Aqueous antistatic flat oil and method for its preparation

Abstract

The application discloses water-based antistatic matt oil, which comprises a main agent and a diluent, wherein the main agent is composed of the following components in parts by weight: water-based polyolefin emulsion 40-60 parts; water-based film forming aid 5-10 parts; water-based wetting agent 1-2 parts; water-based neutralizing agent 0.5-1 part; flatting powder 2-5 parts; deionized water 10-20 parts; water-based defoaming agent 0.5-1 part; water-based thickening agent 0.5-1 part; polythiophene dispersion 5-15 parts; quaternary ammonium compound 2-5 parts; graphene dispersion 5-15 parts; and the diluent is composed of the following components in parts by weight: deionized water 100 parts.

Description

Technical Field

[0001] This invention relates to water-based inks, and more particularly to water-based inks for film materials, specifically a water-based antistatic matte ink and its preparation method. Background Technology

[0002] Water-based inks are mainly used in flexographic and gravure printing.

[0003] Water-based inks have maintained a significant market share in flexographic printing due to their excellent environmental performance. In the United States, 95% of flexographic products and 80% of gravure printing use water-based inks. The main advantages of gravure printing are high print durability, clear prints, and a wide range of substrates. It is now widely used in the packaging of high-end and exquisite products such as food, pharmaceuticals, tobacco, and alcohol, as well as in the printing of electronic products, medical devices, and other machinery and equipment.

[0004] The biggest advantage of water-based inks is that they significantly reduce VOC emissions during ink drying. Because water-based inks use water as a solvent, they avoid the harm to the human body and the pollution to packaged goods caused by the toxic substances in solvent-based inks, thus improving the printing environment and making them environmentally friendly products.

[0005] With the improvement and development of environmental regulations, environmental requirements for the coatings and inks industry are becoming increasingly stringent. Furthermore, people's growing awareness of health and safety has led to a focus on the development of water-based inks for film materials. Compared to solvent-based inks, water-based inks contain little or no organic solvents. During application, they emit less harmful gases, have lower VOC emissions, and are safer. Once fully cured, water-based inks exhibit properties comparable to their solvent-based counterparts.

[0006] However, the water-based inks currently in use have insufficient adhesion stability on non-polar substrates. How to achieve the physicochemical properties of solvent-based inks while also ensuring excellent and stable antistatic effects is an urgent problem to be solved.

[0007] Therefore, there is a need to provide an aqueous antistatic matting oil and its preparation method to solve the above problems. Summary of the Invention

[0008] The purpose of this invention is to provide a water-based antistatic matte oil and its preparation method, which has excellent adhesion to non-polar substrates. It can avoid the safety and environmental protection problems caused by harmful organic solvents in solvent-based inks, and at the same time solve the adhesion problem on difficult-to-adhere non-polar substrates, providing a stable and excellent antistatic effect.

[0009] The present invention achieves the above objectives through the following technical solutions:

[0010] One of the technical solutions:

[0011] A water-based antistatic matte oil, comprising a main agent and a diluent,

[0012] The main component consists of the following parts by weight:

[0013] 40-60 parts of waterborne polyolefin emulsion;

[0014] 5-10 parts of aqueous film-forming aid;

[0015] 1-2 parts of water-based wetting agent;

[0016] 0.5-1 part of water-based neutralizer;

[0017] 2-5 parts matte powder;

[0018] 10-20 parts deionized water;

[0019] 0.5-1 part of water-based defoamer;

[0020] 0.5-1 part of water-based thickener;

[0021] 5-15 parts of polythiophene dispersion;

[0022] 2-5 parts of quaternary ammonium compounds;

[0023] 5-15 parts of graphene dispersion;

[0024] The diluent consists of the following components in parts by weight:

[0025] 100 portions of deionized water.

[0026] Preferably, the aqueous polyolefin emulsion is selected from one or more of the following: Eastman Chemical's 510W, Walsin's HJ5138, Toyobo's NZ-1004, NU-1006, NZ-1015, NZ-1022, Nippon Paper's P-6682, Uniqlo's DA-1010, DC-1010, and Sumitomo Seika's ZAIKTHENE A.

[0027] Preferably, the aqueous film-forming aid is selected from one or more of the alcohol ether solvents DPNB, PNB, DB, BCS, and DPM.

[0028] Preferably, the aqueous wetting agent is selected from one or more of Evonik's TEGO Twin 4100, DYNOL 604, and SURFYNOL 465.

[0029] Preferably, the neutralizing agent is Eastman's DMEA, N,N-dimethylethanolamine.

[0030] Preferably, the matting agent is E-1011 from Tosoh Corporation of Japan.

[0031] Preferably, the aqueous defoamer is one or more of Evonik's TEGO Airex 902W, SURFYNOL 2502, and SURFYNOL 118.

[0032] Preferably, the water-based thickener is selected from one or more of Borchi-0620, Borchi-0630, and Borchi-0435, which are polyurethane associative thickeners from Borchies.

[0033] Preferably, the polythiophene dispersion is Lanh-01 from Wuhan Lanhong Optoelectronic Materials Co., Ltd.

[0034] Preferably, the quaternary ammonium compound is selected from CK-27 of Shanghai Youmiao New Material Technology Co., Ltd. and LanhS-66 of Wuhan Lanhong Optoelectronic Materials Co., Ltd.

[0035] Preferably, the graphene dispersion is GRF-TLGW-01 from Suzhou Greenford Nanotechnology Co., Ltd.

[0036] Technical Solution Two:

[0037] The preparation method of aqueous antistatic matte oil for thin film materials includes the following steps:

[0038] 1) Preparation of water-based base materials

[0039] a. Add the formulated amount of water-based polyolefin emulsion to the paint mixing container;

[0040] b. While stirring, slowly add the water-based film-forming aid and wetting agent in the prescribed amount;

[0041] c. While stirring, slowly add the amount of water-based neutralizer specified in the formula to adjust the pH value to 8-9;

[0042] d. While stirring, slowly add the formulated amount of matting powder, deionized water, and water-based defoamer;

[0043] e. While stirring, slowly add the prescribed amount of water-based thickener to adjust the viscosity to 800-1000 cP (Brook Field viscometer).

[0044] 2) Preparation of water-based conductive paste

[0045] f. In a paint mixing container, slowly add the formulated amounts of polythiophene dispersion, quaternary ammonium compound, and graphene dispersion, and stir thoroughly until homogeneous.

[0046] g. Grind the uniformly mixed semi-finished product using a grinder, controlling the speed of the sand mill at about 1000 r / min, and grind it 4 times until the fineness is ≤5μm.

[0047] 3) Preparation of water-based antistatic matting oil

[0048] h. Under stirring, the water-based conductive slurry prepared in step 2) is slowly added to the water-based base material prepared in step 1), and stirred thoroughly. The mixture is then filtered through a 200-mesh filter to obtain the main component of the water-based antistatic matte oil.

[0049] Compared with existing technologies, this invention has excellent adhesion to non-polar substrates, which can avoid the safety and environmental problems caused by harmful organic solvents in solvent-based inks, and at the same time solve the adhesion problem on difficult-to-adhere non-polar substrates, providing a stable and excellent antistatic effect. Attached Figure Description

[0050] Figure 1 This is a photograph showing the actual product obtained in Example 1;

[0051] Figure 2 The resistance testing instruments used in Example 1 and Comparative Examples 4-6 are shown. Detailed Implementation

[0052] The method of the present invention will be described below through specific embodiments to make the technical solution of the present invention easier to understand and master, but the present invention is not limited thereto.

[0053] In the following examples, the aqueous polyolefin emulsion used was DC-1010 from Uniqlo (Japan); the aqueous film-forming aid used was BCS ethylene glycol butyl ether; the aqueous wetting agent used was SURFYNOL 465 from Evonik; the aqueous neutralizing agent used was DMEA from Eastman; the matting agent used was E-1011 from Tosoh (Japan); the aqueous defoamer used was SURFYNOL 118 from Evonik; the aqueous thickener used was Borchi-0435 from Boscia; the polythiophene dispersion used was Lanh-01 from Wuhan Lanhong Optoelectronic Materials Co., Ltd.; the quaternary ammonium compound used was CK-27 from Shanghai Youmiao New Materials Technology Co., Ltd.; and the graphene dispersion used was GRF-TLGW-01 from Suzhou Greifong Nanotechnology Co., Ltd. Other reagents and materials, unless otherwise specified, were commercially available.

[0054] Example 1

[0055] An aqueous antistatic matte oil for thin film materials, comprising a main agent and a diluent, wherein:

[0056] The main component consists of the following parts by weight:

[0057] 40-60 parts of waterborne polyolefin emulsion;

[0058] 5-10 parts of aqueous film-forming aid;

[0059] 1-2 parts of water-based wetting agent;

[0060] 0.5-1 part of water-based neutralizer;

[0061] 2-5 parts matte powder;

[0062] 10-20 parts deionized water;

[0063] 0.5-1 part of water-based defoamer;

[0064] 0.5-1 part of water-based thickener;

[0065] 5-15 parts of polythiophene dispersion;

[0066] 2-5 parts of quaternary ammonium compounds;

[0067] 5-15 parts of graphene dispersion;

[0068] The diluent consists of the following components in parts by weight:

[0069] 100 portions of deionized water.

[0070] The aqueous antistatic matte oil for thin film materials described in the above embodiments is prepared by the following method:

[0071] 1) Preparation of water-based base materials

[0072] a. Add the formulated amount of water-based polyolefin emulsion to the paint mixing container;

[0073] b. While stirring, slowly add the water-based film-forming aid and wetting agent in the prescribed amount;

[0074] c. While stirring, slowly add the amount of water-based neutralizer specified in the formula to adjust the pH value to 8-9;

[0075] d. While stirring, slowly add the formulated amount of matting powder, deionized water, and water-based defoamer;

[0076] e. While stirring, slowly add the prescribed amount of water-based thickener to adjust the viscosity to 800-1000 cP (Brook Field viscometer).

[0077] 2) Preparation of water-based conductive paste

[0078] f. In a paint mixing container, slowly add the formulated amounts of polythiophene dispersion, quaternary ammonium compound, and graphene dispersion, and stir thoroughly until homogeneous.

[0079] g. Grind the uniformly mixed semi-finished product using a grinder, controlling the speed of the sand mill at about 1000 r / min, and grind it 4 times until the fineness is ≤5μm.

[0080] 3) Preparation of water-based antistatic matting oil

[0081] h. Under stirring, the water-based conductive slurry prepared in step 2) is slowly added to the water-based base material prepared in step 1), and stirred thoroughly. The mixture is then filtered through a 200-mesh filter to obtain the main component of the water-based antistatic matte oil.

[0082] Among them: Waterborne polyolefin emulsion: The selected waterborne polyolefin emulsion is an emulsion made from high-purity polyolefin as raw material. It uses a high molecular weight emulsifier to achieve high dispersion of polyolefin in water and has good adhesion to non-polar substrates that are difficult to adhere to. At the same time, because it contains polar substrates, it can also further improve the adhesion to polar substrates.

[0083] Waterborne film-forming aids: Cosolvents can reduce the viscosity of the entire waterborne coating system, provide wettability to pigments and fillers, improve dispersion, and are also an excellent film-forming aid, lowering the minimum film-forming temperature of MFFT and making the film-forming properties of the coating better.

[0084] Water-based wetting agents: reduce the surface tension of the coating, reduce the sensitivity of water-based coatings to substrate contaminants, enable water-based coatings to spread better on the substrate, and increase the fullness of the coating surface;

[0085] Water-based neutralizer: Adjusts the pH value of water-based coating systems to stabilize it at 8-9, which can improve the stability during later storage and prevent sedimentation and stratification;

[0086] Matting powder: It creates the desired roughness on the surface of the coating film, causing some refraction and diffuse reflection, thereby reducing the gloss of the coating film surface;

[0087] Water-based defoamer: Prevents bubbles caused by high-speed dispersion during the dispersion process, as well as bubbles that may appear during packaging and spraying.

[0088] Water-based thickeners: Thickeners are rheology modifiers that, under appropriate shear force, can increase the viscosity of water-based coatings and prevent sagging during application.

[0089] Polythiophene dispersion: Polythiophene is an organic polymer composed of thiophene monomers linked by covalent bonds. Its unique structure endows it with many distinctive properties and applications, especially its excellent electrical and electronic conductivity, making it an important organic conductive material.

[0090] Polythiophene can also have its properties tuned by introducing different functional groups or by doping. When combined with inorganic materials or ions, carbon nanotubes (graphene), it can produce excellent and stable conductivity.

[0091] Quaternary ammonium compounds: These are formed by the reaction of tertiary amines with alkylating agents (such as chloromethane, benzyl chloride, alkyl sulfates, etc.). They are commonly used as static eliminators and dyeing auxiliaries, and have excellent electrical conductivity and antistatic effects.

[0092] Graphene dispersion: Graphene is an allotrope of carbon, in which carbon atoms are arranged in sp... 2 Hybrid bonding forms a single-layer hexagonal honeycomb lattice graphene;

[0093] The crystal structure of graphene can be used to construct fullerenes (C60), graphene quantum dots, carbon nanotubes, nanoribbons, multi-walled carbon nanotubes, and nanoangles.

[0094] Graphene layers stacked together (more than 10 layers) form graphite, which is held together by van der Waals forces with a crystal plane spacing of 0.335 nanometers.

[0095] Graphene possesses excellent optical, electrical, and mechanical properties, and has significant application prospects in materials science, micro-nano fabrication, energy, biomedicine, and drug delivery. It is considered a revolutionary material for the future.

[0096] Comparative Example 1

[0097] The difference between this comparative example and Example 1 is that the DC-1010 waterborne polyolefin emulsion from Unigico (Japan) is replaced with an equal amount of W-631 waterborne polyurethane resin from Arakawa (Japan).

[0098] Same as Example 1.

[0099] Comparative Example 2

[0100] The difference between this comparative example and Example 1 is that the DC-1010 waterborne polyolefin emulsion from Unigico Japan is replaced with an equal amount of RE-2108 waterborne acrylic emulsion from Hoshiko Japan.

[0101] Same as Example 1.

[0102] Comparative Example 3

[0103] The difference between this comparative example and Example 1 is that the DC-1010 waterborne polyolefin emulsion from Unigico (Japan) is replaced with an equal amount of VINYBLAN 700 waterborne vinyl chloride resin from Nisshin (Japan).

[0104] Same as Example 1.

[0105] Comparative Example 4

[0106] The difference between this comparative example and Example 1 is that the aqueous conductive slurry used in this comparative example is Lanh-01 polythiophene dispersion from Wuhan Lanhong Optoelectronic Materials Co., Ltd.

[0107] Same as Example 1.

[0108] Comparative Example 5

[0109] The difference between this comparative example and Example 1 is that the water-based conductive paste used in this comparative example is entirely made from CK-27 quaternary ammonium compound from Shanghai Youmiao New Material Technology Co., Ltd.

[0110] Same as Example 1.

[0111] Comparative Example 6

[0112] The difference between this comparative example and Example 1 is that the aqueous conductive slurry used in this comparative example is GRF-TLGW-01 graphene dispersion from Suzhou Greifon Nanotechnology Co., Ltd.

[0113] Same as Example 1.

[0114] The above examples and comparative examples were diluted with deionized water to a suitable application viscosity and then applied using an anilox roller to six transparent film materials: PP, OPP, BOPP, PI, PET, and PVC.

[0115] After coating, bake at 80℃ for 5 minutes, and after removing from the production line, continue to cure at 60℃ for 24 hours. After cooling, conduct physical property tests. The adhesion test results are shown in Table 1.

[0116] The antistatic value of the coating on the BOPP film was measured at six different points. The stability of the antistatic value and the magnitude of the resistance value were also measured. The test results are shown in Table 2.

[0117] Table 1: Adhesion test results of products from Example 1 and Comparative Examples 1-3

[0118]

[0119] Table 2: Antistatic Test Results of Products from Example 1 and Comparative Examples 4-6

[0120]

[0121] As shown in Table 1, the waterborne polyolefin emulsion DC-1010 from Uniqlo (Japan) used in Example 1 exhibited an adhesion of 5B on six different film materials. In contrast, the products provided in Comparative Examples 1-3 showed poor adhesion to non-polar substrates such as PP, OPP, BOPP, and PI. The waterborne polyurethane resin W-631 from Arakawa (Japan) used in Comparative Example 1 showed good adhesion only to PET and PVC. The waterborne acrylic emulsion RE-2108 from Hoshikatsu (Japan) used in Comparative Example 2 also showed good adhesion to PET and PVC. The waterborne vinyl chloride resin VINYBLAN 700 from Nisshin (Japan) used in Comparative Example 3 also showed some adhesion to PI and BOPP. Therefore, the waterborne polyolefin emulsion used in this invention exhibits the best versatility in adhesion to different film materials and has the widest range of applications.

[0122] As shown in Table 2, the product provided in Example 1 maintained a stable resistance of 106.2Ω at six different test points, meeting the antistatic resistance requirement of 106-109Ω, demonstrating excellent and stable antistatic performance. In contrast, the resistance values ​​of the products provided in Comparative Examples 4-6 fluctuated to varying degrees, failing to meet mass production requirements. Comparative Example 4 used Lanh-01 polythiophene dispersion from Wuhan Lanhong Optoelectronic Materials Co., Ltd. Due to its conductive mechanism, it easily forms covalent bonds with resin additives and co-solvents in the water-based ink system, leading to fluctuations in its resistance value. Comparative Example 5 used CK-27 quaternary ammonium phosphate from Shanghai Youmiao New Materials Technology Co., Ltd. The compound, belonging to the cationic surfactant class, easily forms complexes with ions in water-based inks, causing fluctuations in resistance. Moisture absorption after the coating dries also leads to resistance fluctuations. The water-based conductive paste used in Comparative Example 6 was entirely composed of GRF-TLGW-01 graphene dispersion from Suzhou Greifong Nanotechnology Co., Ltd., a 10wt% dispersion. After special treatment, its thin-layer structure was coated with water-based resin, resulting in unstable conductivity of the coating. Therefore, the water-based conductive paste used in this invention, through grinding pretreatment, effectively combines the three conductive materials in advance, greatly improving its conductivity stability and exhibiting excellent and stable antistatic effects, showing great application potential in the field of electronic products.

[0123] The above descriptions are merely some embodiments of the present invention. Those skilled in the art can make various modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the scope of protection of the present invention.

Claims

1. A water-based antistatic matte oil, characterized in that, Includes main agent and diluent, The main agent is composed of the following components in parts by weight: 40-60 parts of waterborne polyolefin emulsion; 5-10 parts of aqueous film-forming aid; 1-2 parts of water-based wetting agent; 0.5-1 part of water-based neutralizer; 2-5 parts matte powder; 10-20 parts deionized water; 0.5-1 part of water-based defoamer; 0.5-1 part of water-based thickener; 5-15 parts of polythiophene dispersion; 2-5 parts of quaternary ammonium compounds; 5-15 parts of graphene dispersion; The diluent consists of the following components in parts by weight: 100 portions of deionized water.

2. A method for preparing an aqueous antistatic matting oil, used to prepare the aqueous antistatic matting oil according to claim 1, characterized in that: It includes the following steps: 1) Preparation of water-based base materials a. Add the formulated amount of water-based polyolefin emulsion to the paint mixing container; b. While stirring, slowly add the water-based film-forming aid and wetting agent in the prescribed amount; c. While stirring, slowly add the prescribed amount of water-based neutralizer to adjust the pH value to 8-9; d. While stirring, slowly add the formulated amount of matting powder, deionized water, and water-based defoamer; e. While stirring, slowly add the water-based thickener according to the formula, and adjust the viscosity value to 800-1000 cP using a Brookfield viscometer. 2) Preparation of water-based conductive paste f. In a paint mixing container, slowly add the formulated amounts of polythiophene dispersion, quaternary ammonium compound, and graphene dispersion, and stir thoroughly until homogeneous. g. Grind the uniformly mixed semi-finished product with a grinder, controlling the speed of the sand mill at about 1000 r / min, and grind it 4 times until the fineness is ≤5μm; 3) Preparation of water-based antistatic matting oil h. Under stirring, the water-based conductive slurry prepared in step 2) is slowly added to the water-based base material prepared in step 1), and stirred thoroughly. The mixture is then filtered through a 200-mesh filter to obtain the main component of the water-based antistatic matte oil.

3. The method for preparing an aqueous antistatic matting oil according to claim 2, characterized in that, In step d of the mixing stage, the main agent is prepared by adding the prescribed amount of matting powder and stirring at a dispersion speed of 800-1200 r / min for 10-20 min; the remaining steps are dispersed at a dispersion speed of 400-800 r / min.

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