200 °C, and move it evenly on the glass surface layer to be tested (no pressure should be applied to the iron block during the movement, but rely on the gravity of the iron block itself for friction). The moving stroke is about 60 mm. Determine the friction resistance of the ink layer on the glass surface by recording the number of frictions when a large amount of ink marks appear on the white test paper. If there are serious large-area or continuous linear peeling ink marks on the surface, it indicates that there is a serious color fading phenomenon on the printed ink layer on the product surface. After 400 frictions on the wear resistance of the glass surface, obvious ink removal is not allowed. Record the number of wipes when obvious demoulding occurs. The obtained results are shown in Table 1.

[0168] 5. Acid and alkali resistance test. Take 36 glass bottles, transfer the pattern to their surfaces using three transfer printing papers for each example, then immerse them in 5% sulfuric acid or sodium hydroxide aqueous solution for 24 h and take them out, measure the average of the pattern peeling area. The results are shown in Table 1.

[0169] Table 1 Test data table

[0170] Cobb value (front / back, g / m2) Demolding time (s) Adhesion test (area shedding %) Anti-friction test (number of wiping times) Acid and alkali resistance test (area shedding %) Example 1 19 / 226 32 2.1 >400 3.2 Example 2 20 / 221 35 1.8 >400 3.1 Example 3 17 / 223 31 1.9 >400 3.5 Comparative Example 1 23 / 206 58 7.9 396 3.9 Comparative Example 2 26 / 187 54 5.1 391 3.8 Comparative Example 3 24 / 194 48 13.1 394 3.8 Comparative Example 4 21 / 209 39 2.6 396 3.7 Comparative Example 5 39 / 212 38 2.4 309 11.9 Comparative Example 6 51 / 210 36 2.5 242 4.4 Comparative Example 7 70 / 208 37 2.7 274 9.5 Comparative Example 8 24 / 214 38 2.4 >400 4.0 Comparative Example 9 66 / 191 47 3.9 362 8.4

Claims

1. A preparation method of a four-color water transfer printing paper, characterized in that: The steps are as follows: (1) Mix 100 parts in total of softwood and hardwood at a ratio of 9:1, and make pulp with a beating degree of 32°SR as the standard; (2) Add 0.8 - 1.2 parts of AKD, 4 - 6 parts of heavy calcium carbonate, 0.5 - 1.1 parts of cationic starch, and 0.5 - 1.5 parts of strong wetting agent to the pulp in sequence, and mix evenly to obtain mixture A; (3)Weigh 140 g / m of the mixed material A 2 Sheet it on a square sheet former, and then dry it at 95 °C after sheeting; (4) After drying, perform calendering treatment with a calender, and then place it in a constant temperature and humidity chamber at 23°C and 50% humidity for moisture balance to obtain base paper; (5) After mixing 100 to 150 parts of a water-soluble resin solution at 60 °C with 10 to 16 parts of an antifoaming agent, it is coated on one side of the base paper with a sizing amount of 0.8 to 1.2 g / m 2 and allowed to cool naturally until the water-soluble resin gels and forms a film; (6) Decompose the required printed sample pattern into yellow, magenta, cyan, and black, and then perform four-color printing to restore the pattern on the water-soluble resin layer; After the pattern is formed, 100-150 parts of waterproof film-forming resin are mixed with 10-16 parts of defoamer and applied with a sizing amount of 0.6-1.0 g / m 2 Apply sizing, spray triglycidyl isocyanurate to cure and form a film of the waterproof film-forming resin, and then the four-color water transfer printing paper is obtained.

2. The preparation method of a four-color water transfer printing paper according to claim 1, wherein: The preparation method of the water-soluble resin solution is as follows: (1) Weigh 90 - 110 parts of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 50 - 60 parts of 2-(hydroxymethylamino)ethanol; (2) Place N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane in a reactor, add ethanol as a solvent, and stir at 60°C to completely dissolve it; (3) After 2-(hydroxymethylamino)ethanol is completely dissolved with ethanol, add it to the reactor containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane at a rate of once per second and 3 - 5 parts each time; (4) Keep the coolant of the reactor in condensation reflux circulation, then heat the mixture to 80°C, and continuously stir for the first reaction for 2 h; (5) After the first reaction is completed, cool down to 60°C, add glacial acetic acid dropwise to the reactor to adjust the pH to neutral. After the dropping is completed, heat back to 80°C for the second reaction for 30 min; (6) After the second reaction is completed, place the product in a vacuum oven at 60°C to remove the solvent ethanol, and water-soluble resin can be obtained; (7) Add 1200 - 1400 parts of distilled water and heat to 60°C to prepare a solution, and the water-soluble resin solution is obtained.

3. The preparation method of a four-color water transfer printing paper as described in claim 1, characterized in that: The component of the waterproof film-forming resin is 70 - 80% octadecyl polymethacrylate, and the rest is tetrabutylammonium phosphate.

4. The preparation method of a four-color water transfer printing paper according to claim 1, characterized in that: The defoaming agent is 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol polyoxyethylene ether.