KR20160133669A - A BTX free typed coating composition for ABS, or PC and ABS material parts, and the manufacturing method - Google Patents
A BTX free typed coating composition for ABS, or PC and ABS material parts, and the manufacturing method Download PDFInfo
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- KR20160133669A KR20160133669A KR1020150066488A KR20150066488A KR20160133669A KR 20160133669 A KR20160133669 A KR 20160133669A KR 1020150066488 A KR1020150066488 A KR 1020150066488A KR 20150066488 A KR20150066488 A KR 20150066488A KR 20160133669 A KR20160133669 A KR 20160133669A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C09D7/1233—
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a BTX-free coating composition for automobile wood interior materials of ABS (Acrylonitrile Butadiene Styrene) and PC + ABS (Polycarbonate + ABS), which is excellent in appearance and adhesion using a modified acrylic polyol resin, .
The heat curable coating composition according to the present invention is characterized by comprising 70 to 90 parts by weight of a modified acrylic polyol resin as a binder, 0.1 to 5 parts by weight of a reaction promoter, 0.5 to 5 parts by weight of an ultraviolet absorber, 0.1 to 5 parts by weight of a light stabilizer, 0.1 to 5 parts by weight of a surface slip agent, 0.1 to 5 parts by weight of an antistatic agent and 10 to 30 parts by weight of an ester solvent.
The modified acrylic polyol resin is obtained by modifying (replacing) a styrene monomer with a monomer selected from a methyl methacrylate monomer having no aromatic ring and an ethyl methacrylate monomer and having OH% of 0.5 to 2.0% and OH% of 4 To 8% by weight.
Description
The present invention relates to a BTX-free coating composition for automobile wood interior materials of ABS (Acrylonitrile Butadiene Styrene) and PC + ABS (Polycarbonate + ABS), which is excellent in appearance and adhesion using a modified acrylic polyol resin, .
ABS & PC + ABS material parts including wood-containing materials serve to fix parts such as automobile interior materials and ensure a beautiful appearance. The composition according to the present invention is excellent in adhesion and appearance to ABS & PC + ABS material parts (Leveling) and BTX free type.
BTX is an abbreviation for aromatic chemical products called benzene (B), toluene (T), and xylene (X), and broadly includes aromatic ring derivatives.
The Ministry of Land, Transport and Maritime Affairs voc regulations for automobile interior materials are as follows.
- Toluene / 1,000 ug / m 3
- Ethylbenzene / 1,600 ug / m 3 of reference value
-Xylene / standard value 870 ug per m 3
- Benzene / 30 ug / m 3
- Formaldehyde / 250 ug / m 3
- Styrene monomer / 300 ug / m 3
ABS & PC + ABS, which is used as a car wood interior material, is the most widely used among the practical plastics, is the most widely used, is light and has excellent injection molding processability, and is used as a major plastic material in various industries. Especially, its role as an automobile interior material is wide. This is because it is light and it contains some PC and it can be secured a more solid appearance, and it is attracting attention as a vehicle lightweight material. Laptops, mobile phones and other products that require light weight and high intensity are being applied continuously.
Conventional general plastic products are used in interior parts or invisible parts rather than appearance parts, and in principle, they can be used without painting, and the painted products are not a big problem in quality technology. However, as the years have passed, it has become increasingly demanding to diversify the appearance quality, to have a beautiful and luxurious appearance, and to suppress the new tea odor syndrome. As a result, the wood ink layer is now coated on the plastic material surface to obtain a superior appearance And the solvents used for the coatings were also concentrated in such a way that the smell was less irritating.
As such, the importance of coating and painting technology is increasing due to the trend of design, appearance, fineness, smell and the like which are strictly required. As a result of examining the shortcomings of the prior art so as to contribute to the improvement of the quality of the paint applied to the plastic material itself, the surface appearance quality and the odor and chemical resistance to be provided for the automobile wood interior material, Ratio and selection of BTX free type solvents, the inventors of the present invention have invented a coating material having excellent coating properties such as adhesion, chemical resistance and odor.
An object of the present invention is to provide a paint for use in parts made of ABS (Acrylonitrile Butadiene Styrene) or PC + ABS (Polycarbonate + ABS), including wood-containing materials which serve to fix parts such as automobile interior materials and ensure a beautiful appearance, Which is excellent in adhesion and leveling and has a BTX free type, and a method for producing the same.
According to the present invention,
Wherein the binder comprises 70 to 90 parts by weight of a modified acrylic polyol resin, 0.1 to 5 parts by weight of a reaction promoter, 0.5 to 5 parts by weight of an ultraviolet absorber, 0.1 to 5 parts by weight of a light stabilizer, 2 to 5 parts by weight of a surface modifier, Is a BTX-free thermosetting coating composition for parts of ABS or PC + ABS, which comprises 0.1 to 5 parts by weight of an antistatic agent and 10 to 30 parts by weight of an ester-based solvent.
In this case,
(Substituted) with one kind of monomer selected from methyl methacrylate monomer having no aromatic ring and ethyl methacrylate monomer instead of styrene monomer and having a OH content of 0.5 to 2.0% and an OH content of 4 to 8% .
And a mixed ratio of a modified acrylic polyol resin having an OH content of 0.5 to 2.0% and a modified acrylic polyol resin having an OH content of 4 to 8% in a weight ratio of 1: 0.5 to 1.
And the reaction promoter is dibutyltin dilaurate.
The ultraviolet absorber is benzotriazole and the light stabilizer is tetramethyl piperidine (TMP).
The surface control agent is also characterized by being a polyacrylate or a high boiling point mixture of alkylbenzene and diisobutylketone.
And the surface slip agent is silicon acrylate.
The antistatic agent is a carboxylic acid ester alkylol ammonium salt, and the ester solvent is butyl acetate.
The present invention also provides a process for preparing a BTX-free thermosetting coating composition for ABS or PC + ABS material parts,
(1) Modified (substituted) with one kind of monomer selected from methyl methacrylate monomer having no aromatic ring and ethyl methacrylate monomer instead of styrene monomer and having OH% of 0.5 to 2.0% and OH% of 4 to 8% Adding 70 to 90 parts by weight of the mixture to a vessel and mixing and stirring at 600 to 800 rpm for 5 to 10 minutes;
(2) adding 0.1 to 5 parts by weight of a reaction promoter, 1 to 5 parts by weight of an ultraviolet absorber and 0.1 to 5 parts by weight of a light stabilizer to the stirred mixture in the above step, stirring the mixture at 800 to 1000 rpm for 10 to 20 minutes while stirring;
(3) Thereafter, 2 to 5 parts by weight of a surface modifier, 0.1 to 5 parts by weight of a surface slip agent and 0.1 to 5 parts by weight of an antistatic agent are added and dispersed at 800 to 1000 rpm for 10 to 20 minutes with stirring. And
(4) adding 10 to 30 parts by weight of the ester-based solvent to the dispersion thus dispersed, stirring the mixture at 1000 to 2000 rpm for 10 to 20 minutes at a high speed, and aging the mixture.
More specifically, the styrene monomer may be replaced by a monomer selected from a methyl methacrylate monomer having no aromatic ring and an ethyl methacrylate monomer instead of a conventional styrene monomer, and acrylic (meth) acrylate having an OH content of 0.5 to 2.0% The polyol resin imparts adhesion and chemical resistance of the coating film as a main binder for forming a coating film. Also, the second acrylic polyol resin, which has been modified (substituted) with a monomer selected from methyl methacrylate monomer having no aromatic ring instead of styrene monomer and ethyl methacrylate monomer, and OH% of 4 to 8% It gives a role to assist sex. The two acrylic polyol resins are included in an amount of 70 to 90 parts by weight.
Dibutyltin dilaurate, which is a reaction accelerator, is added in an amount of from 0.1 to 5 parts by weight to make the curing reaction rate more dense to compensate for dryness, adhesion and chemical resistance.
The ultraviolet absorber composed of benzotriazole is 1 to 5 parts by weight and absorbs ultraviolet rays of the coating film to improve the light resistance.
2 to 5 parts by weight of a surface modifier which is a high boiling point mixture of polyacrylate or alkylbenzene and diisobutyl ketone to lower the surface tension so that the paint spreads well on the material.
0.1 to 5 parts by weight of a surface slip composed of silicone acrylate floats on the surface of the coating film to smooth the coating film, thereby enhancing external contamination and blocking.
And 0.1-5 parts by weight of an antistatic agent which is a carboxylate ester alkylol ammonium salt. This suppresses the generation of static electricity during coating work, thereby reducing the occurrence of appearance defects such as foreign matters and improving the workability of painting.
10 to 30 parts by weight of the ester-based solvent dilutes the resin and the paint to achieve dilution stability, and prevents boiling and bubbling during heating and drying.
As a reference, a general dispersing apparatus equipped with an impeller can be used as a dispersing apparatus used for dispersing a modified acrylic polyol resin, a solvent, and an additive in producing and manufacturing the composition of the present invention. In addition, sand mills using ceramic balls, high-speed dispersing machines using dyno mills and impellers, and the like, are advantageous in that they can be easily dispersed without using them.
According to the present invention, it is possible to provide a heat curable paint composition which is excellent in adhesion and leveling and is in a BTX free type as a paint for use in ABS (Acrylonitrile Butadiene Styrene) or PC + ABS (Polycarbonate + ABS) Can be obtained.
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the examples.
In order to demonstrate the efficacy of the present invention, composition and application experiments were conducted as follows.
1) Modified Acrylic Binder A: An acrylic polyol resin having a styrene monomer modified with a monomer selected from methyl methacrylate monomer having no aromatic ring and ethyl methacrylate monomer and having OH content of 0.5 to 2.0%
2) Acrylic binder A: Acrylic polyol resin containing styrene monomer and OH% of 0.5 to 2.0%
3) Modified acrylic binder B: an acrylic polyol resin having an OH% of 4 to 8% obtained by modifying a styrene monomer with a monomer selected from a methyl methacrylate monomer having no aromatic ring and an ethyl methacrylate monomer
4) Acrylic binder B: Acrylic polyol resin containing styrene monomer and OH% of 4 to 8%
5) Reaction accelerator: dibutyl tin dilaurate,
6) Ultraviolet absorber: a mixture composed of benzotriazole (TINUVIN 1130, Ciba)
7) Light stabilizer: a mixture of TMP (tetramethyl piperidine) (TINUVIN 292, Ciba)
8) Surface Conditioning Agent: Polyacrylate (DW-815, Daehang Polymer)
9) Surface modifier: High boiling point compounds such as alkylbenzene and diisobutyl ketone (BYKETOL-OK, BYK-Chemie)
10) Surface slip agent: polyether-modified dimethylpolysiloxane (BYK-333, BYK-Chemie)
11) Antistatic agent: carboxylic acid ester alkylol ammonium salt (BYK-ES-80, BYK-Chemie)
12) Ester solvent: Butyl Acetate
13) Polyhydric alcohol solvent: Dowanol PMA
14) Ketone type solvent: Metyl Iso-butyl ketone
As shown in Table 1, 1 to 4 of the compositions 1 to 15 are added to the dispersion vessel in order, and then mixed for 5 minutes while stirring for 10 minutes. The mixture is stirred for 20 minutes. Then, 8 to 11 are sequentially added while stirring, and the mixture is stirred for 20 minutes. Then, 12 to 14 are added, and the viscosity of the coating material is adjusted by medium-speed stirring. After the completion of the manufacturing process, test the physical properties of the designed paint and compare the standard results. The paint prepared in this manufacturing process contained a large amount of air bubbles. After aging for a certain period of time, the paint was stabilized and then a test piece was prepared to measure the physical properties.
The test specimens are coated with ABS & PC + ABS material with wood ink coating. After air degreasing, they are coated with 20 ~ 30㎛ of film thickness by air spray, then set at room temperature for about 10 minutes and then dried at 70 ℃ for 60 minutes.
Using the compositions of the paints obtained in Examples 1 to 5, the basic properties of the coating material and the coating film specimens were formed, and then the physical properties of the coating film were tested with the specimens. The results of the paint and film properties test are shown in Table 2 below.
1) The scratch resistance of the test specimens prepared in accordance with JIS K 6718 or the test specimens equivalent to JIS K 6718 is measured with a load of 4.9N (0.5kgf), STROKE of 100 ± 5mm, a friction speed of 100 (mm / sec) and a scratch of sapphire And the tip was 0.5R at an angle of 60 degrees and scratched once with a scratching tool having a diameter of 3 mm.
2) The tape peel test is carried out according to ISO 2409 or JIS K 5600-5-6. The surface was cleaned with a soft brush and the tape (JIS Z 1522) was firmly attached, and then the tape was strongly pulled out at an angle of 90 degrees to judge whether or not it was peeled off.
3) Impact resistance is to be measured by using ISO 6272 or JIS K 5600-5-3 with a weight drop of 4.9N (0.5kgf) and a collapsing diameter of 12.7mm. Check the status.
4) Moisture resistance is measured by leaving the specimen in a chamber at a temperature of 50 ± 2 ° C and a relative humidity of RH 95 ± 2%, removing the moisture from the surface by an air blast, and then leaving it at room temperature for 1 hour to check the surface condition of the specimen .
5) Chemical resistance is visually irradiated by rubbing the surface of the specimen with gasoline, engine oil, polish wax, grease, glass cleaner and ethyl alcohol chemicals 10 times with a force of about 5N.
6) Put the two sheets of the same size on the acrylic plate (50mm X 50mm) and apply 0.25g of Nivea SPF47 sun cream to the whole surface. The sun cream application area is placed on the specimen and the acrylic plate is pressed against it. Leave in the thermostat at 80 ± 2 ° C for 1 hour, remove the white cotton cloth and acrylic plate, leave at room temperature for 10 to 15 minutes, wash with neutral detergent and dry. The surface condition of the test piece is examined, and the adhesion and the scratch resistance test are immediately carried out under the above conditions, and the appearance is confirmed.
7) The heat-resistant cycling property is 3 Cycles under the condition of 80 ± 2 ℃ X3h → Room temperature 1h → -40 ± 2 ℃ X3h → Room temperature 1h → 50 ± 2 ℃, 95 ± 2% RHX7h → Room temperature 1h, , The surface condition of the test piece is examined, and the adhesion test is immediately carried out and the appearance is confirmed.
8) The light resistance is determined by the Xenon arc specified in FADE-O-METER (ISO 105, JIS L 0843, ASTM D 6695, SAE J 1885, SAE J 2412) 89 ± 3 ° C, 50 ± 5% RH, 0.55 ± 0.02 W 340nm), the specimen was cleaned with a neutral detergent solution to leave no OIL or water on the surface of the part. After removing the water on the surface by using the AIR BLOW, it was allowed to stand at room temperature for 1 hour. Evaluate and perform an adhesion test and check the appearance.
9) The abrasion resistance is tested by using a reciprocating abrasion tester at a speed of 60 revolutions per minute with a load of 9.8N (1kgf), STROKE 100 ± 5mm, double sided canvas # 10 rubbers and examine whether or not the substrate is exposed.
10) Environmentally harmful substances are requested to be certified by the Ministry of Land, Transport and Maritime Affairs (Korea Construction & Environment Testing Institute, Taesung Environmental Research Institute, etc.) for the inclusion of six regulated substances (benzene, toluene, xylene, ethylbenzene, formaldehyde, styrene) Check.
The results of the physical properties of the paint and the coating film prepared as described above are shown in Table 2. The nonvolatile matter was 47 to 50% by weight and had a viscosity of 53 to 60 KU in a Krebs-Unit viscometer. The specific gravity was in the range of 0.97 to 1.00.
As can be seen from the above results, Example 1, which has been conventionally used, was checked as a reference standard. As a result, in the case of appearance, Example 3 showed the best result and Example 5 showed the worst result .
All of the results of Examples 1 to 5 were very good in gloss.
In the case of scratch resistance, adhesiveness, moisture resistance, chemical resistance, anti-sun cream property, heat resistance cycle resistance, light resistance and abrasion resistance, all Examples 1 to 5 show good results. In the case of impact resistance, Example 4 is slightly As a result of falling.
In the case of the environmentally hazardous substance test, it was found that the regulated substance was contained in the standard of Example 1, and compared with the results of Examples 2 to 5, the six regulated substances of the Ministry of Land, I could see it.
According to the above results, as shown in (Table 2), it is possible to obtain a coating composition having excellent appearance, gloss, scratch resistance, adhesion, impact resistance, moisture resistance, chemical resistance, sunscreen resistance, heat resistance cycle resistance, light resistance, And the presence or absence of the presence or absence of the disease. Example 2 was then followed by excellent results.
The present invention relates to an antifouling coating composition which is excellent in adhesion and leveling of ABS & PC + ABS material parts including wood-containing materials, which serve to secure the appearance of parts such as automobile interior materials, and is required to have a less irritating paint with BTX free type odor Under the current conditions, it can be applied to automobile interior materials of various parts, various kinds of mobile phone parts, electronic devices, and the like, and can be applied to various other fields.
Claims (9)
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
The modified acrylic polyol resin may contain,
(Substituted) with one kind of monomer selected from methyl methacrylate monomer having no aromatic ring and ethyl methacrylate monomer instead of styrene monomer and having a OH content of 0.5 to 2.0% and an OH content of 4 to 8% Features,
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
Wherein the mixed ratio of the modified acrylic polyol resin having OH% of 0.5 to 2.0% and the modified acrylic polyol resin having OH% of 4 to 8% is 1: 0.5 to 1,
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
Characterized in that the reaction promoter is dibutyltin dilaurate.
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
Characterized in that the ultraviolet absorber is benzotriazole and the light stabilizer is tetramethyl piperidine (TMP).
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
Wherein the surface conditioning agent is a polyacrylate or a high boiling point mixture of alkylbenzene and diisobutyl ketone.
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
Characterized in that the surface slip agent is silicone acrylate.
No BTX for ABS or PC + ABS material parts. Thermal curing type coating composition.
The antistatic agent is a carboxylic acid ester alkylol ammonium salt,
And the ester-based solvent is butyl acetate.
ABS or PC + ABS parts. BTX is a heat curing type coating composition.
(2) adding 0.1 to 5 parts by weight of a reaction promoter, 1 to 5 parts by weight of an ultraviolet absorber and 0.1 to 5 parts by weight of a light stabilizer to the stirred mixture in the above step, stirring the mixture at 800 to 1000 rpm for 10 to 20 minutes while stirring;
(3) Thereafter, 2 to 5 parts by weight of a surface modifier, 0.1 to 5 parts by weight of a surface slip agent, and 0.1 to 5 parts by weight of an antistatic agent are added and dispersed with stirring at 800 to 1000 rpm for 10 to 20 minutes; And
(4) adding 10 to 30 parts by weight of an ester-based solvent to the dispersion dispersed in the above step, agitating the mixture at 1000 to 2000 rpm for 10 to 20 minutes at a high speed,
A process for preparing a BTX-free heat curable coating composition for ABS or PC + ABS material parts.
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| KR1020150066488A KR101746918B1 (en) | 2015-05-13 | 2015-05-13 | A BTX free typed coating composition for ABS, or PC and ABS material parts, and the manufacturing method |
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| WO2023020413A1 (en) * | 2021-08-17 | 2023-02-23 | 金发科技股份有限公司 | High-toughness flame-retardant polycarbonate alloy composition, and preparation method therefor and application thereof |
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| KR101978060B1 (en) * | 2017-10-26 | 2019-05-13 | 강남제비스코 주식회사 | 2-liquid type top coating paint for car using high solid Acrylic Polyol resin |
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| KR101160327B1 (en) | 2005-12-30 | 2012-06-26 | 주식회사 케이씨씨 | Ultraviolet and thermal curable resin compositions and coating compositions containing the same |
| KR101152179B1 (en) | 2010-01-22 | 2012-06-15 | 주식회사 케이씨씨 | Composition for undercoating plastic article and two component paint composition comprising the same |
| KR101463179B1 (en) | 2012-10-16 | 2014-11-21 | 주영산업 주식회사 | Two-Component Coating Compositions for chrome coating |
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