TWI304084B - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for forming a surface coating of a special surface, =1 曰 one suitable for coating on, for example, a metal surface , metal painted surface, glass surface or plastic surface, composition. a coating agent for forming the surface coating [Prior Art]

In the art: in the art, for example, metal alloys such as alloys, stainless steels, etc., due to their high strength and good processability, industrially, however, there is an important disadvantage in the use of metal materials: In the middle of the quilt, it is also easily contaminated by oil, resulting in poor appearance of the substrate 2 and durability. In order to improve the above-mentioned defects, there are two common treatment methods in the known technique, namely, powder baking varnish, which is a film treatment, that is, in the prior art, used to protect the surface of the substrate. Although there are many types of treatment methods and paints, it is inevitable that there is oil staining and difficulty in cleaning during use. SUMMARY OF THE INVENTION The object of the present invention is to provide a metal substrate, a metal baking substrate, an alloy baking substrate, a glass substrate, and a plastic substrate surface, and has a good antifouling effect for forming surface coating. The coating composition of the layer. The coating composition of the present invention can be applied to the substrate in any form to form a surface coating having an antifouling effect, and the substrate can be directly coated without being cleaned before coating. Dry molding. The substrate suitable for the present invention can be various carbon steel metals, carbon steel metal baking varnishes, alloy 1304084 baking μ and acrylic resin, epoxy resin, waterborne polyurethane (pu) resin, glass. , or a plastic substrate made of a polymer blend or a copolymer thereof. The above coating composition comprises: 100 weight-damaged surface treatment liquid, the surface treatment liquid comprises: 95 to 99.7 parts by weight of a solvent, and 0 3 to 5% by weight of a bridging agent, wherein the solvent is selected from the group consisting of: a ketone alcohol having 4 to 7 carbon atoms, a ketone having 5 to 7 carbon atoms, and an ester having 3 to 8 carbon atoms, and the specific keto alcohol solvent may be diacetone alcohol ( Diacet〇ne alc〇h〇l), specifically ^ = solvent can be methyl isobutyl ketone (Methyl is〇butyl 匕丨 (10) e), while the body of the solvent is ethyl acetate (Ethyl acetate), acetic acid Zheng Ding (four) called acetate). According to the experimental results, it is shown that the ratio of the above three solvents must be between 1: 0.25 and 0.55: 0.3 to 0.8, in order to achieve the intended object. The bridging agent is a precursor of cerium oxide or aluminum oxide, for example, fluorophthalic acid ester (Flu〇r〇 "" such as benz〇tate), fluorohydroxyl ketone (Fluoro Silane hydr〇) Xyi_ket〇nes), as well as organic or dentate type bismuth and aluminum compounds. In order to achieve better dispersibility, a dispersing agent can be used simultaneously with bismuth and aluminum compounds, so that the formed cerium oxide and the second emulsified one have Better dispersion effect. 40 to 90 parts by weight of a main agent selected from the group consisting of acrylic resin resins (Acrylic poly〇ls f〇rp〇lyurethanes_η) for polyurethane coatings, and acrylic polyurethane polyester resins ( One of Acrylic p〇lyamides_ ployesters resin, or a mixture of the two. 4 to 3 parts by weight of a hardener. The purpose of the ketol solvent in the present invention is to make the surface coating of 6 1304084 $ d, 'and the product is weakly tested, the purpose is to make various types of polyurethane vinegar coated 7 Alcohol tree month, as well as acrylic $ ammonia vinegar polyester resin, etc., easy to form a copolymer structure of wooden bridges, as a protective film composed of a flaw (5) 4 and other stone metal or fluoride ion protection in the stripping agent Sex film. The S-like solvent of the invention can provide the same bridging machine J as the coating material, and the thickness and viscosity of the composition of the δ-hai composition at the time of coating, the above-mentioned bismuth solvent village and other solvents form a bonding effect, and the pending treatment Various types of coatings are used to make the coatings. The coatings d used in the present invention are also provided with a bridging mechanism and viscosity control with other compositions to: bond polyurethane urethane coatings Acrylic polyol resin and acrylic ammonia 曰 曰 ♦ According to the eucalyptus tree, the ratio m between the ketone alcohols, ketones and ester solvents is limited, and the purpose is to control the polarity of the composition. The vinegar and the bridging agent (precursor) can be mixed uniformly, and the composition can be easily laid on the surface of the substrate, and the amount of use between the bridging agent and the solvent is limited, mainly to control the water splashing of the composition. And the effect of pouring oil. The value of the present invention is that the above-mentioned composition of the present invention is not only low in environmental pollution, but also can form an antifouling on the surface of the substrate. Paint composition is coated The reason for the excellent antifouling effect is that the composition can be coated on the surface of the substrate to form nano-sized "cerium oxide" 4 "aluminum oxide" particles, and a so-called lotus effect is produced. (Lotus Effect), the self-cleaning effect of the surface, which prevents the oil from adhering and seeping into the coating. Therefore, when the oil stain falls on the surface coating, it is only a light l3〇4〇84 It can be easily removed, so the composition of the present invention also has an excellent antifouling effect. The solvent of the present invention can be further added with respect to the ketones of the ketones of the ketones. In the eve of the eve-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Adhesion on the surface - The bridging agent selected for use in the present invention has similar chemical properties to the main agent, and I aims to improve the copolymerization bonding effect between the other components of the composition and the main agent. The purpose of using the hard agent in the present invention is Make the composition have When the hardness is higher than the set upper limit, the composition is too saturated to form a hard block, and if the amount used is lower than the set lower limit, the hardness of the composition after coating is insufficient. The composition is kneaded and polymerized according to a set ratio, and can be manufactured into a coating composition suitable for coating on, for example, a surface of a metal substrate, a surface of a metal baking substrate, a surface of a glass substrate, and a surface of a plastic substrate to form a surface coating. The surface of the substrate on which the coating composition is preliminarily coated is subjected to a step of degreasing, water washing and drying, that is, the preparation action of the substrate is completed, and then the coating composition is attached to the base by dip coating or spraying. The surface of the material, the thickness of the plating layer is preferably 1 to 30 / / m, and then the composition is dried, so that the composition of the surface coating agent is firmly attached to the surface of the substrate to achieve antifouling half Efficacy. In the process of hardening the coating, the mechanism for simultaneously forming the nano antifouling structure on the surface of the substrate is very complicated. According to the inventors' speculation, the appearance and efficacy of the final surface may be related to the formulation and configuration steps of the coating. 8 1304084 In the structure of the formulation of the present invention, the oblique #f χ. -^r is a precursor to the formation of surface nanoparticles, and it is necessary to adjust to a uniformity of mixing which is stable enough to be preserved in a macroscopic homogeneous long time. In the actual process of coating and baking, 0 must ensure organic stone and organic! The nano-precursor with the main component of Lu can form a nano-structure on the surface of the substrate by condensation and hydrolysis, so that it can be displayed on the upper surface of the lotus structure, and achieve oil-proof purpose.

[Embodiment] Hereinafter, the present invention will be described in detail with reference to the examples and comparative examples. [Example 1] As shown in Table 1, 49 g of diacetone alcohol, 17 g of methyl isobutyl g, and 25 g of ethyl acetate were mixed and used. Then, 4g of bridging agent of "Si-E1000", which is sold under the trade name "Jingming Nano Biotechnology Co., Ltd." and "Si-E1000", and 2〇g are manufactured by "Yu Trading Co., Ltd." in 65g of acrylic polyol resin. YT-20H hardener (a kind of methylated melamine-formaldehyde resin, Chinese name is methylated hydrazine, amine-methyl resin), and finally added with dipropanol, methyl isobutyl ketone and ethyl acetate After the solvent is uniformly mixed, the coating composition required for the present invention can be prepared. Take a piece of stainless steel test piece with a thickness of 6cm x 10cm and a thickness of 〇_5~lmm, and carry out the pretreatment work on the test piece by the steps of degreasing, washing and drying. Then, a surface composition having an average thickness of 20 // m was sprayed on the surface of the test piece. After spraying, the test piece was allowed to stand at room temperature (about 25 to 28 ° C) for a minute, and then baked. The surface coating is formed by dry curing. In the present embodiment, the A^9:304084 operation may be different depending on the heating temperature, or the ancient and western knives are the same type of drying and the low temperature type bait & species, complex φ, ancient, and western agents.仏,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The time and temperature control for the low temperature type dry work is 1 minute for hunger, 2 minutes for machine, and 55 minutes for 55 minutes. The coating process of the paint composition is completed by the above steps.

The performance test of each test piece was carried out. The performance test included: adhesion, surface hardness, antifouling (oil splashing) and water repellency. The test results are shown in the table.

10 1304084 Table # Example Surface treatment liquid main agent (g) Hardener (g) Solvent (g) Bridging agent (g) Diacetone alcohol oxime isobutyl ketone ethyl acetate n-butyl ester xylene 1 49 17 25 0 0 4 65 20 91 2 60 13 30 0 0 5 44 10 103 3 38 20 16 0 0 0.3 65 25 74 4 60 , 15 20 0 0 4 50 5 95 5 38 18 30 0 0 3 65 20 86 6 49 17 15 10 10 4 80 26 101 7 45 17 15 0 14 3 64 26 91 8 49 17 15 0 7 4 64 25 88 11 1304084 Table 2 Test items Adhesive surface hardness Antifouling (oil splashing) Water repellency Example 1 OK 1H There is a slight residual image OK Example 2 OK 1H There is a slight residual image OK Example 3 OK 1H There is a slight residual image OK Example 4 OK 1H There is a slight residual image OK Example 5 OK 1H There is a slight residual image OK Example 6 OK 2H OK OK Example 7 OK 2H OK OK Example 8 ---- OK — ----- A 2H OK OK <Test Method> 1·Adhesion (Baige Test Method): Apply on the surface of the substrate A number of criss-crossed glues v are applied to the layer, and then the tape is peeled off the surface coating. When the surface coating is almost free of peeling, it is represented by "〇κ", and a small part is peeled off. "NG" means 〇2. Surface hardness: The surface coating is scraped with a pencil of various hardnesses, that is, if there is no scratch when scratching the surface coating with a 2h pencil, it is indicated by "211", if the surface coating is applied by 1H pencil If there is no scratch, it is indicated by "1H". 3. Anti-fouling (oil-repellent): Mark the coating on the test piece with an oil-based pen. It can be wiped with "OK" and cannot be wiped with "ng". 4. Water repellency · The test piece is immersed in pure water and then taken out. When there is water residue on the coating of the test piece, it is represented by "NG", and when the water droplets do not adhere to the coating, it is indicated by the factory OK. . 12 1304084 [Examples 2 to 8]

The preparation method and the test piece are manufactured in the same manner as in the first embodiment, except that the formulation has a proportional relationship (as shown in Table 1), wherein the main components of the examples 5 to 8 are changed to an acrylic polyurethane resin, and the test piece is The substrate is different, wherein the embodiment 2 is a stainless steel substrate, the embodiment 3 is a carbon steel substrate, the embodiment 4 is a baked aluminum alloy substrate, the embodiment 5 is an aluminum-magnesium alloy substrate, and the embodiment 6 is cast iron. The substrate, the glass substrate of Example 7 and the polypropylene substrate of Example 8 were used. Example 5~6 bridging agent was changed to "Jingming Nano Biotechnology Co., Ltd." "Si-E1000A"; Example 7~8 bridging agent was changed to "Jingming Nano Biotechnology Co., Ltd." "Si-E1〇〇 OB". Example 6 further had 10 g of n-butyl acetate. The performance tests of the various embodiments are also shown in Table 2. [Comparative Examples 1 to 12] The preparation method and the test piece were produced in the same manner as in Example 1, except that the ratio of the formulations was as shown in Table 3, and the test results of the test pieces are shown in Table 4 Table 3 ^

13 1304084

87 5 60 13 25 0 0 7 50 20 98 6 42 20 18 0 0 0.1 55 20 80 7 38 18 16 0 0 2 78 20 72 8 60 15 25 0 0 5 25 20 100 9 60 15 25 0 0 5 5 0 3 100 10 38 20 16 0 0 3 60 30 74 11 45 17 15 0 20 3 64 26 97 12 49 17 19 0 3 4 64 20

14 1304084

Table 4 Test items Adhesive surface hardness Antifouling (oil splashing) Water repellency Comparative Example 1 NG 1 Η - but uneven ΟΚ - but uneven 〇 κ - but unevenness Comparative Example 2 Insufficient viscosity, difficult to adhere, and insufficient thickness Test Comparative Example 3 The viscosity was too high, it was difficult to spray, and bubbles were generated to make the appearance uneven. No comparison was made. Comparative Example 4 Insufficient viscosity, difficult to adhere, and insufficient thickness were not tested. Comparative Example 5 NG 1Η - Uneven NG NG Comparative Example 6 NG 1Η - Uneven ΟΚ ΟΚ Comparative Example 7 OK 0 Η ΟΚ ΟΚ Comparative Example 8 NG 1 Η NG NG Comparative Example 9 OK 0 Η ΟΚ (but with afterimage) ΟΚ Comparative Example 10 NG 1 Η ΟΚ ΟΚ Comparative Example 11 OK 1 Η - uneven ΟΚ ΟΚ Example of car exchange 12 OK 1Η-unevenness ΟΚ 15 .1304084 The test results of Comparative Examples 1 to 4 show that when the range of the invention is _alcohol solvent, ketone solvent, and A, the ratio of -4 is not Falling into this «W into, and the viscosity of the object is not enough, / smooth formation of the predetermined 〇 on the substrate... Test Society ^ ◊厗. From Comparative Examples 5 and 6, "the effect is not, when the amount of solvent used is less than 95% of the surface treatment liquid = ^ is higher than 99, 7 wt% ^ cut __ (four) _ two! Agent and: main agent dissolved Uneven hook. Test by Comparative Examples 7, 8

',, mouth Wo Chuan know that when the use of the main agent #田旦 is lower than the set value of the present invention, the thickness of := is too thick, the hardness is lowered, and when the amount of the main agent is used, the door is 1S When the set value is used, not only the antifouling property is not good, but also the adhesive tongue: in addition, when the amount of the hardener used in the present invention is less than 4 denier per serving, not only the surface hardness is poor, but also the antifouling test may be caused. The shirt, and when the amount of the hardener used is too high, the rapid reaction of the solvent to t is disadvantageous for coating the composition, which is confirmed by the test results of Comparative Example 9 and: 0 of the present invention. The comparative example is called 2 mainly in ° and clear, and the amount of xylene added by the present invention is not in this case! When X is within the range of the boundary, the hardness of the new product is not uniform. As is apparent from the disclosure of the various embodiments of the present invention, the present invention adds a composition according to a predetermined ratio, and it is indeed possible to produce a paint composition having a better antifouling effect. However, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention, All remain within the scope of the invention patent. 16

Claims (1)

1304084 X. Patent application scope: 1 · A paint composition comprising: iuu Dong heavy heart coat from a treatment liquid, the surface treatment liquid is coated with 95 to 99.7 wt% of a solvent, and 〇.3 to 5 wt% of a bridging agent The solvent comprises: a ketone having 4 to 7 carbon atoms, wherein a ketone having 5 carbon atoms, and an ester having 3 to 8 carbon atoms, and a double The ratio of the two solvents used is 1: 〇_25~0.55: 〇3n. · * • ~υ.8, and the shelf The bridge agent is a precursor of cerium oxide or aluminum oxide; 4 〇 to 90 parts by weight of a main agent selected from the group consisting of polyamino carboxylic acid _ acrylic polyol resin for coating, and acrylic polyurethane polyester One of the resins' or a mixture of the two; and 4 to 35 parts by weight of the hardener. 2. The coating composition according to the scope of the claims of the patent, wherein the ketone solvent refers to a dipropyl type I alcohol, and the ketone solvent refers to mercapto isobutyl ketone, and the vinegar solvent refers to acetic acid. Ethyl ester. 3_ The coating composition according to claim 1, wherein the keto alcohol/mixture refers to diacetone alcohol, and the ketone solvent refers to mercapto isobutyl ketone, and the vinegar solvent refers to acetic acid Vinegar and n-butyl acetate. 4. The toluene composition is further added in an amount of from 0.1 to 0.3 parts by weight based on 1 part by weight of the ketol solvent. 17