Water-based PI matt varnish

Abstract

The water-based PI matt varnish comprises the following components: water-based halogen-free modified polyolefin resin, water-based anionic self-extinction hydroxy acrylic resin, water-based low-temperature deblocking closed type polyisocyanate resin, a water-based organic silicon defoaming agent, a water-based organic silicon modified wetting dispersant and an organic silicon modified base material wetting agent. The water-based organic silicon modified wetting dispersant and the organic silicon modified base material wetting agent are combined to form a wetting leveling agent; the cleaning agent further comprises deionized water A, deionized water B, deionized water C, deionized water D, an alcohol ether cosolvent and a thickening agent. The matte ink is coated on the surface of a PI film through a micro-gravure coating process to form a matte ink coating, the surface tension of the coating is greater than or equal to 50Dyn after thermocuring film formation, the surface is easily wetted, and the subsequent coating or printing process is facilitated.

Description

Technical Field

[0001] The invention relates to conductive ink, in particular to a water-based PI matte oil. Background Art

[0002] PI film, full name polyimide film, is a high-performance polymer film material with excellent temperature resistance, mechanical properties and electrical properties. It is widely used in electronic products, aerospace, medical, optical and new energy fields.

[0003] However, due to the chemical and physical structure of the PI film itself, its high chemical inertness, low surface energy, film flexibility and environmental conditions, traditional inks are difficult to adhere directly. Surface treatment, including plasma, flame and corona treatment, or the use of a primer as an adhesive is required to improve adhesion. The process is complex and the material cost is high. At the same time, the high VOC content and strong odor of the ink are unfriendly to operators and the environment, which limits its application.

[0004] PI film materials have dense molecular arrangement, poor absorption, and a small number of functional groups on the surface that can form chemical bonds. They are chemically inert and it is difficult for general inks to form good adhesion and bonding strength. The commonly used treatment method is to treat PI film materials with plasma, flame and corona to change the structure of the surface of PI materials and produce some active groups to improve the adhesion of inks. However, the disadvantages of this method are also obvious, such as short effectiveness, poor stability, and poor durability. Alternatively, a primer layer can be added as a transition layer to act as an adhesive, but this will increase the process and material costs, and at the same time increase the film thickness of the entire coating and thus increase the thickness of the PI film, limiting its use. In addition, in order to enhance the adhesion of PI, it is possible to use chlorinated polyolefin resins, which introduce halogen components and release a large amount of hydrogen chloride gas when burned, causing serious pollution to the environment.

[0005] At the same time, traditional inks usually contain a large amount of ketone and ester volatile solvents, which cause flammable and explosive risks in production, transportation, storage and use. In addition, traditional inks have average chemical resistance and can only pass the alcohol abrasion test. They are easily corroded by other chemicals used in post-processing or daily applications. In order to improve chemical resistance, some inks are made into two components and additional curing agents are added. This has an activation period limit. As time goes by, the viscosity of the diluted ink continues to rise or even gel, and the performance decreases. Its usable time cannot exceed 24 hours; the surface energy of the traditional ink coating is too high, and the dyne value is not high, which is not conducive to the subsequent application of glue coating or logo character printing process.

[0006] Therefore, it is necessary to provide a water-based PI matte oil to solve the above problems. Summary of the invention

[0007] The purpose of the present invention is to provide a water-based PI matte oil.

[0008] The present invention achieves the above object through the following technical solutions:

[0009] One of the technical solutions:

[0010] A water-based PI matt oil, the components of which include: water-based halogen-free modified polyolefin resin, water-based anionic self-matting hydroxy hydroxy acrylic resin, water-based low-temperature deblocking blocked polyisocyanate resin, water-based organosilicon defoaming agent, water-based organosilicon modified wetting dispersant, organosilicon modified substrate wetting agent;

[0011] The water-based organosilicon-modified wetting and dispersing agent and the organosilicon-modified base material wetting agent are combined to form a wetting and leveling agent;

[0012] It also includes deionized water A, deionized water B, deionized water C, deionized water D, alcohol ether cosolvents, and thickeners;

[0013] A matte ink coating is formed on the surface of the PI film through a micro-concave coating process. After thermal curing, the surface tension of the coating is ≥50Dyn, and the surface is easily wetted, which is convenient for subsequent coating or printing processes.

[0014] Furthermore, in terms of percentage, the groups are:

[0015] 10-50 parts of water-based halogen-free modified polyolefin resin;

[0016] 40-80 parts of water-based anionic self-matting hydroxy hydroxy acrylic resin;

[0017] 5-20 parts of water-based low-temperature deblocking blocked polyisocyanate resin;

[0018] 0.3-0.5 parts of water-based silicone defoamer;

[0019] Wetting and leveling agent 0.3-0.5 parts;

[0020] 5-10 parts of alcohol ether cosolvent;

[0021] Deionized water A 5-10 parts;

[0022] Amine pH regulator 0.3-0.5 parts;

[0023] Deionized water B 0.3-0.5 parts;

[0024] Deionized water C 10-20 parts;

[0025] Thickener 0.5-2 parts;

[0026] Deionized water D 0.5-2 parts;

[0027] Furthermore, deionized water A, deionized water B, deionized water C, and deionized water D are added at different steps in the preparation process.

[0028] Furthermore, the water-based anionic self-matting hydroxy hydroxy acrylic resin has a suitable minimum film-forming temperature, may have a glass transition temperature between 30 and 50°C, has excellent quick-drying properties, workability, wear resistance and hardness, and has excellent adhesion to various types of plastics. It also contains hydroxyl groups and can react chemically with polyisocyanate-type curing agents to improve the chemical properties of the final coating, such as resistance to alcohol and butanone, and the hydroxyl value is not less than 66KOH mg / g.

[0029] Furthermore, the aqueous anionic self-matting hydroxyl acrylic resin includes a hydroxyl acrylic resin with a special core-shell structure and a number average molecular weight of about 50,000 to 100,000, which exists in the form of an aqueous emulsion, and its particle size exists in the emulsion in two main particle size distribution ranges of 50 to 150 nm and 800 to 3000 nm. No additional matte material is required, and SiO2 matte powder is the most common. A matte effect can be formed after the resin film is formed.

[0030] Furthermore, when the amount of the aqueous anionic self-matting hydroxy hydroxy acrylic resin is less than 10%, the first coating formed by the coating composition has low hardness and slow surface drying, which makes it easy to stick when winding; at the same time, it reduces the crosslinking density of the overall coating, thereby causing a decrease in chemical resistance such as alcohol resistance and butanone resistance; when the amount is higher than 60%, the hardness of the first coating formed by the coating composition is too high, resulting in poor adhesion to the PI substrate and peeling.

[0031] Furthermore, the water-based anionic self-matting hydroxy acrylic resins are selected from: HHA 9191 and DN8080 from Argo; SM 6826w / 43WA from Allnex; X-PU650 from Hua; and SA 5112 from Youmiao.

[0032] Furthermore, the water-based halogen-free modified polyolefin resin is halogen-free, has a number average molecular weight of 8,000 to 10,000, and has a softening point of 50 to 90°C, which can effectively help drying while reducing the risk of re-sticking during winding. It does not contain an emulsifier, and the hydrophilic groups on the resin molecular chain can react with a cross-linking agent, thereby ensuring that the formed coating has excellent water resistance and chemical resistance. It exists in the form of an aqueous dispersion, and it exists in the emulsion with a particle size in the range of 200 to 500 nm, which can increase the stability of the emulsion and give the coating an excellent appearance.

[0033] Furthermore, the water-based low-temperature deblocking blocked polyisocyanate resin is isophorone diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, tetraalkylphenylene diisocyanate such as meta-tetramethylphenylene diisocyanate, para-phenylene diisocyanate, polymethylene polyphenyl isocyanate, diphenyl pentamethyl diisocyanate, 2,6-toluene diisocyanate, dianisole diisocyanate, ditoluene diisocyanate, naphthalene-1,4-diisocyanate, bis(4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate, and hexamethylene diisocyanate.

[0034] Furthermore, water-based low-temperature deblocking blocked polyisocyanate resins are selected from: WH-2940, WH-2937, HF-3192, WH-2943 from Haohui; WM44-L70G from Asahi; BL-8115, BL-8085 from Guanzhi; PT-1085 from Lubao.

[0035] Compared with the prior art, the present invention is a water-based system and does not contain environmentally controlled substances: a fully water-based system, water-based resins and additives are used as film-forming materials, deionized water is used as a solvent, which is safe and environmentally friendly, complies with GB 38507-2020, and has extremely low VOC emissions; it does not contain heavy metals, halogens and other environmentally controlled substances, fully meets the requirements of Rhos and Reach regulations, and meets export requirements; the construction process is simple, efficient and economical: single component, no need to add additional curing agent, easy to prepare, no activation period problem, and can be recycled; micro-concave coating process, high ink utilization rate, no waste, simple and mature process, can achieve fast and continuous operation; good adhesion, no need for additional processing process, or adding primer, which improves production efficiency and further reduces production costs; excellent physical properties: coated on the surface of the PI film material by micro-concave coating, after drying and ripening, a stable coating is formed on the surface of the PI material. Its adhesion (100-grid test ≥4B), scratch resistance (slight scratches by nails), resistance to alcohol and butanone wiping (≥100 times, load 500g), and high value (≥50). DETAILED DESCRIPTION

[0036] Example:

[0037] A water-based PI matte oil, the components of which can be found in the following table:

[0038] Components Weight Percent Waterborne hydroxy acrylic resin 10 Waterborne polyolefin resin 60 Water-based low temperature deblocking blocked isocyanate 5 BYK024 0.3 BYK348 0.3 Ethylene glycol butyl ether 5 Deionized water A 5 DMEA 0.3 Deionized water B 0.3 Deionized water C 10.8 AS1130 1.5 Deionized water 1.5 total 100

[0039] The preparation process is:

[0040] 1) According to the proportion, water-based hydroxy acrylic resin, water-based polyolefin resin and water-based low-temperature unblocking blocked isocyanate are filtered with a 300-mesh filter cloth and added to a stainless steel mixing tank. Stir at 200-400 speed for 10-20 minutes. Water-based hydroxy acrylic resin, water-based polyolefin resin and water-based low-temperature unblocking blocked isocyanate are selected from water-based halogen-free modified polyolefin resin, water-based anionic self-extinction hydroxy acrylic resin, water-based low-temperature unblocking blocked polyisocyanate resin

[0041] 2) Weigh BYK 024 and BYK 348 in the above table according to the weight percentage, increase the dispersion speed to 400-600 rpm, and slowly add them into the stainless steel mixing tank while dispersing. Stir at 400-600 rpm for 10-20 minutes, and scrape the fineness plate to ensure that there are no shrinkage holes, particles or other abnormalities.

[0042] 3) Weigh the ethylene glycol butyl ether in the above table according to the weight percentage, mix it evenly with deionized water in a weight ratio of 1:1, reduce the dispersion speed to 200-400 rpm, filter and add it into a stainless steel mixing tank while dispersing.

[0043] 4) Weigh the DMEA in the table above according to the weight percentage, and mix it with deionized water at a weight ratio of 1:1. Note that this process will release heat. After cooling to room temperature, use a 300-mesh filter cloth to filter and add it to a stainless steel mixing tank while dispersing.

[0044] 5) Weigh the deionized water in the above table according to the weight percentage, add it into a stainless steel mixing tank while dispersing and filtering.

[0045] 6) Weigh the AS1130 in the above table according to the weight percentage, mix it evenly with deionized water in a weight ratio of 1:1, use a 300-mesh filter cloth, filter it while dispersing, and add it into a stainless steel mixing tank.

[0046] 7) After continuing to disperse for 10 to 20 minutes, scrape the fineness plate to confirm the fineness, and measure the pH value, viscosity and solid content.

[0047] Preparation of matt oil coating: water-based PI matt oil and deionized water are divided into 100:5-10 by mass, stirred evenly, filtered through 300-mesh nylon mesh, and micro-concave coating is carried out on the machine. The coating method is the existing method and no primer is required; the ink is applied to the substrate by a roller, and the ink coating thickness is 2-4 microns. After that, it is baked in a 90-100℃ hot air oven for 20-30 seconds and the surface is dry without re-stickiness; after the surface is dry, it is rolled up, and the rolled material is placed in a 50±2℃ oven for aging for 12 hours to complete the curing, and relevant performance tests can be carried out; the substrate is a 0.025 mm transparent PI film.

[0048] Deionized water A, deionized water B, deionized water C, and deionized water D are added in different steps during the preparation process.

[0049] The water-based anionic self-matting hydroxy hydroxy acrylic resin has a suitable minimum film-forming temperature and can have a glass transition temperature between 30 and 50°C. It has excellent quick-drying properties, workability, wear resistance and hardness, and has excellent adhesion to various types of plastics. It also contains hydroxyl groups and can react chemically with polyisocyanate curing agents to improve the chemical properties of the final coating, such as resistance to alcohol and butanone. The hydroxyl value is not less than 66KOH mg / g.

[0050] The aqueous anionic self-matting hydroxyl acrylic resin includes a hydroxyl acrylic resin with a special core-shell structure and a number average molecular weight of about 50,000 to 100,000. It exists in the form of an aqueous emulsion, and its particle size exists in the emulsion in two main particle size distribution ranges of 50 to 150 nm and 800 to 3000 nm. No additional matte material is required, and SiO2 matte powder is the most common. A matte effect can be formed after the resin film is formed.

[0051] When the amount of the aqueous anionic self-matting hydroxy hydroxy acrylic resin is less than 10%, the first coating formed by the coating composition has low hardness and slow surface drying, which makes it easy to stick back when winding; at the same time, it reduces the crosslinking density of the overall coating, thereby causing a decrease in chemical resistance such as alcohol resistance and butanone resistance; when the amount is higher than 60%, the first coating formed by the coating composition has too high hardness, resulting in poor adhesion to the PI substrate and peeling.

[0052] The water-based anionic self-matting hydroxy hydroxy acrylic resins are: HHA 9191 and DN 8080 from Argo; SM 6826w / 43WA from Allnex; X-PU650 from Hua; SA 5112 from Youmiao.

[0053] The water-based halogen-free modified polyolefin resin is halogen-free, has a number average molecular weight of 8,000 to 10,000, and a softening point of 50 to 90°C, which can effectively help drying while reducing the risk of re-sticking during winding. It does not contain emulsifiers, and the hydrophilic groups on the resin molecular chain can react with the cross-linking agent, thus ensuring that the formed coating has excellent water resistance and chemical resistance. It exists in the form of an aqueous dispersion, and it exists in the emulsion with a particle size in the range of 200 to 500 nm, which can increase the stability of the emulsion and give the coating an excellent appearance.

[0054] The water-based low-temperature deblocking blocked polyisocyanate resin is isophorone diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, tetraalkylphenylene diisocyanate such as meta-tetramethylphenylene diisocyanate, para-phenylene diisocyanate, polymethylene polyphenyl isocyanate, diphenyl pentamethyl diisocyanate, 2,6-toluene diisocyanate, dianisylphenyl diisocyanate, ditolyl diisocyanate, naphthalene-1,4-diisocyanate, bis(4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate, and hexamethylene diisocyanate.

[0055] The water-based low-temperature deblocking blocked polyisocyanate resins are: WH-2940, WH-2937, HF-3192, WH-2943 from Haohui; WM44-L70G from Asahi; BL-8115, BL-8085 from Guanzhi; PT-1085 from Lubao.

[0056] For ink inspection, please refer to:

[0057] Table 1: Ink inspection indicators

[0058]

[0059] Table 2: Ink performance test results

[0060]

[0061]

[0062] It can be determined from Table 1 and Table 2 that the product of the present invention is superior to the commercially available product in various properties tested.

[0063] Compared with the prior art, the present invention is a water-based system and does not contain environmentally controlled substances: a fully water-based system, water-based resins and additives are used as film-forming materials, deionized water is used as a solvent, which is safe and environmentally friendly, complies with GB 38507-2020, and has extremely low VOC emissions; it does not contain heavy metals, halogens and other environmentally controlled substances, fully meets the requirements of Rhos and Reach regulations, and meets export requirements; the construction process is simple, efficient and economical: single component, no need to add additional curing agent, easy to prepare, no activation period problem, and can be recycled; micro-concave coating process, high ink utilization rate, no waste, simple and mature process, can achieve fast and continuous operation; good adhesion, no need for additional processing process, or adding primer, which improves production efficiency and further reduces production costs; excellent physical properties: coated on the surface of the PI film material by micro-concave coating, after drying and ripening, a stable coating is formed on the surface of the PI material. Its adhesion (100-grid test ≥4B), scratch resistance (slight scratches by nails), resistance to alcohol and butanone wiping (≥100 times, load 500g), and high value (≥50).

[0064] The above are only some embodiments of the present invention. For those skilled in the art, several modifications and improvements can be made without departing from the creative concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A water-based PI matte oil, characterized in that: The components include: water-based halogen-free modified polyolefin resin, water-based anionic self-extinction hydroxy hydroxy acrylic resin, water-based low-temperature deblocking blocked polyisocyanate resin, water-based organosilicon defoamer, water-based organosilicon modified wetting dispersant, organosilicon modified substrate wetting agent; The water-based organosilicon-modified wetting and dispersing agent and the organosilicon-modified base material wetting agent are combined to form a wetting and leveling agent; It also includes deionized water A, deionized water B, deionized water C, deionized water D, alcohol ether cosolvents, and thickeners; A matte ink coating is formed on the surface of the PI film through a micro-concave coating process. After thermal curing, the surface tension of the coating is ≥50Dyn, and the surface is easily wetted, which is convenient for subsequent coating or printing processes.

2. A water-based PI matte oil according to claim 1, characterized in that: In terms of percentage, the groups are:

3. A water-based PI matte oil according to claim 1, characterized in that: Deionized water A, deionized water B, deionized water C, and deionized water D are added in different steps during the preparation process.

4. A water-based PI matte oil according to claim 1, characterized in that: The water-based anionic self-matting hydroxy hydroxy acrylic resin has a suitable minimum film-forming temperature and can have a glass transition temperature between 30 and 50°C. It has excellent quick-drying properties, workability, wear resistance and hardness, and has excellent adhesion to various types of plastics. It also contains hydroxyl groups and can react chemically with polyisocyanate curing agents to improve the chemical properties of the final coating, such as resistance to alcohol and butanone. The hydroxyl value is not less than 66KOH mg / g.

5. A water-based PI matte oil according to claim 1, characterized in that: The aqueous anionic self-matting hydroxyl acrylic resin includes a hydroxyl acrylic resin with a special core-shell structure and a number average molecular weight of about 50,000 to 100,000. It exists in the form of an aqueous emulsion, and its particle size exists in the emulsion in two main particle size distribution ranges of 50 to 150 nm and 800 to 3000 nm. No additional matte material is required, and SiO2 matte powder is the most common. A matte effect can be formed after the resin film is formed.

6. A water-based PI matte oil according to claim 1, characterized in that: When the amount of the aqueous anionic self-matting hydroxy hydroxy acrylic resin is less than 10%, the first coating formed by the coating composition has low hardness and slow surface drying, which makes it easy to stick back when winding; at the same time, it reduces the crosslinking density of the overall coating, thereby causing a decrease in chemical resistance such as alcohol resistance and butanone resistance; when the amount is higher than 60%, the first coating formed by the coating composition has too high hardness, resulting in poor adhesion to the PI substrate and peeling.

7. A water-based PI matte oil according to claim 1, characterized in that: The water-based anionic self-matting hydroxy hydroxy acrylic resins are: HHA 9191 and DN 8080 from Argo; SM 6826w / 43WA from Allnex; X-PU650 from Hua; SA 5112 from Youmiao.

8. A water-based PI matte oil according to claim 1, characterized in that: The water-based halogen-free modified polyolefin resin is halogen-free, has a number average molecular weight of 8,000 to 10,000, and a softening point of 50 to 90°C, which can effectively help drying while reducing the risk of re-sticking during winding. It does not contain emulsifiers, and the hydrophilic groups on the resin molecular chain can react with the cross-linking agent, thus ensuring that the formed coating has excellent water resistance and chemical resistance. It exists in the form of an aqueous dispersion, and it exists in the emulsion with a particle size in the range of 200 to 500 nm, which can increase the stability of the emulsion and give the coating an excellent appearance.

9. A water-based PI matte oil according to claim 1, characterized in that: The water-based low-temperature deblocking blocked polyisocyanate resin is isophorone diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, tetraalkylphenylene diisocyanate such as meta-tetramethylphenylene diisocyanate, para-phenylene diisocyanate, polymethylene polyphenyl isocyanate, diphenyl pentamethyl diisocyanate, 2,6-toluene diisocyanate, dianisylphenyl diisocyanate, ditolyl diisocyanate, naphthalene-1,4-diisocyanate, bis(4-isocyanatephenyl)methane, 4,4'-diphenylpropane diisocyanate, and hexamethylene diisocyanate.

10. A water-based PI matte oil according to any one of claims 1 to 9, characterized in that: The water-based low-temperature deblocking blocked polyisocyanate resins are: WH-2940, WH-2937, HF-3192, WH-2943 from Haohui; WM44-L70G from Asahi; BL-8115, BL-8085 from Guanzhi; PT-1085 from Lubao.

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