KR100406685B1 - Composition for the 1-coat surface treatment of acrylonitrile-butadiene-styrene mold products - Google Patents

Abstract

The present invention relates to a surface treatment agent composition of an acrylonitrile-butadiene-styrene (ABS) molding, comprising: 1) 10 to 90% by weight of a binder resin comprising a cellulose acetate butyrate addition-modified acrylic polyol resin and an acrylic polyol or polyester polyol resin 2) 8 to 30% by weight of an organic solvent, 3) 1 to 15% by weight of a metal powder pigment, 4) 1 to 15% by weight of an additive, and 5) a resin containing a hydroxyl group and an isocyanate group in a 1: 1 equivalent ratio of the binder. When the surface of the ABS molded product is treated with the composition of the present invention, only 1-coat coating can bring about excellent surface treatment effect.

Description

COMPOSITION FOR THE 1-COAT SURFACE TREATMENT OF ACRYLONITRILE-BUTADIENE-STYRENE MOLD PRODUCTS}

The present invention relates to a surface treating agent composition of an acrylonitrile-butadiene-styrene (ABS) molding, specifically comprising cellulose acetate butyrate addition-modified acrylic polyol resin as a binder, thereby effectively The present invention relates to a surface treating agent composition which prevents protrusion and improves gloss so that a 1-coat coating alone produces a sufficient surface treatment effect.

Generally, acrylonitrile-butadiene-styrene (ABS) molding injection moldings are surface-treated with a resin composition containing a metal powder pigment in terms of surface protection and gloss provision.

Conventional surface treatment agents contain acrylic polyols or polyester polyol resins as binder components together with metal powder pigments, which do not allow the binder to comprehensively cover the particles of the metal powder when sprayed on the surface of the ABS molding (spray Lack of surface treatment wetting) Color pigments containing metallic pigments (referred to as "hado") because pigment particles protrude on the surface and fail to maintain specular smoothness and thus do not exhibit the inherent purpose of protection and appearance. Has been used to coat the ABS molding surface and then wet coat the undercoat protective coating (referred to as "top" or "clear layer") in the wet state.

Although the two-coat 1-baking method brings about an improvement in mirror smoothness and gloss, there is a problem in that the process is complicated and the loss of the surface treatment agent is high. Existing coating containing acrylic polyol or polyester polyol resin as a binder The glass transition temperature is lower than 50 ℃ and the top coat has a disadvantage that it is difficult to control the physical and chemical properties of the surface treatment coating film.

Accordingly, the present inventors have intensively studied, and as a result, a surface treating agent composition comprising a cellulose acetate butyrate addition-modified acrylic polyol resin as a binder together with an acrylic polyol or polyester polyol resin, which is used in the past, is effectively applied to the surface of the ABS molding. The present invention has been completed by discovering that the protruding of the particles and improving the gloss can bring about sufficient surface treatment effect with only 1-coat coating.

It is an object of the present invention to provide an improved surface treatment composition which can achieve smoothness and high gloss of the surface with only one coat coating when applied to the surface of ABS moldings.

1 is a schematic view showing the smoothing effect of the surface achieved by the surface treatment composition of the present invention,

2 is a schematic view of the manufacturing process of the surface treating agent composition of the present invention,

3 and 4 are SEM photographs of the coating films formed in Example 7 and Comparative Example 3, respectively.

[Explanation of symbols on the main parts of the drawings]

1: acrylonitrile-butadiene-styrene moldings

2: solvent volatilization

3: wet surface treatment agent composition

4: metal powder pigment

5: cellulose acetate butyrate addition modified acrylic polyol resin

In the present invention to achieve the above object,

1) 10 to 90% by weight of a binder resin comprising cellulose acetate butyrate addition-modified acrylic polyol resin and acrylic polyol or polyester polyol resin,

2) 8 to 30% by weight of an organic solvent,

3) 1 to 15% by weight of the metal powder pigment,

4) 1 to 15 weight percent of the additive, and

5) Resin containing a hydroxyl group and 1: 1 equivalent ratio of isocyanate groups in the binder

It provides a surface treatment agent composition of the acrylonitrile-butadiene-styrene (ABS) molding comprising a.

Hereinafter, the present invention will be described in detail.

The composition of the present invention comprises 1) 10 to 90% by weight of a binder resin, which binder comprises cellulose acetate butyrate addition-modified acrylic polyol resin and acrylic polyol or polyester polyol resin in a weight ratio of 5:95 to 40:60. Include.

The cellulose acetate butyrate addition-modified acrylic polyol resin facilitates the flow of the metal powder pigment to induce the position of the pigment particles from the granular phase to the normal phase during the volatilization of the solvent, and maintains the position of the pigment particles thus induced, thereby protruding the surface of the metal powder pigment. To prevent. This effect achieved by the cellulose acetate butyrate addition-modified acrylic polyol resin, that is, the effect of improving the smoothing of the surface due to the prevention of protrusion of the metal powder pigment, can be explained from the schematic diagram of FIG. 1.

The cellulose acetate butyrate addition-modified acrylic polyol resin used in the present invention can be prepared by dissolving cellulose acetate butyrate in an organic solvent, and then adding an acrylic monomer dropwise thereto at one time or according to time, and polymerizing it for 2 to 4 hours. Can be.

The type of cellulose acetate butyrate is modified according to the content of cellulose acetate and butyrate and additionally determined according to the viscosity seconds (based on ASTM D 817 and D 1343).

As the acrylic monomer, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, macro nitrile, methacrylonitrile, cyclohexyl methacrylate, acrylic acid, methacrylic acid, hydroxyl methacrylate, hydroxy Hydroxyl ethyl acrylate, hydroxyl propyl methacrylate, hydroxyl propyl acrylate, styrene monomer, maleic acid, itaconic acid, acrylamide, n-methylol acrylamide, diacetone acrylamide, glycidyl methacrylate, vinyl Toluene, vinyl acetate, vinyl chloride and the like can be used in combination.

As the organic solvent, non-polar solvents such as n-heptane, toluene, xylene, petroleum compounds and n-hexane, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dibasic ester, 3 -A polar solvent such as methoxy butyl acetate, amyl acetate, butyl glycol acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, diisobutyl ketone, isophorone and cyclohexanone, and a mixture of the nonpolar solvent and the polar solvent It can select suitably according to the characteristic of a binder, or a volatilization rate.

In order to perform the polymerization reaction, a polymerization initiator is used. As the polymerization initiator, azobis isobutylonitrile, benzoyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, p-methane hydroperoxide, di-t-butyl peroxide, 1,1-bis (t-butyl peroxy) -3,3,5-trimethyl cyclohexane, lauroyl peroxide, diisopropyl peroxydicarbonate , 3,5,5-trimethyl hexanoyl peroxide, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxy pibarate, t-butyl peroxyacetate, cumyl peroxyneody Carbonate, t-butyl peroxyl 2-ethyl hexanoate, t-butyl peroxybenzoate and the like can be used.

The acrylic polyol resin used in the present invention may be prepared by polymerizing an acrylic monomer in an organic solvent for 2 to 4 hours, in which case the above-described type may be used as the acrylic monomer, the organic solvent and the polymerization initiator.

The polyester polyol resin used in the present invention may be prepared by polymerizing a saturated dibasic acid, unsaturated dibasic acid and glycol in an organic solvent to synthesize unsaturated linear polyester, and then dissolving the composite in a vinyl monomer. . At this time, the above-mentioned kind can be used as the organic solvent and the polymerization initiator, and as the saturated dibasic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, adipic Acids, sebacic acid, het acid and tetrabromo phthalic anhydride; Unsaturated dibasic acids include maleic anhydride, phthalic acid and itaconic acid; Glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butadiol, 1,4-butadiol, 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A propylene Oxide adducts, dibromo neopentylglycol, pentaerythritol aryl ether, aryl glycidyl ether and the like; Styrene, vinyltoluene, chlorostyrene, t-butylstyrene, methyl methacrylate, polyaryl phthalate, triaryl cyanurate, etc. can be used as a vinyl monomer.

2) The organic solvent according to the present invention may be used in an amount of 8 to 30% by weight as described above.

The composition of the present invention includes 3) metal powder pigment in an amount of 1 to 15% by weight, and a metal pigment or pearl may be used as the metal powder pigment, and in the case of metallic pigment, 5 to 15% by weight may be used. 1 to 10% by weight is preferred. Metallic pigments are produced through processes such as milling, dispersion, filtration and concentration, solid content adjustment, weighing and packaging, etc., which are 1260MS, 63-337, 7640 NS and 1100MA manufactured by Toyo, Japan; 550N, MH-8805, and 205N from Japanese Digestion Co .; US Silver Line 1652AR and 1339AR are mainly used. In addition, Pearl is mainly used in the IRIODIN series of Merck, USA. Since the brightness and color of the surface-treated cured film depend on the particle size of the particles of the metal powder pigment, particles having a suitable particle size should be appropriately selected.

The composition of the present invention includes 4) 1 to 15% by weight of additives for supplementing physical properties, and the types of additives include enhancement of dispersibility of metal powder pigment, supplementation of appearance of dried surface treatment agent, supplementation of UV resistance, thermosetting drying It is distinguished for the purpose of promoting, controlling the time of spray coating, improving storage properties of metal powders, controlling particle arrangement of metal powders, and improving fluidity of surface treatment agents, and they are appropriately used depending on the type of binder and pigment used.

The composition of the present invention comprises 5) a resin containing an isocyanate group as a curing agent in a ratio of 1: 1 equivalent to the hydroxyl group of the binder, which resin is toluene diisocyanate, 4,4'-dipentylmethane diisocyanate, 4,4 ' It may be a homopolymer of a compound selected from the group consisting of dicyclohexylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate or modified form thereof.

In addition to the above essential components, the composition of the present invention may further include a color pigment having a color component insoluble in the solvent for the purpose of assisting the metal powder pigment. As the color pigment, conventional inorganic pigments and organic pigments may be used, and may be added in the preparation of the composition of the present invention in the form of colored pigment semi-finished products. The color pigment semi-finished product is premixed with a part of the binder, part of the dispersing additive and part of the solvent and dispersed using various dispersers (e.g., three roll mills, zeta mills, turbo mills, dyno mills, etc.) , By measuring the volatilization and non-volatile content of the solvent in accordance with the dispersion (see KSM-5000 2113 standard) can be produced by correcting the shortage. The colored pigment accounts for 5 to 90% by weight of the final colored pigment semifinished product, and the colored pigment semifinished product corresponds to 1 to 30% by weight based on the content of the surface treating agent composition.

The surface treating agent composition of the present invention having the above components can be prepared through the following process; First, a part of a binder, a part of a solvent, a colored pigment semi-finished product and a part of various additives are mixed and sufficiently stirred. While continuing to stir the mixture, a metal pigment mixture in the form of a slurry prepared by mixing a metal pigment, a part of a solvent and a part of various additives and stirring at a low speed for 5 minutes or more (freeing the metal pigment) is added thereto, and then the surface fluidity Add additives such as regulators slowly and stir sufficiently. Subsequently, to this mixture, a curing agent mixture consisting of an isocyanate group-containing resin, a part of a solvent and a part of various additives is added and stirred to prepare a surface treatment composition of the present invention. A schematic diagram of the manufacturing process of such a surface treating agent composition is shown in FIG. At this time, the curing agent composition should be mixed immediately before applying to the surface of the ABS molding.

According to the present invention, the surface of the ABS moldings is coated with the composition of the present invention using conventional surface treatment tools (eg manual air spray, automatic air spray, robotic surface treatment). In this case, the above-described organic solvents may be used as the diluent depending on the surface treatment conditions, and a manual air spray method is preferred. The coating solution is then dried at 70 to 80 ° C. for 30 to 50 minutes using heat or infrared light. During the drying process, the flow of the metal powders is smoothed, which inhibits the surface protruding phenomenon and can bring high gloss.

The surface treating agent composition according to the present invention can achieve smoothness and high gloss of the surface of the ABS molded article only by 1-coat coating, thereby shortening the surface treatment process and easily providing a high quality surface treated ABS molded article.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.

Production Example

(1) Preparation of cellulose acetate butyrate addition modified acrylic polyol resin solution

35% by weight of toluene was added to a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas introducing system, and then 10.5% by weight of methyl methacrylate, 5.18% by weight of butyl acrylate, and 2-hydroxyethyl methacrylate in the presence of nitrogen. 8.75 wt% of rate, 1.4 wt% of methyl methacrylic acid and 0.42 wt% of butyl peroxybenzoate as polymerization initiator were added dropwise at 110 ° C. for about 3 hours. Then, a solution obtained by dissolving 8.75% by weight of cellulose acetate butyrate powder in 30% by weight of butyl acetate was added to the mixture and reacted for 3 hours to prepare a cellulose acetate butyrate addition-modified acrylic polyol resin solution.

(2) Preparation of Butyl Methacrylate Modified Acrylic Polyol Resin Solution

35% by weight of toluene was added to a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas introducing system, and then 30% by weight of butyl methacrylate, 6.3% by weight of methyl methacrylate, and 12% by weight of butyl acrylate in the presence of nitrogen. , 9% by weight of 2-hydroxyethyl methacrylate, 1.2% by weight of methyl methacrylic acid and 1.4% by weight of butyl peroxybenzoate as a polymerization initiator were added dropwise at 110 ° C for about 3 hours. Subsequently, a solution in which 0.1% by weight of butyl peroxybenzoate was dissolved in 5% by weight of toluene was added and reacted for 3 hours to prepare a butyl methacrylate-modified acrylic resin solution.

(3) Preparation of methyl methacrylate modified acrylic polyol resin solution

45% by weight of toluene was added to a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas introduction system, and then 30% by weight of methyl methacrylate, 7.5% by weight of butyl acrylate, and 2-hydroxyethyl methacrylate in the presence of nitrogen. 10.25% by weight, 1% by weight of methyl methacrylic acid and 1.2% by weight of butyl peroxybenzoate as a polymerization initiator were added dropwise at 110 DEG C for about 3 hours. Then, a solution obtained by dissolving 0.05% by weight of butyl peroxybenzoate in 5% by weight of toluene was added and reacted for 3 hours to prepare a butyl methacrylate-modified acrylic resin solution.

(4) Preparation of methyl methacrylate modified acrylic polyol resin solution

40% by weight of toluene was added to a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas introducing system, and then 27.5% by weight of methyl methacrylate, 13.97% by weight of butyl acrylate, and 2-hydroxyethyl methacrylate in the presence of nitrogen. 11% by weight rate, 1.1% by weight of methyl methacrylic acid and 1.38% by weight of butyl peroxybenzoate as a polymerization initiator were added dropwise at 110 DEG C for about 3 hours. Then, a solution obtained by dissolving 0.05% by weight of butyl peroxybenzoate in 5% by weight of toluene was added and reacted for 3 hours to prepare a butyl methacrylate-modified acrylic resin solution.

(5) Preparation of cellulose acetate butyrate resin solution

40% by weight of toluene and 40% by weight of methyl ethyl ketone were added to the reactor to which the stirrer was attached, and then 20% by weight of cellulose acetate butyrate powder was slowly added thereto while stirring at high speed, followed by stirring for 1 hour to react the cellulose acetate butyrate resin solution. Prepared.

Examples 1-7

The surface treatment agent composition was prepared using the component of Table 1, and its usage-amount, respectively. Some of the binder, some of the solvent and some of the various additives were mixed and stirred for 1 hour. While continuing to stir the mixture, a slurry of a metal powder pigment prepared by mixing a metal powder, a part of a solvent, and a part of various additives was added thereto, followed by stirring for 1 hour. A surface treatment composition was prepared by adding a HDI Trimer N-3300 curing agent (manufactured by Bayer) to toluene at 50% solids concentration to the resulting mixture.

After adjusting the viscosity of the prepared surface treatment composition to 15 to 16 seconds (FORD CUP # 4) coated on an ABS molding, it was dried for 30 minutes at 70 ℃ and left for 72 hours at room temperature. Various physical properties of the formed coating film having a thickness of 20 to 30 μm were measured, and the results are shown in Table 1 below. In the case of Example 7, the SEM photograph of the formed coating film is shown in FIG.

Comparative Examples 1 to 3

The surface treatment agent composition was prepared in the same manner as in the above Example, using the ingredients shown in Table 1 and the corresponding amounts of use thereof. The composition was coated on an ABS molded product as a color paint and dried at room temperature for 5 minutes, then coated with A / T 6257 Clear (manufactured by Samsung Chemical Paint Co., Ltd.) as a clear paint thereon, and dried at 70 ° C. for 30 minutes. It was left at room temperature for 72 hours or more. Various physical properties of the formed coating film having a thickness of 20 to 30 μm were measured, and the results are shown in Table 1 below. In the case of the comparative example 3, the SEM photograph of the formed coating film is shown in FIG.

From the results of Table 1, it can be seen that the coating film of the present invention has excellent physical properties in spite of the 1-coat coating treatment, and in particular from the comparison of FIGS. 3 and 4, the surface treatment composition according to Example 7 is considerably smooth. It can be seen that it has a surface.

The surface treating agent composition according to the present invention can achieve smoothness and high gloss of the surface of the ABS molded article only by 1-coat coating, thereby shortening the surface treatment process and easily providing a high quality surface treated ABS molded article.

Claims (8)

1) 10 to 90% by weight of a binder resin comprising cellulose acetate butyrate addition-modified acrylic polyol resin and acrylic polyol or polyester polyol resin, 2) 8 to 30% by weight of an organic solvent, 3) 1 to 15% by weight of the metal powder pigment, 4) 1 to 15 weight percent of the additive, and 5) Resin containing a hydroxyl group and 1: 1 equivalent ratio of isocyanate groups in the binder Surface treatment agent composition of the acrylonitrile-butadiene-styrene (ABS) molding comprising a. The method of claim 1, A composition characterized in that the weight ratio of cellulose acetate butyrate addition modified acrylic polyol resin and acrylic polyol or polyester polyol resin is 5:95 to 40:60. The method of claim 1, The resin containing an isocyanate group is a group consisting of toluene diisocyanate, 4,4'-dipentylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate A composition characterized in that it is a homopolymer of a compound selected from or a variant thereof. The method of claim 1, The cellulose acetate butyrate addition-modified acrylic polyol resin is prepared by dissolving cellulose acetate butyrate in an organic solvent and then adding an acrylic monomer thereto and polymerizing for 2 to 4 hours. The method according to claim 1 or 4, The organic solvent is a nonpolar solvent selected from the group consisting of n-heptane, toluene, xylene, petroleum compounds and n-hexane, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dibasic esters, Polar solvent selected from the group consisting of 3-methoxy butyl acetate, amyl acetate, butyl glycol acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, diisobutyl ketone, isophorone and cyclohexanone, or polar with the non-polar solvent A composition characterized in that it is a mixture of solvents. The method of claim 4, wherein Acrylic monomers are methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Uryl methacrylate, methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, macro nitrile, methacrylonitrile, cyclohexyl methacrylate, acrylic acid, methacrylic acid, hydroxyl methacrylate, hydroxyl ethyl Acrylate, hydroxyl propyl methacrylate, hydroxyl propyl acrylate, styrene monomer, maleic acid, itaconic acid, acrylamide, n-methylol acrylamide, diacetone acrylamide, glycidyl methacrylate, vinyl toluene, Selected from the group consisting of vinyl acetate and vinyl chloride. Characterized in that the composition. A method of coating a 1-coat of an acrylonitrile-butadiene-styrene (ABS) molding comprising coating the surface treating agent composition of claim 1 on the surface of the acrylonitrile-butadiene-styrene (ABS) molding and then drying the coating. . Surface-treated acrylonitrile-butadiene-styrene (ABS) molded article prepared by the method of claim 7.