TWI358432B - Uv harden type nano paint and methods for manufact - Google Patents

Description

1358432 - 100 years. June 15th, nuclear replacement page 6. Description of the invention: [Technical field of invention] [0001] The present invention relates to a coating system, in particular to a UV which is resistant to dirt, water and durability. Photocuring type nano coating, preparation method and use method thereof. [Prior Art] [0002] With the improvement of living standards, people have higher and higher aesthetic requirements for the decoration of living environment, indoor furniture such as piano, etc., and put forward higher anti-fouling, waterproof and durability of paints. The requirements, while the traditional coating benefits can not meet the visual needs of consumers. [0003] Coatings of conventional coatings generally include primers and topcoats, which are the beginning of the entire coating and are directly attached to the surface of the substrate, and are usually used to provide color, seal the substrate, enhance the adhesion of the topcoat to the substrate, etc. . The topcoat is typically a clear natural or metallic lacquer that is blended with the primer to give the entire coating a high gloss. The coating process is as follows: firstly, the surface of the substrate is treated to remove surface oil, mold release agent, dust, and debris; the primer is uniformly stirred; sprayed; and dried at room temperature for 10 to 20 minutes; Add special curing agent to the paint, stir evenly with the top coat; spray; dry it for 10~15 minutes after spraying, put it into the oven at normal temperature, warm it to 50-60 degrees, keep it for 60 minutes, and get the coating. [0004] However, the conventional paint has poor stain resistance, water resistance and durability, and after raining, dust adhesion and sunlight, the surface of the coating will adhere to dirt and lose its original luster. In view of the above, it is necessary to provide an ultraviolet light-hardening type nano-coating which is excellent in stain resistance, water repellency and durability, a preparation method thereof and a method of using the same. 094129214 Form Number A0101 Page 4 of 19 1003212650-0 1358432 [0006] [0007]

[0009] [0010]

[0011] 100 years, June, and 5th, the correction of the page is made. [Explanation] Hereinafter, an ultraviolet light-curable nano-coating which is excellent in stain resistance, water resistance, and durability, a preparation method thereof, and a method of using the same will be described by way of examples. In order to achieve the above, an ultraviolet curing type nano coating is provided, and the ultraviolet curing type nano coating comprises a double bond propylene oligomer having a content of 5 to 25%, and the content is 5 to 25%. The propylene monomer, the content of 0. 5% of the pigment particles, the content of 0. 5% of the photoinitiator and the balance of the solvent. The carbon black particles having a particle diameter of 191.4 nm or less. In addition, a method for preparing the ultraviolet light-curable nano-coating material is provided, which comprises the steps of: 5% to 25% of the total system containing double bond propylene oligomer, 5 to 25% of propylene monomer, 0 5% of the pigment particles and 0. 5% of the photoinitiator are sequentially added to the reactor previously charged with an appropriate amount of solvent; and stirred to make it uniformly mixed. And a method for using the ultraviolet light-curable nano-coating material, comprising: coating the coating material on a surface of a workpiece to form a coating; forming a coating film; and polymerizing by ultraviolet light to form an ultraviolet hardening layer. The formed ultraviolet hardening layer includes a resin having the following structural formula and pigment particles dispersed in the resin: 094129214 Form No. A0101 Page 5 of 19 Page 1003212650-0 1358432 [0012] Η 100 years. June 15th nuclear Positive replacement page m

Ten C——C 0=C 0==0 0 = 0 is called RF· ό. χ (4)

In the formula, R is an alkyl chain having a carbon number of 4, a χ value of 1 to 3, and an m value of 83 to 277. [0014] Compared with the conventional topcoat of the prior art, the ultraviolet curable nano-coating of the present invention can be directly cured by ultraviolet light, and the ultraviolet hardening layer contains a fluorine side which is poor in compatibility with the resin and has a low specific gravity. The fluorinated side chain forms a acicular structure layer that floats on the surface of the ultraviolet hardened layer. The acicular structure layer has the advantages of low surface tension and good hydrophobicity; and the pigment particles having a particle diameter of 191. 4 nm or less are cured together with the resin. The surface of the ultraviolet hardened layer forms a micro-protrusion structure of "Lotus effect". This kind of structure is conducive to the development of the "Lotus Effect". Moreover, compared to conventional coatings, the nano-coating has a short drying time and fast drying. Therefore, the nano-coating designed by the molecular structure of the technical solution has the advantages of fast drying, anti-fouling, waterproof, and durability. [Embodiment] [0015] The ultraviolet curable nano coating of the present invention includes a propylene-based oligomer containing a double bond, a propylene monomer, a pigment particle, a photoinitiator, and a solvent. [0016] The structural formula (I) of the double bond-containing propylene oligomer is: 094129214 Form No. A0101 Page 6 of 19 1003212650-0 1358432 001

ο IIH.—r.!0LQ J II C =- · “γ H丨cjG·丨R . II 100 years. June 15th revised replacement page it tSiO) [0018] where R is a carbon atom The alkyl chain of ~4 has an x value of 1 to 3, and since the structural formula contains an active double bond, it is easily polymerized with other active materials. The double bond-containing propylene-based oligomer content is 5 to 25% by weight, preferably 10 to 20% by weight based on the total amount of the coating. [0019] The structural formula (Π) of the propylene monomer is: [0020] wherein R and R2 are each an alkyl chain having a carbon number of 4, since the structural formula contains a reactive active conjugated double The bond is therefore highly active and easily polymerizes with other active substances. The propylene monomer content is 5 to 25% by weight, preferably 10 to 20% by weight based on the total amount of the coating. 4纳米。 [0022] The particle size of the nano-particles of the carbon black is 191. 4nm. 5〜4. 5%。 By weight, the amount of the pigment is 0. 1~5%, preferably 0. 5~4. 5%. [0023] The photoinitiator may be Benzophenone (BP), diphenyl 094129214 Form No. A0101 Page 7 / 19 pages 1003212650-0 1358432 [0024] [0025] [0027] [0028] ] 100 years. June 15th revision _ page 乙乙二明 (Diphenylgly〇xal) or restoring photoinitiator, ~~- by weight, it initiator content is the total amount of paint q 5%, preferably 0. 5*·4. 5%. In order to obtain a better coating appearance, a solvent of methyl ethyl ketone (Methyl Ethyl, ship) and methyl isobutyl group is used to make a mixture of thyl is butyl ket _ The ratio is preferably 1: methyl ethyl hydrazine, also known as methyl ethyl ketone, and has a density of 面. Methyl isobutylmethyl, also known as iso-hexyl or methyl isoamyl ketone, scientific name 4-methyl-2_pentanyl. Molecular enthalpy CH3C0CH2CH(CH3)2, relative density (water = υΛ〇 (25 υ. 孀 技术 « « « 料 料 料 料 料 料 料 料 料 料 料 料 料 料 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备5 gamma (4) monomer, 〇. 5% of the pigment particles and 5% of the light 5% of the light agent are added to the reactor in advance to the required solvent, and maintain the _ state, so that they are mixed = _ Fine _ mix _ mix, ^ _ when the ship is not large, you can use electromagnetic search or super, time system is always fixed, can be several hours to = · The use of the paint includes the following steps: The good mixture is applied to the surface of the part to obtain a coating. Nowadays, it is preferable to make the process of dip coating (4), and the appearance of the coating formed by different coating processes may be different. , the process uses low temperature heat treatment to form a film preferably ~(10) 094129214

Form No. A010I Page 8 of 19 1003212650-0 1358432

The temperature of the replacement page is corrected on the i5 day of the 00, .6, and the time is preferably 5 to 10 minutes, and can be sent to an oven or hot air. [0029] Finally, the workpiece is subjected to ultraviolet light treatment, and the workpiece is sent to the ultraviolet exposure machine for illumination through a conveyor belt, the conveyor belt speed is 7-15 ft / min, and the exposure machine irradiation energy is 0.4 joules per square centimeter, which is induced by light. Under the action of the agent, the double bond-containing propylene-based oligomer is photopolymerized with the propylene monomer, and the light is cured, and the time required is only about 1 second, and finally an ultraviolet hardened layer is obtained. [〇〇3〇] The formed ultraviolet hardened layer includes a resin having the following structural formula (m) and pigment particles dispersed in the resin:

In the formula, R and R2 are each an alkyl chain having a carbon number of 4, an X value of 3, and an m value of 83 to 277. [0033] in the formed ultraviolet hardened layer, the fluorine side chain contained therein is strongly polar, and thus the compatibility with the obtained resin is not good, and the specific gravity of the fluorine is lower than that of the obtained resin, thereby being polymerized. The fluorinated side chain floats from the surface of the resin to form a needle-like structure on the surface layer, thereby forming a low surface tension of 094129214. Form No. A0101 Page 9 of 19 1003212650-0 1358432 • '[ϊάο年.06月is is The surface of the fluorine is the surface layer. The fluorine-based surface layer has a hydrophobic β-correcting pin because of its low surface tension, and the pigment particles having a particle diameter of 191.4 or less are coated in the obtained ultraviolet-curing layer and uniformly dispersed after being cured by ultraviolet light. After the pigment particles dispersed in the surface layer of the ultraviolet hardened layer are cured, they appear as microprojections on the surface of the ultraviolet hardened layer. [0037] The coating system having such a structure is similar to the structural feature of the "Lotus effect" occurring in natural phenomena, and has the advantages of anti-fouling waterproofing and high durability. The first embodiment of the ultraviolet curing type nano coating of the present invention is: sequentially adding 1 gram of propylene-based oligomer (I) and 20 g of propylene in a reactor containing 85.6 ml of methyl ethyl ketone solvent. Monomer (n), 〇 5 g of carbon black particles having a particle size of 137. Omn and 0.5 g of dicumyl ketone were maintained for 5 hours to be thoroughly mixed. The stirred mixture nozzle is applied to the surface of the workpiece to be processed, and then sent to the oven, heat-treated at 6 (about 5 minutes for TC, and finally sent to the exposure machine for exposure curing treatment, the transmission catch is 15 ft / min, and the exposure machine is 0.4 Joules per square centimeter, obtained - UV hardened layer A » The obtained UV hardened layer A was placed under an atomic force microscope to observe its surface morphology 'to obtain an atomic force microscope photograph as shown in the first figure. · This technical scheme UV hardening type The second embodiment of the rice coating is as follows: in a reactor containing 73. 1 ml of methyl isobutyl ketone solvent, 20 g of propylene oligomer (I), 20 g of propylene monomer (jj), 1 are sequentially added. The gram% is 17 〇 nm carbon black particles and 0.5 gram of benzophenone, and is maintained for 8 hours to make it fully mixed. The mixed mixture is applied to the surface of the workpiece to be added, and then fed. Oven, heat treatment at 6 (rc for 5 minutes, last 15 minutes with 15w medical germicidal UV lamp, enter exposure curing treatment 094129214 Form No. A0101 Page / Total 19 pages 1003212650-0 I35S432 .1:00-year.06 On the i5th of the month ^ page, to obtain an ultraviolet hardened layer B. The obtained ultraviolet hardened layer B was placed under an atomic force microscope to observe its surface morphology, and an atomic force microscope photograph as shown in Fig. 2 was obtained. [0038] The present invention is an ultraviolet light curing type. The contrast implementation of nano paint is as follows:

In a reactor containing 85.6 ml of methyl ethyl ketone solvent, 10 g of propylene-based oligomer (I), 20 g of propylene monomer (Π), and 0.5 g of carbon black having a particle diameter of 191.4 nm were sequentially added. The particles and 0.5 g of diphenyl fluorenone were stirred for 5 hours to make them fully mixed. The stirred mixture is sprayed on the surface of the workpiece to be processed, then sent to the oven, heat treated at 60 ° C for 5 minutes, and finally sent to the exposure machine for exposure curing treatment, the transfer speed is 15 feet / minute, 0 in the exposure machine. 4 joules per square centimeter gives a UV hardened layer C. The obtained ultraviolet hardened layer C was placed under an atomic force microscope to observe its surface morphology, and an atomic force microscope photograph as shown in Fig. 3 was obtained. [0039] Observing the atomic force microscope photographs shown in the first, second, and third figures, wherein the floating needle-like structure is generated by the floating side chain of the fluorine from the surface of the resin, and the micro-protrusion below the needle-like structure That is, carbon black nanoparticles are cured by a resin coating. This kind of structure can produce a “Lotus Effect”, which is good for the anti-staining and waterproofing of paints. Comparing the above photos, it is found that when the particle size of the carbon black particles is 137. Onm, the structural features of the "Lotus effect" are most prominent, the needle-like structure is the most prominent, and the micro-protrusions on the surface are also the most obvious; when the particle size is 170 nm , having the structure of the "Lotus effect", but relatively weak; and when the particle size is 191.4 nm, the structural features are less obvious. Therefore, it can be concluded that the smaller the particle size of the pigment particles, the more favorable the "Lotus effect" occurs, and the particle size is less than or equal to 191.4 nm. That is, the particle size of the pigment particles is hard for ultraviolet 094129214. Form No. A0101 Page 11 of 19 1003212650-0 [0040] [0044] [0044] [0044]

* 11 years. On June 15th, it is important to repair the anti-fouling waterproof effect and durability of the replacement layer I. Compared with the conventional topcoat of the prior art, the ultraviolet hardening layer of the ultraviolet curing type nano coating of the technical solution contains a fluorine side chain which is compatible with the resin and has a low specific gravity, and the fluorine side chain is formed to float out. a needle-like structural layer on the surface of the ultraviolet hardened layer, the needle-shaped structural layer has the advantages of low surface tension and good hydrophobicity; the pigment particles having a particle diameter of 191.4 (10) or less are solidified together with the resin to make the surface of the ultraviolet hardened layer form a ''Lotus Effect, the microprotrusion structure. This kind of structure is conducive to the "rainlet effect". Moreover, compared to conventional coatings, the nano-coating has a short drying time and fast drying. Therefore, the nano-coating obtained by the molecular structure design of the technical solution has the advantages of quick dryness, anti-fouling, waterproofness and high durability. In summary, the present invention complies with the requirements of the invention patent and submits a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described embodiments, and those skilled in the art will be equivalently modified or changed in accordance with the spirit of the invention. All should be included in the scope of the following patent application.

BRIEF DESCRIPTION OF THE DRAWINGS H The first figure is an atomic force micrograph of the ultraviolet hardened layer obtained in the first embodiment of the present technical solution. The second figure is an atomic force micrograph of the ultraviolet hardened layer obtained in the second embodiment of the present technical solution. The third figure is an atomic force micrograph of the ultraviolet hardened layer obtained in the second embodiment of the present technical solution. [Description of main component symbols] 094129214 Form No. A0101 Page 12 of 19 1003212650-0 135&432 [0045]None 100 years. June 15th revised replacement page

094129214 Form No. A0101 Page 13 of 19 1003212650-0

Claims (1)

1358432 . ; _ _ . .i 100 years. June 1 '5 revision replacement page VII, the scope of application for patents: 1. An ultraviolet curing type nano coating, the UV curing type nano coating includes The photoinitiator having a content of 5 to 25% of a propylene monomer having a double bond, a propylene monomer having a content of 5 to 25%, a content of 0. And a balance of the solvent, wherein the double bond propylene-based oligomer has a fluorine side chain. 2. The ultraviolet light-curable nano coating according to claim 1, wherein the double bond propylene oligomer has the structural formula: Η: Η II c = c:=c. J .1 O = CG = Ο t · ** ·- II RF Ο Ι where R is an alkyl chain having a carbon number of 4 and an x value of 1 to 3. 3. The ultraviolet light-curable nano-coating material according to claim 1, wherein the content of the double-bonded propylene-based oligomer in i is 10 to 20%. 4. The ultraviolet light-curable nano coating according to claim 1, wherein the propylene monomer has the structural formula: - R Ο 1' II H2C = C-C > 0 - 3⁄4 wherein R, R2 is an alkyl chain having 1 to 4 carbon atoms. 5. The ultraviolet light-curable nano-coating material as described in claim 1 of the patent scope, 094129214, Form No. A0101, page 14/19 pages, 1003212650-0, I35S432, revised on June 15, the propylene monomer The content is 10 to 20%. 6. The ultraviolet light-curable nano-coating material according to claim 1, wherein the pigment particles are made of carbon black. The particle size of the pigment particles is 191.4 nm or less, as described in the above-mentioned patent application. 8. The ultraviolet light-curable nano-coating material according to claim 1, wherein the content of the pigment particles is from 55 to 4.5%. 5〜4. 5%。 The 5% of the 5%. The ultraviolet light-curable nano coating according to claim 1, wherein the photoinitiator is benzophenone, diphenylethylenedione or benzoin ether. The ultraviolet curable nano coating according to claim 1, wherein the solvent is a mixed system of mercaptoethyl ketone and methyl isobutyl ketone. 12. A method for preparing a UV-curable nano-coating, comprising the following steps 5~25% of the total system containing double bond propylene oligomer, 5~25% propylene monomer, 0. 5% pigment particles and 0. 5% photoinitiator are added sequentially The reactor pre-charged with the solvent; and stirred to mix well. The carbon black particles having a particle diameter of 191.4 nm or less are prepared by the method of the present invention. The method for producing a UV-curable nano-coating material according to claim 12, wherein the solvent is a mixed solvent of methyl ethyl ketone and decyl isobutyl ketone. 094129214, the UV-curable nano-coating material described in Patent Application No. 12, Form No. A0101, Page 15 of 19, 1003212650-0, 1358432, 100-year, June 15th, the method of nuclear replacement, The stirring is stirred by a stirring rod or stirred by ultrasonic vibration. 16 . A method for using a UV-curable nano-coating material, comprising: coating an ultraviolet-curable nano-coating material according to claim 1 of the patent application on a surface of a workpiece to form a coating; The film; and ultraviolet light polymerization to form an ultraviolet hardened layer. The method of using the ultraviolet curable nano-coating material according to claim 16, wherein the formed ultraviolet hardening layer comprises a resin having the following structural formula and pigment particles dispersed in the resin: R Η Η- f H2 v . f ^ s _^_c c —〇-)-fm 〇—〇 c==o c=o 03⁄4 RF/ .0.. (4) X In the formula, R and R2 are each an alkyl chain having a carbon number of 4, an X value of 3, and an m value of 83 to 277. The method of using the ultraviolet curable nano-coating material according to claim 16, wherein the coating is spray dip coating or brush coating. The method of using the ultraviolet light-curable nano-coating material according to claim 16, wherein the coating film-forming film is subjected to low-temperature heat treatment to form a film. The method of using the ultraviolet curable nano-coating material according to claim 19, wherein the low-temperature heat treatment has a temperature of 60 to 80 °C. 21. For example, the UV-curable nano-coating agent described in claim 20, 094129214, Form No. A0101, Page 16 of 19, 1003212650-0 1358432 22 23, 100, June 15, revised method of replacement page Wherein the low temperature heat treatment time is 5 to 10 minutes. The method of using the ultraviolet curable nano-coating material according to claim 16, wherein the ultraviolet light polymerization is carried out in an ultraviolet exposure machine. The method of using the ultraviolet light-curable nano-coating material according to claim 22, wherein the exposure machine irradiation energy is 0.4 Joules/cm 2 . 094129214 Form No. A0101 Page 17 of 19 1003212650-0