TWI472587B - Colored aqueous uv curable coating composition - Google Patents

Description

UV curable pigmented waterborne coating composition

This invention relates to an ultraviolet (UV) curable pigmented aqueous coating composition, and more particularly to an ultraviolet curable pigmented aqueous coating composition for use in a single application.

Today in the information age, various electronic products are widely used in people's lives, such as digital cameras, notebook computers, mobile phones, handheld digital assistants (PDAs), home appliances, etc., and their outer casings are mostly made of plastic, plastic materials. The utility model has the advantages of easy molding, low cost, light weight, and low corrosion resistance, but the aging resistance and mechanical properties are inferior to the metal materials, and the appearance texture is also inferior to the performance of the metal materials. Therefore, in order to overcome the above problems, the currently used process is to form a protective and/or decorative coating on the surface of the plastic part by coating baking.

In the past, most of the coatings used for substrates were solvent-based coatings. However, volatile organic solvents (VOCs) emitted by solvent-based coatings into the atmosphere have adverse effects on the environment. In recent years, due to human attention to environmental protection and energy, countries around the world have strictly controlled the content of VOC in coatings, which has led to the transfer of coatings from conventional solvent-based coatings to water-based coatings. Compared with solvent-based coatings, water-based coatings have the advantage of not containing VOC or VOC, and have low environmental pollution.

Conventional coating on the surface of plastic parts generally requires two-baked or three-baked three-baked procedures. For example, in the case of two coatings, the primer is applied first. The primer serves to provide the desired color on the surface of the substrate and because of its adhesion to the substrate and the topcoat, the substrate can be sealed and then coated. The adhesion of the topcoat to the substrate, etc. After the primer is baked, the top coat is sprayed, and the top coat and the primer are combined to make the overall coating exhibit various colors and luster, and the coating has high hardness, high wear resistance and high chemical resistance. . Since it has to undergo two operations of two coatings and two baking processes, not only the amount of coating material is large, but also the labor time is very high, thereby increasing the cost. Therefore, the industry is committed to developing a coating composition that achieves a combination of aesthetics and performance by one application. For example, Taiwan Patent No. I290566 discloses a pearl paint ultraviolet light coating composition for one-time spraying, although the coating on the plastic member can be obtained by using a process of applying the pearl paint ultraviolet light coating composition once after one coating and baking. However, such a composition is limited to the use of a translucent pearlescent pigment. If the pearlescent pigment is replaced by a solid pigment having no transparency, the ultraviolet light is absorbed on the surface of the coating due to the light absorbing property of the solid pigment. The coating cannot be penetrated, so that the monomer or the oligomer cannot be effectively polymerized during the curing process of the coating, and the problem that the coating film is not dry or semi-dry is easily generated, and the quality of the coating cannot be obtained. make sure.

It is a primary object of the present invention to provide an ultraviolet curable pigmented aqueous coating composition comprising the following components:

(a) an aqueous oligomer comprising at least one unsaturated double bond selected from the group consisting of aqueous epoxy acrylate oligomers, aqueous polyurethane acrylate oligomers, aqueous polyesters a group of acrylate oligomers, aqueous polyacrylate oligomers, aqueous urethane acrylate oligomers, aqueous thiol acrylate oligomers, and mixtures thereof;

(b) an aqueous medium;

(c) a photoinitiator;

(d) an aqueous thermoplastic resin, as needed;

(e) Colorants

Wherein component (c) is from 3 to 10 parts by weight based on 100 parts by weight of component (a); component (d) is from 0 to 30 based on 100 parts by weight of component (a). The component (e) is contained in an amount of 2 to 50 parts by weight based on 100 parts by weight of the total of the components (a) and (d).

The application of the ultraviolet curable pigmented water-based coating composition of the invention adopts a construction method, and when applied by one spray, a coating film with both aesthetic appearance and high performance can be obtained, compared with the conventional secondary or tertiary coating method. The invention has the advantages of high production efficiency, low energy consumption and low cost, and the obtained paint film has the characteristics of good appearance, good scratch resistance, good wear resistance and solvent resistance, and the colored aqueous coating composition has no The low volatile organic compound (VOC) or VOC content has low environmental pollution and can be used as an environmentally friendly material.

An aqueous oligomer of at least one unsaturated double bond of component (a) contained in the ultraviolet (UV) curable pigmented aqueous coating composition of the present invention, preferably having an aqueous bond of 1 to 10 unsaturated double bonds The oligomer is more preferably an aqueous oligomer having 2 to 5 unsaturated double bonds. The weight average molecular weight of the aqueous oligomer used in the present invention is not particularly limited, and is usually from 100 to 10,000, preferably from 300 to 7,500, more preferably from 400 to 6,500, particularly preferably from 500 to 5,000.

The aqueous oligomer used in the present invention is selected from the group consisting of an aqueous epoxy acrylate (Epoxy Acrylate) oligomer, an aqueous polyurethane acrylate (Polyurethane Acrylate) oligomer, and an aqueous polyester acrylate (Polyester). Acrylate) a group of oligomers, aqueous polyacrylate oligomers, aqueous Amine Acrylate oligomers, aqueous Acrylate oligopolymers, and mixtures thereof, Preferably, the aqueous oligomer is a group of aqueous polyurethane acrylate oligomers, aqueous polyester acrylate oligomers, aqueous polyacrylate oligomers, and mixtures thereof, preferably The aqueous oligomer is an aqueous polyurethane acrylate oligomer, and the aqueous polyurethane acrylate oligomer can be an aqueous aliphatic polyurethane acrylate oligomer. A polymer or an aqueous aromatic urethane acrylate oligomer, wherein the aqueous aliphatic polyurethane acrylate oligomer is less susceptible to yellowing problems, and is preferred.

Examples of commercially available aqueous oligomers containing at least one unsaturated double bond include: aqueous polyurethane acrylate oligomers: ETERCURE DR-W401, ETERCURE DR-W402, and ETERCURE DR-W403 (Changxing chemicals ^{Ltd.); UCECOAT TM 7570, UCECOAT TM} 7578, UCECOAT TM 6558, UCECOAT TM 6569, UCECOAT TM 7177, UCECOAT 7571 TM, UCECOAT TM 7631, UCECOAT TM 7655, UCECOAT TM 7660, UCECOAT TM 7699, UCECOAT TM 7849, UCECOAT TM ^{7770, UCECOAT TM 7772, UCECOAT TM} 7773, UCECOAT TM 7825 and the like UCECOAT ^TM 7849 (manufactured by CYTEC Corporation). CN9245 and CN9245W80, etc. (manufactured by Sartomer Co., Ltd.); VP LS2280, XP2629, XP2420, UV 2282, VP LS 2317, VP LS 2348, XP 2689, XP2687, XP2649, XP2661 and XP2720, etc. (manufactured by Bayer Corporation). Water-based polyester acrylate oligomer: CN2255, CN2256, etc. (Sartomer); aqueous polyacrylate oligomer: CN2716, CN2717, CN132, SB500K60, etc. (Sartomer).

The present invention can utilize an aqueous medium to adjust the viscosity of the coating to a range suitable for operation. The aqueous medium can be added during the preparation of the ingredients, or can be added at the end of the spraying, and further adjusted to the viscosity of the spray when the viscosity is finally adjusted, so that the solid content is in the range of about 10% to about 40%. The aqueous medium as the component (b) in the ultraviolet curable pigmented aqueous coating composition of the present invention is preferably a group consisting of water, deionized water and optionally a hydrophilic solvent and a mixture thereof. The above hydrophilic solvent is not particularly limited and may be any one known to those skilled in the art to which the present invention pertains, for example, selected from the group consisting of alcohols, alcohol ethers, alcohol esters, ketols, and mixtures thereof. Groups including, but not limited to, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, ethylene glycol and ethers thereof, propylene glycol and ethers thereof, 2,2,4-tri Methyl-1,3-pentanediol monoisobutyrate, diacetone alcohol or a combination thereof. Among them, ethylene glycol and ethers thereof include, but are not limited to, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, Diethylene glycol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and combinations thereof. Among them, propylene glycol and ethers thereof, including, but not limited to, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl Ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, and combinations thereof. In the ultraviolet curable pigmented aqueous coating composition of the present invention, the solid content is from about 20% to 60%.

The photo initiator used in the present invention is not particularly limited, and is a radical which generates a radical after irradiation with light, and initiates a polymerization reaction by transmission of a radical. It is, for example, selected from the group consisting of benzophenone-amine conjugated systems, benzoin ethers, benzoin and its ketals, and acetophenone derivatives.

According to the present invention, the amount of the component (c) photoinitiator to be used is not particularly limited, and may be adjusted depending on the kind and amount of the aqueous oligomer contained in the ultraviolet curable pigmented aqueous coating composition. In general, the component (c) is contained in an amount of from 3 to 10 parts by weight based on 100 parts by weight of the component (a). Since different photoinitiators have different degrees of absorption of light in different wavelength bands, the photoinitiators selected for the different color pigments are also different, and two or more photoinitiators may be selected as needed.

Examples of commercially available photoinitiators include: benzoin dimethyl ether: DAROCUR MBF and IRGACURE 754 (manufactured by BASF Corporation). Α-hydroxyketones: IRGACURE 2959, DAROCUR 1173, IRGACURE 500, IRGACURE 184 (manufactured by BASF Corporation), and RUNTECURE 1103 (manufactured by Changzhou Huatti Co., Ltd.). Benzophenones: DAROCUR BP, (manufactured by BASF Corporation). 2,4,6-trimethylbenzimidyldiphenylphosphine oxide: DAROCUR TPO (manufactured by BASF Corporation). Bis(2,4,6-trimethylbenzhydrazide)phenylphosphine oxide BAPO: IRGACURE 819 and IRGACURE 819DW (manufactured by BASF Corporation). 1-Hydroxycyclohexylacetophenone: CHIVACURE 184 (manufactured by Double Bond Chemicals (DBC) Co., Ltd.). For the selection of the above initiator, one or several compositions may be selected as needed.

The ultraviolet curable pigmented aqueous coating composition of the present invention can be used as an aqueous coating for coating a surface of a substrate. Suitable substrates include plastic substrates (including ABS, AS, PC, PP, PMMA, PS, HIPS, PVC, PA, PPO, PPS, PC/ABS or mixtures thereof, preferably ABS, PC, PC/ ABS), a group of tiles, wood, leather, stone, glass, metal, alloy, paper, fiber, cotton, and mixtures thereof. The formulation of the present invention may not contain an aqueous thermoplastic resin, and a preferred formulation is to add an aqueous thermoplastic resin, and depending on the substrate, add component (d) an aqueous thermoplastic resin as needed; in general, component (d) is grouped. The component (a) is contained in an amount of from 0 to 30 parts by weight based on 100 parts by weight. The aqueous thermoplastic resin is selected from the group consisting of acrylic resin, chloroacetate resin, chlorinated polypropylene resin, polyester resin, cellulose acetate butyrate (CAB), nitrocellulose (NC), and mixtures thereof. The weight average molecular weight of the aforementioned aqueous thermoplastic resin is not particularly limited, but is preferably from 1,000 to 200,000, and may be a homopolymer or a copolymer.

According to an embodiment of the present invention, an acrylic resin is selected as the aqueous thermoplastic resin, and is particularly suitable for coating the surface of a plastic substrate. The aqueous thermoplastic acrylic resin used in the present invention has good compatibility with an oligomer and can be directly blended. Blending in the coating composition does not react with the oligomer and therefore acts as a buffering medium to release stresses due to rapid curing during UV curing. On the other hand, since such a resin has a strong surface drying ability, it is possible to promote the removal of the solvent from the coating film during the drying process, thereby avoiding the phenomenon of sag. The above acrylic resin has a glass transition temperature of more than 20 ° C, and the main function is to increase the adhesion of the treatment coating film to the substrate and prevent the coating film from cracking, and it is also possible to add a higher glass transition temperature (Tg) acrylic resin, for example, for example. It has a glass transition temperature of more than 60 ° C, preferably has a glass transition temperature of 70 ° C to 150 ° C, and can accelerate the drying speed of the coating film. The glass transition temperature is too low, the heat resistance, abrasion resistance, solvent resistance and hardness of the coating film are not good, and the protection is insufficient; on the contrary, the glass transition temperature is too high, but the problem of processing is not easy.

The aforementioned aqueous thermoplastic acrylic resin may be a homopolymer or a copolymer derived from at least one polymer selected from the group consisting of acrylic acid, methacrylic acid, alkyl acrylate, and alkyl methacrylate. The alkyl group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, most preferably 1 to 8 carbon atoms. a linear alkyl group, a branched alkyl group or a cycloalkyl group of 6. The alkyl group may be selected from one or more selected from the group consisting of a hydroxyl group, a halogen atom, a C1 to C30 (preferably C1 to C20, more preferably a C1 to C12, particularly preferably a C1 to C8, an optimum C1 to C6) alkoxy group, and a C6. Substituents for the -C14 aryl, cyano, carboxyl, nitro and sulfo groups are substituted.

The alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group or an iso-hexyl group. Base, n-heptyl, isoheptyl, n-octyl, isooctyl, n-decyl, isodecyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, n-tridecane Base, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, cyclopropyl, cyclobutane Base, cyclopentyl, cyclohexyl, cyclooctyl, borneol, isobornyl, and the like.

Examples of commercially available water-based thermoplastic acrylic resins include ETERSOL 6923, ETERSOL 1155, ETERSOL 1155-1, ETERSOL 1191, etc. (manufactured by Changxing Chemical Co., Ltd.); Carboset CR-781, and Carboset PC-23 (manufactured by Lubrizol Co., Ltd.). Bayhydrol AH XP2754 and Bayhydrol AH XP2741 (manufactured by Bayer Corporation). Primal WL-51, Primal WL-91, Primal WL-100 (Rohm and Haas Company (now Dow Chemical)).

According to another embodiment of the present invention, a chloroacetic resin is used as the aqueous thermoplastic resin, and the chloroacetic resin may be a homopolymer or a copolymer, such as, but not limited to, a copolymer of vinyl chloride and vinyl acetate or vinyl chloride. And a terpolymer of vinyl acetate and dicarboxylic acid. Examples of commercially available aqueous thermoplastic chloroacetic resins which can be used in the present invention include: UCAR AW-875 (manufactured by The Dow Chemical Co., Ltd.); in addition, cellulose acetate butyrate can also be used as the aqueous thermoplastic resin, which can be used in the commercially available acetic acid of the present invention. Examples of the cellulose butyrate include: CMCAB 641-0.2, CMCAB 641-0.5 (manufactured by EASTMAN).

The color component (e) used in the present invention may be a transparent, translucent or opaque material, and is a pigment which can impart the composition of the present invention and the surface of the coating formed by the composition or the surface of the material. , dye or filler. The pigment, dye and filler may be used singly or in combination of two or more.

According to an embodiment of the present invention, the colorant used in the present invention is a pigment which is applied to a substrate and covers the primary color of the substrate. Color-imparting pigments are known to those of ordinary skill in the art and may be organic or inorganic pigments. Inorganic pigments are generally mineral materials, including titanium white pigments, iron oxide pigments, chromium pigments, black titanium, carbon black, silver paste, and the like. Specific examples of the inorganic pigment include CI Pigment Yellow 34 and CI Pigment Red 104. Aluminum silver paste STAPA HYDROLAN series: STAPA HYDROLAN 2154, STAPA HYDROLAN 156, STAPA HYDROLAN 2197, STAPA HYDROLAN 3580, STAPA HYDROLAN 3590, etc. (manufactured by ECKART Co., Ltd.). Aluminum silver paste ZW954, ZW955, ZW956, ZW959 series (made by Changsha Xing Metal Materials Co., Ltd.); organic pigments mainly include: azo pigments, cyanine pigments, etc. Examples of organic pigments include CI Pigment Yellow 184, CI Pigment Yellow 109 , C.1. Pigment Yellow 74, CI Pigment Yellow 110, CI Pigment Yellow 42, CI Pigment Orange 73, CI Pigment Red 254, CI Pigment Red 112, CI Pigment Red 166, CI Pigment Red 101, CI Pigment Red 264, CI Pigment Green 7, CI, Pigment Blue 15, C.1. Pigment Blue 15:3, CI Pigment Violet 23, CI Pigment Black 7, etc. In order to meet various color requirements, one or more colorants can be used.

Examples of commercially available colorants include: UNISPERSE series: GREEN GS, BLUE BS, YELLOW GO-S, RED 3RS-S, ULTRA BLUE 15:3, etc. (CAS BA); Hostafine series: Yellow HR 130-CN, Yellow HR , Red F5RK, Red FGR, Red FGR-131-CN, Black T30, Black TS30. Colanyl Black N 131-CN, Colanyl white TQ-CN, etc. (manufactured by Clariant Co., Ltd.); DOR1, DBK1, DOY1, DBC1, CH2, etc. (manufactured by Spirent, Finland).

The coloring material used in the invention can be matched with a filler in addition to the pigment, and the filler can be used as a body pigment, having the advantages of acid and alkali resistance, increasing coating film thickness, improving coating hardness, filling the substrate hole, and reducing cost; Examples suitable as fillers include transparent fillers (e.g., feldspar, laksa, sand, crystalline limestone, glass beads, synthetic resin beads), colored fillers (e.g., marble powder, granite powder, serpentine powder, fluorite, colored laksa) Powder and colored ceramic powder), extender (such as calcium carbonate, talc, barium sulfate, mica, clay, diatomaceous earth and barite), Portland cement or zinc oxide.

The coating composition of the present invention may further comprise one or more component (f) additives as an aqueous auxiliary agent in accordance with the use of the desired finished coating film. The auxiliary agent selected is selected from the group consisting of a dispersing agent, a matting agent, an antifoaming agent, an antioxidant, a shaking aid, a stabilizer, a bactericide, a leveling agent, a wetting agent, a adhesion promoter, an anti-floating agent and The group of the mixture, the types of these auxiliaries are well known to those skilled in the art, and the amount thereof is also easily determined by those skilled in the art according to different needs. Preferably, the color is curable by ultraviolet light. The content of the component (f) additive is from 0 to 13 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by total of the aqueous coating composition.

The aqueous dispersant used in the present invention is mainly used as a pigment dispersion deflocculant, and the dispersant may be selected from a polymer copolymer component containing a pigment affinity group, an unsaturated polyamine and an amine, and a high molecular weight unsaturated polycarboxylate. Acidic and nonionic organic surfactants.

Examples of commercially available dispersants include: ANTI-TERRA-206, ANTI-TERRA-250, BYK-151, BYK-154, Disperbyk 180, Disperbyk 181, Disperbyk 183, Disperbyk 184, Disperbyk 185, Disperbyk 187, Disperbyk 190, Disperbyk 191, Disperbyk 192, Disperbyk 193, Disperbyk 2015, Disperbyk 2090 , Disperbyk 2091, Disperbyk 2095, Disperbyk 2096 (manufactured by BYK); TEGO Dispers 650, TEGO Dispers 651, TEGO Dispers 652, TEGO Dispers 655, TEGO Dispers 660C, TEGO Dispers 715W, TEGO Dispers 735W, TEGO Dispers 740W, TEGO Dispers 745W, TEGO Dispers 750W , TEGO Dispers 752W, TEGO Dispers 755W, TEGO Dispers 760W, TEGO Dispers 762W, Colorol E, Lipotin A, TEGO Wet 500 and TEGO-Foamex 840 (made by TEGO); HYDROPALAT-1080, HYDROPALAT-3065, HYDROPALAT-3204, HYDROPALAT -3216 and HYDROPALAT-3275 (manufactured by COGNIS); AQ-320, AQ-330 (made by Kusumoto Kasei Co., Ltd.); EFKA-4500, EFKA-4510, EFKA-4520, EFKA-4530, EFKA-4540, EFKA-4550 EFKA-4560, EFKA-4570, EFKA-4580, EFKA-4590 and EFKA-5071 (made by EFKA Auxiliary Company, the Netherlands). The aqueous dispersion agents may be used singly or in combination of two or more.

The invention uses an aqueous wetting agent as needed to reduce the surface tension of the substrate, so that the coating film is easily spread on the surface of the substrate, and the invention can also use an aqueous leveling agent as needed, which is beneficial to the wetting and coating of the substrate. Leveling. Examples of commercially available aqueous wetting agents or aqueous leveling agents include: EFKA3031, EFKA3034, EFKA3035, EFKA3288, EFKA3570, EFKA3772, and EFKA3580 (made by EFKA, the Netherlands); BYK-346, BYK-348, BYK-349, BYK333, BYK- 380, BYK-381, BYK-381N, BYK307, BYK350 0, BYK3530 and BYK-SILCLEAN 3710 (made by BYK); TEGO 410, TEGO 450, TEGO 250, TEGO 260, TEGO 265, TEGO 270, TEGO 500, TEGO 505, TEGO 510 and TEGO Rad 2200N (manufactured by TEGO Corporation); AFCONA-3580 (manufactured by AFCONA). The aqueous wetting agent or aqueous leveling agent may be used singly or in combination of two or more.

The water-based matting agent used in the present invention can achieve low gloss and matting effect on the coating film, and the matting agent can be selected from the group consisting of SYLOID C503, SYLOID C803, SYLOID C807, SYLOID C809, SYLOID W300 and SYLOID W500 (manufactured by GRACE); OK412, OK500, OK520 and OK607 (made by DEGUSSA) and some water-based matt wax. The aqueous matting agents may be used singly or in combination of two or more.

The aqueous antifoaming agent used in the invention can inhibit the generation of bubbles in the coating process to cause coating film defects, and the antifoaming agent can be selected from the group consisting of polyether-oxyalkylene copolymer emulsions, dimethyl polyoxanes, A group consisting of organically modified polyoxyalkylenes, polymeric compounds, and modified polyoxyalkylenes. Examples of commercially available aqueous defoamers include: BYK-011, BYK-017, BYK-018, BYK-020, BYK-024, BYK-025, BYK-028, BYK-044, BYK-045, BYK-080A, BYK -093, BYK-1730, BYK-1770, BYK-3520 and BYK-3521 (made by BYK); Airex-901W, Airex-902W, Airex-903W, TEGO-Foamex 800, TEGO-Foamex 825 TEGO-Foamex 822 (manufactured by TEGO Corporation); EFKA 2526, EFKA 2035, EFKA 2527, EFKA 2721, and EFKA 2526 (manufactured by EFKA, The Netherlands). The above aqueous antifoaming agents may be used singly or in combination of two or more.

The aqueous rhineology additive used in the present invention allows the coating to have a stable structure, protect the dispersed pigment particles, maintain excellent leveling, and prevent sedimentation of the colorant. The rocking aid can be an organic bentonite series, castor oil and its derivatives, polyamines, polylong-chain olefins and modified urea solutions. Examples of commercially available aqueous shake auxiliaries include: BYK-420 and BYK-425 (manufactured by BYK); TEGO ViscoPlus 3000, TEGO ViscoPlus 3010, TEGO ViscoPlus 3030 and TEGO ViscoPlus 3060 (manufactured by TEGO); VISCALEX HV100, VISCALEX HV200, VISCALEX HV300, VISCALEX HV30, VISCALEX VM, VISCALEX VG2, RHEOVIS 112, RHEOVIS 132, RHEOVIS 152, RHEOVIS PU10, and RHEOVIS PU20 (made by EFKA, Netherlands); Disparlon AQ-607 (made by Nanben Chemical Co., Ltd.). The aqueous shaking assistant may be used singly or in combination of two or more.

In addition, in the ultraviolet curable pigmented aqueous coating composition, a component (g) acrylate reactive monomer or oligomer which is hydrophilic or dispersible in water may be added as needed, and used in combination to improve the crosslinking. Joint density. In general, the content of the acrylate reactive monomer or oligomer is from 0 to 20 parts by weight based on 100 parts by total of the total of the ultraviolet curable pigmented aqueous coating composition. The reactive monomer may be 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, trimethylolpropane three Acrylate, ethoxylated trimethylolpropane triacrylate; polyethylene glycol (600) dimethacrylate, 2 (2-ethoxyethoxy) ethyl acrylate), polyethylene glycol (400 Dimethacrylate, polypropylene glycol (400) dimethacrylate, polyethylene glycol (1000) dimethacrylate, and the like.

Examples of commercially available reactive monomers are: 1,6-hexanediol diacrylate: EM221 (manufactured by Changxing Chemical Industry Co., Ltd.). Tripropylene glycol diacrylate: EM223 (manufactured by Changxing Chemical Industry Co., Ltd.). Polyethylene glycol (400) diacrylate: EM226 (manufactured by Changxing Chemical Industry Co., Ltd.) and SR344 (manufactured by Sartomer Co., Ltd.). Polyethylene glycol (600) diacrylate: EM227 (manufactured by Changxing Chemical Industry Co., Ltd.) and SR610 (manufactured by Sartomer Co., Ltd.). Trimethylolpropane triacrylate: EM231 (manufactured by Changxing Chemical Industry Co., Ltd.). Ethoxylated trimethylolpropane triacrylate: EM2380 and EM2386 (manufactured by Changxing Chemical Co., Ltd.), SR415 and SR9035 (manufactured by Sartomer Co., Ltd.). Polyethylene glycol (600) dimethacrylate: SR252 (manufactured by Sartomer Co., Ltd.). 2(2-ethoxyethoxy)ethyl acrylate: SR256 (manufactured by Sartomer Co., Ltd.). Polyethylene glycol (400) dimethacrylate: SR603 (manufactured by Sartomer Co., Ltd.). Polypropylene glycol (400) dimethacrylate: SR644 (manufactured by Sartomer Co., Ltd.). Polyethylene glycol (1000) dimethacrylate or the like: SR740 (manufactured by Sartomer Co., Ltd.).

The ultraviolet curable pigmented aqueous coating composition of the present invention can be applied to the surface of a substrate by any method well known to those skilled in the art to which the present invention pertains. For example, it can be administered via a method comprising the following steps:

(1) adding at least one unsaturated double bond aqueous oligomer, an aqueous medium, a photoinitiator and a colorant to be uniformly mixed at a high speed;

(2) adding an aqueous thermoplastic resin, an aqueous auxiliary agent or an acrylate reactive monomer or oligomer as needed, stirring uniformly, and adjusting to an appropriate viscosity to form a liquid polymerizable composition;

(3) The liquid polymerizable composition obtained in the step (2) is diluted with a suitable solvent and applied to a substrate in a suitable manner for surface treatment to form a coating;

(4) heating as needed to volatilize the solvent, the temperature is controlled at about 50 ° C to about 70 ° C, the reaction at a fixed temperature for about 3 to about 12 minutes;

(5) The resulting coating is irradiated with energy rays to cure the coating.

The coating method used in the above step (3) may be a bar coating, a slide coating, a curtain coating or a spray coating. The coating method may be used singly or in combination of two or more, preferably by spray coating (spraying). The substrate is not particularly limited and may be, for example, ceramic tile, wood, leather, stone, glass, metal, alloy, paper, plastic, fiber, cotton, etc., preferably plastic. The plastic substrate, especially a plastic substrate for 3C electronic products, home appliances and cosmetics, such as ABS, AS, PC, PP, PMMA, PS, HIPS, PVC, PA, PPO, PPS, PC/ABS or Mixed, preferably ABS, PC, PC/ABS. The above metal substrate is, for example but not limited to, stainless steel, zinc alloy, aluminum, aluminum alloy, magnesium alloy, and chromium. The above composite substrate refers to a fiber-containing plastic substrate such as, but not limited to, nylon or PC containing glass fibers.

Preferably, the step of curing the coating of step (5) is carried out by photopolymerization by irradiating an energy ray, which refers to a light source of a certain range of wavelengths, such as ultraviolet light or hot line (radiation or radiation). Etc., preferably ultraviolet light (wavelength of 200 to 400 nm). The irradiation intensity may be from 500 to 1200 mJ/cm ² , preferably from 600 to 1000 mJ/cm ² .

The following examples are intended to further illustrate the invention, but are not intended to limit the scope of the invention. All modifications and variations that may be readily made by those skilled in the art are included within the scope of the disclosure of the present disclosure and the scope of the appended claims.

The test methods involved in the present invention are as follows.

[1] film thickness

The film thickness test piece was sprayed and measured by a film thickness meter (QuaNix 8500).

[2] Adhesion of coating film to substrate

Use a knife to draw 100 squares of 1mm ² squares. See the substrate. Use Scotch 3M Tape600 tape to stick to the scribe for 30 to 90 seconds, and press until no bubbles. Pull it up in the direction of 180 degrees. The proportion of paint peeling off is not More than 15% is OK.

[3] Film hardness

Use the Mitsubishi pencil marked with hardness value, at a 45-degree angle, 500g load, and 6.5mm on the surface of the product, wipe off the pen marks with an eraser, the paint should not fall off, and the hardness of the pencil is marked as the paint film. Hardness value.

[4] Film gloss

The surface gloss of the product was measured with a gloss meter (ZEHNTNER ZGM 1020) at an induction angle of 60°, and the difference from the standard color plate was not more than 2 for OK.

[5] Coating resistance

A pressure of 500 g was applied using a wear tester for 1 roundback/2 s test. Wiping with 99.9% alcohol for 500 times did not pass through, and methyl ethyl ketone was wiped 200 times without passing through.

[6] Film heat resistance

After being placed in an oven at 80 ° C for 48 hours, the surface condition of the paint film was inspected with the naked eye to check that the appearance was free of cracks, peeling, etc.

[7] Appearance

The appearance of the coating film was observed with the naked eye under a D65 light source.

In order to facilitate the understanding of the description in the following examples, the components of the ultraviolet curable pigmented aqueous coating composition provided by the present invention are numbered for easy understanding, wherein (a) contains at least one unsaturated double bond. An aqueous oligomer; (b) an aqueous medium; (c) a photoinitiator; (d) a thermoplastic resin; (e) a colorant; (f) an additive; and (g) an acrylate reactive monomer or oligomer.

Example 1

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 8 to 15 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 70

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with silver half-light effect

Example 2

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 10-15 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧F

Film gloss: 80

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a blue all-light effect.

Example 3

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 10 to 15 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 90

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a red all-optical effect.

Example 4

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The physical property test results are as follows:

Film thickness: 10 to 15 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 85

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a blue all-light effect.

Example 5

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 12 to 20 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 80

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a yellow all-light effect.

Example 6

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 10 to 15 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧F

Film gloss: 75

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a red all-optical effect.

Example 7

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 12 to 20 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 65

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a green all-optical effect.

Example 8

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 12 to 20 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 75

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a yellow all-light effect.

Example 9

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 12 to 20 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: 80

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a red all-optical effect.

Example 10

The above obtained composition was added with a diluent (deionized water/ethanol = 1/1 (volume ratio)) to the Iwata Cup for about 10 seconds, and sprayed on a plastic substrate with an air spray gun, followed by an oven at 60 ° C. Pre-baked for ~10 minutes, then exposed to a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 12 to 20 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧F

Film gloss: 70

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with a blue all-light effect.

Example 11

The composition obtained above was diluted with diluent (ethanol) to the Iwata Cup for about 10 seconds, sprayed on a plastic substrate with an air spray gun, and then pre-baked in a 60 C oven for 5 to 10 minutes. The mercury lamp (800 mJ/cm ² ) was pressed for exposure. Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 8 ~ 10 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Coating gloss: ≧85

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with silver full light effect

Example 12

The above-obtained composition was diluted with a diluent (water/ethanol) to an Iwatani Cup for about 10 seconds, sprayed on a plastic substrate with an air spray gun, and then pre-baked in an oven at 60 ° C for 5 to 10 minutes. The exposure was carried out by a medium pressure mercury lamp (800 mJ/cm ² ). Then, the exposed substrate having the coating film was subjected to physical property test.

The results of the physical property test are as follows:

Film thickness: 8 ~ 10 μm

Adhesion of coating film to substrate: 100/100

Film hardness: ≧H

Film gloss: ≧75

Coating film resistance: pass (no scratches, no peeling off)

Film heat resistance: through

Appearance: flat, with silver full light effect

Various modifications or variations of the structure of the invention are possible without departing from the spirit or scope of the invention. In view of the foregoing, all variations and modifications of the present invention are covered by the scope of the claims and the scope of the claims.

Claims (11)

A one-time construction ultraviolet curable pigmented aqueous coating composition comprising: (a) 100 parts by weight of an aqueous oligomer comprising at least one unsaturated double bond and selected from aqueous epoxy acrylate oligomerization , aqueous polyurethane acrylate oligomer, aqueous polyester acrylate oligomer, aqueous polyacrylate oligomer, aqueous amide acrylate oligomer, aqueous thiol acrylate oligomer and a group consisting of a mixture of at least two aqueous oligomers of the above aqueous oligomer; (b) an aqueous medium, wherein the aqueous medium is water, deionized water or a mixture of water and a hydrophilic solvent; 3 to 10 parts by weight of a photoinitiator selected from the group consisting of a benzophenone-amine conjugated system, a benzoin ether, a benzoin, a ketal of a benzoin, and an acetophenone derivative. Ethnic group; (d) ~ 30 parts by weight of the aqueous thermoplastic resin, wherein the aqueous thermoplastic resin is selected from the group consisting of acrylic resin, chloroacetate resin, chlorinated polypropylene resin, polyester resin, cellulose acetate butyrate, nitrocellulose, and the above aqueous thermoplastic resin. a group consisting of a mixture of at least two aqueous thermoplastic resins, and the glass transition temperature of the aqueous thermoplastic resin is greater than 20 ° C; (e) 2 to 50 parts by weight of the colorant, when the components (a) and (d) are combined When 100 parts by weight. The ultraviolet light curable pigmented aqueous coating composition according to claim 1, wherein the aqueous oligomer containing at least one unsaturated double bond is 1 ~10 aqueous oligomers with unsaturated double bonds. The ultraviolet curable pigmented aqueous coating composition according to claim 1, wherein the aqueous oligomer containing at least one unsaturated double bond is an aqueous oligomer having 2 to 5 unsaturated double bonds. The ultraviolet curable pigmented aqueous coating composition of claim 1, wherein the aqueous oligomer is an aqueous polyurethane acrylate oligomer. The ultraviolet curable pigmented aqueous coating composition of claim 1, wherein the aqueous polyurethane acrylate oligomer is an aqueous aliphatic polyurethane acrylate oligomer. The ultraviolet curable pigmented aqueous coating composition according to claim 1, wherein the hydrophilic solvent is selected from the group consisting of alcohols, alcohol ethers, alcohol esters, ketols, and mixtures thereof. The ultraviolet curable pigmented aqueous coating composition of claim 1, wherein the acrylic resin is a homopolymer or a copolymer derived from at least one polymer selected from the group consisting of acrylic acid, methacrylic acid, Alkyl acrylate and alkyl methacrylate. The ultraviolet curable pigmented aqueous coating composition of claim 1, wherein the colorant is selected from the group consisting of pigments, dyes, fillers, and mixtures thereof The group that is formed. The ultraviolet curable pigmented aqueous coating composition of claim 1, wherein the ultraviolet curable pigmented aqueous coating composition further comprises an additive selected from the group consisting of a dispersant, a matting agent, an antifoaming agent, an antioxidant, and a shaker. A group of variable auxiliaries, stabilizers, bactericides, leveling agents, wetting agents, adhesion promoters, anti-floating agents, and mixtures thereof. The ultraviolet curable pigmented aqueous coating composition of claim 1, wherein the ultraviolet curable pigmented aqueous coating composition further comprises an acrylate reactive monomer. The ultraviolet curable pigmented aqueous coating composition according to claim 10, wherein the acrylate reactive monomer is selected from the group consisting of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol (400). Diacrylate, polyethylene glycol (600) diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate; polyethylene glycol (600) dimethacrylate, 2 ( 2-ethoxyethoxy)ethyl acrylate, polyethylene glycol (400) dimethacrylate, polypropylene glycol (400) dimethacrylate, polyethylene glycol (1000) dimethacrylate And a group of its mixtures.