KR100403667B1 - Photocurable coating composition using urethane acrylate oligomer - Google Patents

Abstract

PURPOSE: Provided is a photocurable coating composition using urethane acrylate oligomer, which allows the molded product to have excellent appearance, durability, heat resistance, and other physical property. CONSTITUTION: The photocurable coating composition comprises 10-70 wt% of urethane acrylate oligomer of formula 1, 10-60 wt% of reactive monomer, 0.1-20 wt% of photoinitiator, and 0-10 wt% of leveling agent. In the formula 1, R3 is aliphatic, alicyclic, aromatic compounds, or oligomer of these compounds, X is fluorine compound of formula 4: CpF(2P+1)-R8-OH or formula 5, or a mixture thereof, R8 is C1-C10 alkylene group, p is an integer of 1-10, R9 is any one of F, CF3, CH2F, CHF2, q is an integer of 1-5, R10 is C1-10 alkylene, Y is polyester polyol of formula 2 or polyether polyol of formula 3: HO-£-R6-O-C(=O)-R4-C(=O)-O-R5-O-|n-H, each of R4 and R5 is C2-C10 aliphatic or aromatic compounds, n is 1-20, each of R6 and R7 is C2-C10 aliphatic or aromatic compounds, o is 1-20, R1 is hydrogen or methyl group, R2 is C2-C6 alkylene group, and each of l and m is 1-6.

Description

Photocurable coating film composition using urethane acrylate oligomer

The present invention relates to a photocurable coating composition, and more specifically, to a coating composition comprising a urethane acrylate oligomer, a reactive monomer, a photoinitiator, a leveling agent, and an additive, fiber reinforced plastic (FRP), polybutylene terephthalate (PBT) , Molded grades coated on heat-resistant grade plastic moldings, such as polyamide (NYLON 66), polyphenylene oxide (PPO), or polyphenylene sulfide (PPS), ie automotive products, electrical / electronic products, and other industrial products The present invention relates to a photocurable coating composition using a urethane acrylate oligomer which has excellent aesthetics, durability, heat resistance and other physical properties.

Surfaces are coated on electronic components and industrial products requiring metal vacuum deposition and heat resistance of electric devices and automobile lamp reflectors. Conventionally, thermosetting paints containing acrylic thermosetting resins, silicone resins, and melamine resins have been mainly used. .

However, these thermosetting paints have to be exposed to heat for a long time in order to form a coating film. As a result, the production yield decreases due to long-term heating, and high temperatures may adversely affect the physical properties of the plastic molded products. It is emerging.

In order to solve the above problems, a coating film composition containing general photocurable oligomers, for example, Korean Patent Nos. 73183 and 74985, US Patent Nos. 3,782,061, 3,850,770, 3,891,523, 3,907,574, Coating compositions disclosed in Nos. 3,932,356 and 4,301,209, Japanese Patents No. 59-117,561, and Digestion Nos. 63-221,119 are poor in physical properties such as heat resistance, water resistance and chemical resistance, and thus are not particularly applicable to plastic molded articles requiring heat resistance. .

Accordingly, the present invention has been made to actively solve the problems of the prior art, and its object is to provide heat resistance that can be coated on electronic components and industrial products requiring coating and heat resistance for metal vacuum deposition of electric devices and automobile lamps and reflectors. It is to provide a photocurable coating film composition using excellent special urethane acrylate oligomer, reactive monomer, photoinitiator and the like.

The urethane acrylate oligomer, reactive monomer, photoinitiator, leveling agent and additives for achieving the object of the present invention is a photocurable coating composition 10 to 70% by weight of the special urethane acrylate oligomer of the general formula (1), reactive monomer 10 It is characterized by containing -60 wt%, photoinitiator 0.1-20 wt%, leveling agent 0-5 wt% and a small amount of additives.

Wherein R ³ is aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds,

X is a fluorine compound of the general formula (4), (5) or a mixture thereof,

Y is a polyester polyol of formula (2) or a polyether polyol of formula (3),

R ¹ is hydrogen or a methyl group,

R ² is an alkylene group having 2 to 6 carbon atoms,

l, m is 1-6.

The urethane acrylate oligomer of the general formula (1) is a polyisocyanate functional group of the aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds with the polyester polyol of the general formula (2) or the polyether polyol of the general formula (3) NCO), and then react some of the unreacted isocyanates with the fluorine compounds of the following general formulas (4) and (5) with at least one component or mixture thereof, and react the remaining unreacted isocyanates with hydride of the general formula (6) It is prepared by addition reaction with a hydroxy group-containing acrylate, and is used in an amount of 10 to 70% by weight of the total coating film composition. In this case, when used at 10% by weight or less, heat resistance, water resistance, and chemical resistance are lowered. When used at 70% by weight or more, the appearance and adhesion of the coating film become poor. It is preferable.

R ⁴ and R ⁵ here are aliphatic or aromatic compounds having 2 to 10 carbon atoms,

n is 1-20.

R ⁶ and R ⁷ are aliphatic or aromatic compounds having 2 to 10 carbon atoms,

o is 1-20.

R ⁸ is an alkylene group having 1 to 10 carbon atoms,

p is an integer of 1-10.

Where R ⁹ is one of F, CF ₃ , CH ₂ F, CHF ₂ ,

q is an integer of 1 to 5,

R <^10> is a C1-C10 alkene group.

Where R ¹ is hydrogen or a methyl group,

R ¹¹ is an alkylene group having 2 to 6 carbon atoms.

The polyester polyol of the general formula (2) used in the preparation of the urethane acrylate oligomer of the general formula (1) is an acid having two carboxyl groups, that is, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and fumaric acid. Obtained by esterification condensation reaction such as glycol having two hydroxyl groups, phthalic acid, terephthalic acid and the like, that is, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and nucleated methylene glycol. It is preferable to use the polyester polyol of -600 and molecular weight 200-4,000.

Polyether polyol of the general formula (3) is obtained by etherification condensation reaction of glycol having two hydroxyl groups, ie, ethylene glycol, tetrahydrofuran, etc. Preference is given to using 4,000 polyether polyols.

Fluorine compounds of the general formula (4) include 2-nonafluoro butyl ethanol, 2-tridecafluoro hexyl ethanol, 2-heta deca fluoro octyl ethanol, 2-henacosa fluoro decylethanol,

Fluorine compounds of the general formula (5) include 2,3-difluoro benzyl alcohol, 2-fluoro benzyl alcohol, 1- (pentafluorophenyl) -ethanol, 2- (trifluoromethyl) benzyl alcohol and the like. .

The hydroxy group-containing acrylate of the general formula (6) is hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, hydroxy butyl methacrylate Hydroxy pentyl acrylate, hydroxy pentyl methacrylate, hydroxy hexyl acrylate, hydroxy hexyl methacrylate and the like.

On the other hand, as the diisocyanate used for the synthesis of the urethane acrylate oligomer of the general formula (1), isophorone diisocyanate, 4,4-dihexyl methane diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene Diisocyanate, 2,4,4-trimethyl 1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 1,4-cyclonuylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene Diisocyanates and oligomers of these compounds. In particular, oligomers of isocyanate compounds are trifunctional of 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, biuret of toluene diisocyanate, and isocyanurate structure. Triisocyanates or composite structures thereof and the like may be used.

The equivalent ratio of the isocyanate compound to the polyester polyol or polyether polyol is suitably 0.5 to 1.5 equivalents of the polyester polyol or polyether polyol to 2 equivalents of the isocyanate compound, and if the polyol is 0.5 equivalent or less, the adhesion and mechanical properties of the coating film are poor. In addition, if it is 1.5 equivalent or more, sclerosis | hardenability is bad. A more preferable equivalent ratio is 0.8-1.2 equivalent of polyester polyol or polyether polyol to 2 equivalent of isocyanate. In addition, an unreacted isocyanate of the intermediate obtained by the addition reaction of the polyester polyol or the polyether polyol is further reacted with the fluorine compound of the general formulas (4) and (5) and the hydroxy group-containing acrylate of the general formula (6). The urethane acrylate oligomer is prepared by a known method, wherein an equivalent ratio of isocyanate compound, fluorine compound and hydroxy group-containing acrylate is 0.5-1.5 equivalents of fluorine compound and hydroxy group-containing acrylate equivalent to 2 equivalents of isocyanate compound. If the compound and the hydroxy group-containing acrylate are 0.5 equivalent or less, the curability is poor, and if it is 1.5 equivalent or more, the adhesion and mechanical properties are poor. More preferable equivalent ratio is 0.8-1.2 equivalent of fluorine compound and hydroxy group containing acrylate with 2 equivalent of isocyanate.

Here, the ratio of fluorine compound and hydroxy group-containing acrylate equivalent is about 1: 9 to 5: 5, and when it is out of this range, heat resistance, water resistance, curability and other physical properties are poor. That is, when there are few fluorine compounds, heat resistance and water resistance are poor, and when there are few hydroxyl group containing acrylates, curability, adhesiveness, mechanical properties, etc. are poor. Therefore, in consideration of heat resistance, water resistance and curability, the equivalent ratio is preferably 2: 8 to 4: 6.

Such water-containing urethane acrylate oligomer of the general formula (1) has excellent heat effect, water resistance and chemical resistance by fluorine compound, and has low surface tension and excellent workability when applying paint. That is, the composition excellent in physical properties can be obtained by applying this oligomer to a coating film composition.

On the other hand, as the reactive monomer which is a component of the present composition, 2-ethylhexyl acrylate, octyldecyl acrylate, stearyl acrylate, behenyl acrylate, trilycyl methacrylate, nonylphenol ethoxylate monoacrylate, beta -Carboxyethyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 4-butylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl Monofunctional monomers such as acrylate, ethoxyethoxyethyl acrylate, ethoxylated monoacrylate,

1,6-hexanediol diacrylate, triphenylglycol diacrylate, butanediol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate Ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate Bifunctional monomers such as methacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, and

Trimethyl propane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tri (2-hydroxyethyl Trifunctional monomers such as isocyanurate triacrylate,

Polyfunctional monomers, such as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, alkoxylated tetraacrylate, can be used,

In consideration of the physical properties of the product, it is preferably 10 to 60% by weight based on the total.

As photoinitiators, conventional polymerization initiators activated by ultraviolet rays are used, and in particular, benzophenone series, benzyl dimethyl ketal series, acetophenone series, adraquinone series, thioxanthone series, acyl phosphine oxide series, and amino alkylphenes 2-hydroxy 1,2-diperphenyl ethanone, 2-ethoxy 1,2-diphenyl ethanone, 2-isopropyl 1, such as non-based, hydroxy alkyl phenone, dialkoxy acetophenone, benzyl ketal, etc. , 2-phenyl ethanone, 2-butoxy 1,2-diphenyl ethanone, 2-isobutoxy 1,2-diphenyl ethanone, 2,2-dimethoxy 1,2-diphenyl ethanone, 2, 2-dibutoxy 1-phenyl ethanone, 1-hydroxy cyclohexyl phenyl ketone, dimethoxy hydroxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy 2-methyl propanone, 2-methyl 1 -[4- (methylthio) phenyl] -2-morpholino propane, 2-benzyl 2-dimethylamino 1- (4-morpholinophenyl) -butanone or 3,6-bis [2-methyl- 2-morpholino (propa) Carbonyl) - butyl carbazole can be employed.

As the leveling agent, a silicone diacrylate-based or silicone polyacrylate-based compound is used in an amount of 0 to 10% by weight of the total composition. When semi-gloss or matte is required for the coating composition, a matting agent is added in the range of 0 to 10% by weight. 10% by weight can be used.

Coating operations on plastic molded parts consist of spraying, dipping or roller coating, which can be advantageously selected depending on the material of the plastic, the shape of the molded part and the coating thickness.

Different viscosity is required depending on the coating method, which can be used by adjusting the viscosity by adding an appropriate amount of volatile solvent. In addition, the volatile solvent increases the adhesion of the coating film by giving a chemical impact on the plastic material before curing during painting work. Solvents which can be used are ketones, acetates, aromatic compounds, etc., One or more are mixed and used. The usage-amount can be used for the varnish / solvent weight ratio as 4/1-1/4.

In addition, as an additive, an antifoamer etc. can be used according to the characteristic of a well-known compound.

Hereinafter, the present invention will be described in detail through preferred embodiments.

In the following examples to compare the physical properties of the photocurable coating composition and the conventional coating composition using a special urethane acrylate oligomer of the present invention to examine the effects of the present invention, these examples do not limit the scope of the present invention.

Example 1

1 equivalent of polyester polyol having a molecular weight of 1000, 2-trideca fluorohexylethanol produced by condensation of adipic acid and neopentyl glycol to 2 equivalents of isophorone diisocyanate trimer (product of OLIN, U.S. name: LUXATE ITM 800) (Product of ATOCHEM, France) 50 parts by weight of urethane acrylate made from 0.3 equivalents, 0.7 equivalents of hydroxyethyl acrylate, 20 parts by weight of pentaerythritol tetraacrylate (manufactured by UCB, Belgium), 1,6-hexanediol diacrylate 4.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by CIBA-GEIGY, Switzerland, product name: IRGACURE 184) and silicone polyacrylate (manufactured by UCB, Belgium, product name: EBECRYL 350) 0.5 weight part was fully stirred to prepare a photocurable coating composition.

Example 2

Photocurable coating composition was prepared in the same composition, content and method as in Example 1, except that 0.3 equivalent of 2,3-difluoro benzyl alcohol (manufactured by Japan Chemical Industries, Ltd.) was used instead of 0.3 equivalent of 2-trideca fluorohexyl ethanol. It was.

Example 3

Photocuring was carried out in the same composition, content and method as in Example 1 except that 0.3 equivalent of 1,4-bis (trifluoromethyl) benzyl alcohol (manufactured by Nippon Shokai Industries) was used instead of 0.3 equivalent of 2-trideca fluorohexyl ethanol. The coating composition was prepared.

Comparative Example 1

A photocurable coating composition was prepared in the same composition, content and method as in Example 1, except that 1 equivalent of hydroxy ethyl acrylate was used instead of 0.3 equivalent of 2-trideca fluorohexyl ethanol and 0.7 equivalent of hydroxy ethyl acrylate.

Comparative Example 2

Except for using 50 parts by weight of the urethane acrylate of Example 1 except that 30 parts by weight of urethane acrylate (manufactured by SARTOMER, product name: CN-964) and 20 parts by weight of non-reactive acrylic resin (molecular weight: about 10,000) was used. Photocurable coating film composition was prepared in the same composition, content and method as described above.

The photocurable coating composition of the present invention prepared above and the conventional photocurable coating composition were applied to the metal vacuum deposition of the automobile headlamp reflector and subjected to a physical property comparison test.

In the following test, 50 wt% of the mixed solvent methyl ethyl ketone (MEK) and toluene were mixed in a photocurable coating composition to a weight ratio of 1/1 to a weight ratio. Using spray sprayer, apply 15 micrometer (μm) thickness, evaporate the solvent at 50 ℃ for 2 minutes, dry it, and then UV-cured at 800mJ / cm2 of curing energy (UV irradiation device: American American Violet Corporation). Aluminum was vacuum-deposited (vacuum deposition machine: manufactured by Hanil Corporation) at 10 ^-4 Torr.

Since the test results comparing the physical properties are as shown in 31.

Table 1. Comparison of Physical Properties According to Examples and Fertilizers

In the test, the coating thickness of the specimen used was 15㎛. The heat resistance was measured after 96 hours in the oven at 180 ℃, the adhesion was measured by the J D 0202 (JIS D 0202) test method, 240 ℃ in hot water at 40 ℃ hot water resistance After passing, the adhesion was measured. Acid resistance in chemical resistance was measured after 10 minutes of immersion in 1% sulfuric acid solution at room temperature, and alkali resistance was measured after 10 minutes in 1% sodium hydroxide solution at room temperature. It was measured after 10 minutes of deposition.

As can be seen from Table 1, it can be seen that the photocurable coating composition according to the present invention was excellent in heat resistance, hot water resistance, and chemical resistance.

As described in detail above, the coating composition according to the present invention can improve the heat resistance, water resistance, and chemical resistance when used for vacuum deposition of electric elements and automotive lamps reflectors and other materials requiring heat resistance.

Claims (5)

Urethane acrylate oligomer containing 10 to 70% by weight of urethane acrylate oligomer of general formula (1), 10 to 60% by weight of reactive monomer, 0.1 to 20% by weight of photoinitiator and 0 to 10% by weight of leveling agent Photocurable coating film composition used. here, R ³ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X is a fluorine compound of the general formula (4) or (5) or a mixture thereof, R ⁸ is an alkylene group having 1 to 10 carbon atoms, p is an integer of 1-10. Wherein R ⁹ is one of F, CF ₃ , CH ₂ F, CHF ₂ , q is an integer of 1-5, R ¹⁰ is an alkylene group having 1 to ¹⁰ carbon atoms. Y is a polyester polyol of formula (2) or a polyether polyol of formula (3), Here, R ⁴ and R ⁵ are aliphatic or aromatic compounds having 2 to 10 carbon atoms, n is 1-20. Here, R ⁶ and R ⁷ are aliphatic or aromatic compounds having 2 to 10 carbon atoms, o is 1-20. Where R ¹ is hydrogen or a methyl group, R ² is an alkylene group having 2 to 6 carbon atoms, l and m are 1-6. The method of claim 1, Reactive monomers include 2-ethylhexyl acrylate, octyldecyl acrylate, stearyl acrylate, behenyl acrylate, tridecyl methacrylate, nonylphenolethoxylate monoacrylate, beta-carboxyethyl acrylate, isobornyl acrylic Tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 4-butylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, ethoxyethoxyethyl acrylic At least one monofunctional monomer selected from the group consisting of latex, ethoxylated monoacrylates; 1,6-hexanediol diacrylate, triphenylglycol diacrylate, butanediol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate Ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate Two or more bifunctional monomers selected from the group consisting of methacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, ethoxylated neopentylglycol diacrylate; Trimethylol propane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (20 hydroxyethyl) At least one trifunctional monomer selected from the group consisting of isocyanurate triacrylate; Using urethane acrylate oligomers selected from the group consisting of at least one polyfunctional monomer selected from the group consisting of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate and alkoxylated tetraacrylate Photocurable coating composition. The method of claim 1, Photoinitiators are 2-hydroxy 1,2-diperphenyl ethanone, 2-ethoxy 1,2-daephenylethanone, 2-isopropyl 1,2-phenyl ethanone, 2-butoxy 1,2-diphenyl Ethanone, 2-isobutoxy 1,2-diphenyl ethanone, 2,2-dimethoxy 1,2-diphenyl ethanone, 2,2-dibutoxy 1-phenyl ethanone, 1-hydroxy cyclohexyl phenyl Ketone, dimethoxy hydroxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy 2-methyl propane, 2-methyl 1- [4- (methylthio) phenyl] -2-morpholino pro From the group consisting of panon, 2-benzyl 2-dimethylamino 1- (4-morpholinophenyl) -butanone or 3,6-bis [2-methyl-2-morpholino (propanoyl) -butylcarbazole Photocurable coating film composition using a urethane acrylate oligomer, characterized in that at least one selected. Metal vacuum deposition molded article of the electrical element and automotive lamp reflector which coated the photocurable coating composition of Claim 1. A heat resistant plastic molded article coated with the photocurable coating composition of claim 1.