JPH093358A - Coating material composition, synthetic resin molded article having cured coating thereof on the surface, and method for producing the same - Google Patents

Abstract

PURPOSE: To obtain a coating composition which can give a coating film having improved antifogging properties, antistatic properties, hydrophilicity, durability and adhesion by mixing a specified monomer mixture with a fluorine-containing surfactant and a photopolymerization initiator. CONSTITUTION: A monomer mixture is obtained by mixing 20-100wt.% polyethylene glycol di(meth)acrylate of the formula I with 80-0wt.% monomer having at least one (meth)acryloyloxy group in the molecule and being other than the former monomer. 80-99.89 pts.wt this monomer mixture is mixed with 0.01-5 pts.wt. fluorine-containing surfactant of the formula II (X is an alkali metal or ammonium) and 0.1-15 pts.wt. photopolymerization initiator to obtain 100 pts.wt. coating composition. This composition is applied to the surface of a synthetic resin molding and cured by irradiation with an actinic radiation to form a cured coating film of a thickness of 1-25μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material composition, a synthetic resin molded article having a cured coating film on the surface thereof, and a method for producing the same.

[0002]

2. Description of the Related Art Synthetic resin moldings made of polycarbonate resin, acrylic resin, polystyrene resin, etc. are excellent in transparency and easy to process, so that they are not easily used in the field of lenses. Widely used in the building materials field. However, when these synthetic resin molded products are used in a hot and humid place or in an atmosphere with a large difference in temperature and humidity, there is a drawback that water condenses on the surface and the surface becomes cloudy and the transparency is lost. Further, since these synthetic resin molded products are easily charged with electricity, there is a drawback in that dust and dirt are attached and the appearance is lost.
Further, since the above synthetic resin lacks hydrophilicity (wettability), it cannot be used for applications requiring hydrophilicity, such as petri dishes and preparations.

Therefore, in order to improve the drawbacks of the above-mentioned synthetic resin molded products, a method of applying an anti-fog agent or an antistatic agent to the surface of the synthetic resin molded product, and a method of applying plasma to the surface of the synthetic resin molded product have been proposed. Alternatively, a method of performing treatment such as corona discharge has been proposed. However, the method of applying the anti-fog agent and the antistatic agent to the surface of the synthetic resin molded product has a problem that the performance is deteriorated by wiping or the like, or the performance is deteriorated with time. The method of performing plasma or corona discharge treatment on the surface of
There are problems that expensive equipment is required, uniform processing cannot be performed due to the shape, and the cost is increased.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have made it possible to perform antifogging property, antistatic property, hydrophilic property (wettability),
As a result of intensive studies aimed at providing a synthetic resin molded article having excellent durability and adhesiveness, as a result, a cured coating film of a coating material composition comprising specific compounding components is provided on the surface of the synthetic resin molded article. As a result, they have found that the above-mentioned object can be achieved and completed the present invention.

That is, the present invention provides (A) the following general formula (I)

Embedded image 20 to 100% by weight of at least one polyethylene glycol di (meth) acrylate (a-1) represented by
And 80 to 99.89 parts by weight of a monomer mixture comprising 80 to 0% by weight of a monomer (a-2) having one or more methacryloyloxy groups in one molecule other than the above, and (B) 0.01 to 5 parts by weight of a fluorinated surfactant represented by the general formula (II) C ₈ F ₁₇ SO ₃ X (II) (wherein X represents an alkali metal or an ammonium group), and (C) A coating material composition comprising 0.1 to 15 parts by weight of a photopolymerization initiator (provided that the total of components (A) to (C) is 100 parts by weight), and the above coating material composition. And a synthetic resin molded article having the cured coating film on the surface, characterized in that the above coating composition is applied to the surface of the synthetic resin molded article and irradiated with active energy rays. In the manufacturing method.

The polyethylene glycol di (meth) acrylate (a-1) represented by the above general formula (I) of the component (A) used for constituting the coating material composition of the present invention.
Is a hydrophilic monomer and is a component that improves the antifogging property, antistatic property and hydrophilicity of the cured film. Polyethylene glycol di (meth) acrylate used (a-1)
In the general formula (I), n is 2 to 20, preferably n is 9 to 14, and when n exceeds 20, the curability is deteriorated. These polyethylene glycol di (meth) acrylates may be used alone or in combination of two or more.

Further, the monomer (a-) having one or more (meth) acryloyloxy groups in one molecule other than the above general formula (I) of the component (A) used in the present invention.
2) (hereinafter, simply referred to as (meth) acrylate-based monomer (a-
Abbreviated as 2). ) Has good curability by ultraviolet rays,
A component for imparting excellent smoothness, flexibility, adhesion, scratch resistance, chemical resistance, and heat resistance to a cured film without deteriorating the antifogging property, antistatic property and hydrophilicity of the cured film. Is.

Examples of the (meth) acrylate-based monomer (a-2) used include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t. -Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, isooctyl (meth)
Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentanyl (meth)
Acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, hydrogenated product thereof, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxy. Ethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth) acryloylmorpholine and other monofunctional (meth) ) Acrylate monomer;
1,3-propylene glycol di (meth) acrylate, 1,4-heptanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
2-butyne-1,4-di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate,
1,5-pentanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, tricyclodecanyldi (meth) acrylate, hydrogenated products thereof, trimethylolpropane di (meth) acrylate, dipropylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis- (4
-(Meth) acryloxypropoxyphenyl) propane, 2,2-bis- (4- (meth) acryloxy (2-
Hydroxypropoxy) phenyl) propane, bis-
Bifunctional (meth) acrylate monomers such as (2-methacryloyloxyethyl) phthalate; and trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol Polyfunctional (meth) acrylate monomers such as motor (meth) acrylate; and the like. These monomers can be used alone or in combination of two or more.

The proportion of the polyethylene glycol di (meth) acrylate (a-1) represented by the above general formula (I) and the (meth) acrylate monomer (a-2) used is such that the monomer mixture (A) is used. Medium, (a-1) / (a-2) = 20-
It is in the range of 100/80 to 0 (wt%), and preferably (a-1) / (a-2) = from the viewpoint of the balance of antifogging property, antistatic property, adhesion property and surface appearance of the cured film. 70-95
The range of / 30 to 5 (% by weight) is preferable. The proportion of the component (A) used is 100 parts by weight of the total amount of the components (A) to (C).
80 to 99.85 parts by weight, preferably 95 to 97 parts by weight. When it is less than 80 parts by weight, the appearance and adhesion of the cured coating deteriorate, and when it exceeds 99.85 parts by weight, the curability of the cured coating deteriorates. Come to do.

Further, the fluorosurfactant (B) used for constituting the coating material composition of the present invention is a compound represented by the above general formula (II), and the cured coating has an antifogging property, It is a component that improves antistatic properties, hydrophilicity, and leveling properties. Examples of the fluorine-based surfactant (B) used include, for example, lithium perfluorooctane sulfonate,
Examples thereof include potassium perfluorooctane sulfonate, sodium perfluorooctane sulfonate, and ammonium perfluorooctane sulfonate. Among these, potassium perfluorooctane sulfonate and sodium perfluorooctane sulfonate are preferably used from the viewpoint of compatibility. The amount of the fluorinated surfactant (B) used is 0.0 based on 100 parts by weight of the total amount of the components (A) to (C).
It is 1 to 5 parts by weight, preferably 0.3 to 1.7 parts by weight. When the amount of the fluorosurfactant (C) used is less than 0.01 part by weight, the antifogging property, antistatic property and hydrophilicity are insufficient, and when it exceeds 5 parts by weight, the cured film becomes white and the appearance deteriorates. Like

Examples of the photopolymerization initiator (C) used for constituting the coating material composition of the present invention include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone and p-methoxy. Benzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-
Carbonyl compounds such as methyl-1-phenylpropan-1-one and 2-ethylanthraquinone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; acyl such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide Examples include phosphine oxide, which are used alone or in a mixture of two or more. Among these, it is more preferable to use benzophenone or methylphenylglyoxylate. The amount of the photopolymerization initiator (C) used is from (A) to
0.1 to 15 parts by weight, preferably 2 to 10 parts by weight in 100 parts by weight of the total amount of the component (C), and when the amount of the photopolymerization initiator (C) used is less than 0.1 parts by weight, curing will be insufficient. If the amount exceeds 15 parts by weight, the adhesion of the cured coating will be reduced.

Although the above are the essential components constituting the coating material composition of the present invention, an organic solvent may be contained in order to further adjust the viscosity. Organic solvents that can be used include:
For example, ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, dioxane; toluene, xylene , Etc., aromatic compounds; pentane, hexane, etc., aliphatic compounds; methylene chloride, chlorobenzene,
Examples thereof include halogenated hydrocarbons such as chloroform.

The coating composition of the present invention further comprises a leveling agent, an antifoaming agent, an antisettling agent, a lubricant, an abrasive,
You may add additives, such as a rust preventive and an antistatic agent.

The synthetic resin molded article having the cured coating film of the coating material composition of the present invention on the surface is obtained by applying the above coating material composition to the surface of the synthetic resin molded article and irradiating it with an active energy ray to cure. Can be obtained by

The coating material composition can be applied by brush coating, spray coating, dip coating, spin coating,
Although methods such as curtain coating, roll coating and screen printing are used, the spray coating method is preferred from the viewpoints of coating workability, smoothness of coating and uniformity.

The coating amount of the coating material composition is such that the thickness of the cured coating film is 1 to 25 μm, preferably 3 to 15 μm, and particularly preferably 5 to 10 μm. The thickness of the cured film is 1μ
If it is less than m, sufficient antifogging property, antistatic property and hydrophilicity cannot be obtained, and if it exceeds 25 μm, the adhesiveness is deteriorated.

As a means for curing the coating film applied to the surface of the synthetic resin molded article, a known method of irradiating with active energy rays such as α, β and γ rays can be used. The coating material composition of the present invention It is preferable to use ultraviolet rays as a means for curing the resin. Practical as a UV source,
UV lamps are commonly used from the economical aspect,
Specific examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a metal halide lamp. The atmosphere for irradiation may be in the air,
It may be an inert gas such as nitrogen or argon.

After coating the coating material composition of the present invention on the surface of the synthetic resin molded product and before curing with ultraviolet radiation energy, an infrared ray or hot air drying oven is used for the purpose of improving the adhesion of the cured coating to the substrate. Using, 20 ℃ ~ 120
You may perform heat processing for 1 minute-60 minutes at (degreeC).

The synthetic resin moldings used in the present invention are acrylic resin, polystyrene resin polycarbonate resin,
Polyester resin, polyethylene resin, ABS resin, acrylonitrile-styrene copolymer resin, polyamide resin, polyarylate resin, polymethacrylimide resin,
It is obtained by molding a polyallyl diglycol carbonate resin or the like, and as an example, a sheet-shaped molded product,
Examples include film-shaped molded products and various molded products such as mirrors, glasses, goggles, sun visors, showcases, meter covers, cosmetic containers, petri dishes, and preparations.

[0020]

The present invention will be described in more detail with reference to the following examples. The evaluations in Examples and Comparative Examples were performed by the following methods. Parts in the examples represent parts by weight.

(1) Appearance of cured coating The coating composition was applied and the appearance after curing was visually evaluated. ○: The surface is smooth and transparent. Δ: The surface is uneven and not smooth. ×: not smooth, whitening and tingling are observed.

[0022] (2) Put Chris cut reaching the substrate at 1mm intervals of the cured film provided on the adhesion synthetic resin molded product, a cross-cut of 1mm ² to 10
0 pieces were made, cellophane tape was stuck on it, and it was peeled off rapidly, and the number of peeled crosses was counted. ○: No peeling. △: Number of peeled 1 to 50 ×: Number of peeled 51 to 100

(3) Anti-fogging property A test piece for measuring anti-fogging property was set so as to face down in a constant temperature water bath having a water temperature of 40 ° C. installed at room temperature of 25 ° C., and then sealed until cloudy. The time was measured. ○: 10 minutes or more △: 1 minute to 10 minutes × ... 1 minute or less

(4) Antistatic Avantest TR-8601 type (applied voltage 100V, 2
The surface resistance value was measured and evaluated using 5 ° C. and 50% RH). ○ ... 1 × 10 ¹³ Ω or less ^{△ ... 1 × 10 13 Ω~1 ×} 10 14 Ω × ... 1 × 10 14 Ω or more

(5) Hydrophilicity The contact angle of the cured coating film with water was measured and evaluated. ○: 40 ° or less Δ: 40 ° to 60 ° × ... 60 ° or more

(6) Durability The cured coating film was lightly rubbed 100 times with absorbent cotton impregnated with water, and the antifogging property, antistatic property and hydrophilicity were evaluated by the above evaluation methods.

The abbreviations shown in Tables 1 and 2 represent the following compounds. PEGDA 400: Polyethylene glycol diacrylate (Formula (I) n = 9) PEGDA 600: Polyethylene glycol diacrylate (Formula (I) n = 14) PEGDA 800: Polyethylene glycol diacrylate (Formula (I) n = 19) PEGDA 1200 : Polyethylene glycol diacrylate (formula (I) n = 29) HPA: 2-hydroxypropyl acrylate PPGDA 400: Polypropylene glycol diacrylate (molecular weight 400) PPGDA 600: Polypropylene glycol diacrylate (molecular weight 600) DPHA: Dipentaerythritol hexaacrylate B1: Lithium perfluoroalkylsulfonate (manufactured by Dainippon Ink and Chemicals, Inc., Megafac F-11) B2: Potassium perfluoroalkylsulfonate (manufactured by Dainippon Ink and Chemicals, Inc., Megafac F-11) ) B3: perfluoroalkyl sodium sulfonate Co. Tochem Products Ltd. EF-103) BNP: Benzophenone MPG: Methyl phenyl glyoxylate

[Examples 1 to 7 and Comparative Examples 1 to 6] Coating material compositions having the compositions shown in Tables 1 and 2 were prepared. Then, these coating material compositions are spray-coated on an injection-molded plate (50 mm × 50 mm × 3 mm (thickness)) of a polycarbonate resin plate (trade name: Lexan LS-11, manufactured by GE), and 60 ° C. in a hot air dryer. And dried for 2 minutes. Then, it was irradiated in the air using a high pressure mercury lamp of 80 mW (manufactured by Western Quartz Co., Ltd.) (peak irradiation intensity on the substrate surface: 150 mW / cm ² , integrated light quantity 1500 mJ / c).
m ² and irradiation time 10 seconds), and various polycarbonate resin plates having a cured coating of 7 μm on the surface were obtained. The evaluation results of the obtained polycarbonate resin plate are shown in Tables 1 and 2.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

The coating material composition of the present invention having the above-mentioned constitution can be easily cured by irradiation with active energy rays and can form a cured coating film excellent in antifogging property, antistatic property and hydrophilicity. , Molded product applications where these characteristics are highly demanded,
In particular, it is extremely useful for forming articles such as mirrors, glasses, goggles, sun visors, showcases, meter covers, cosmetic containers, petri dishes, and preparations.

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Claims (3)

[Claims] (A) The following general formula (I): 20 to 100% by weight of at least one polyethylene glycol di (meth) acrylate (a-1) represented by
And 80 to 99.89 parts by weight of a monomer mixture comprising 80 to 0% by weight of a monomer (a-2) having one or more methacryloyloxy groups in one molecule other than the above, and (B) 0.01 to 5 parts by weight of a fluorinated surfactant represented by the general formula (II) C ₈ F ₁₇ SO ₃ X (II) (wherein X represents an alkali metal or an ammonium group), and (C) A coating material composition comprising 0.1 to 15 parts by weight of a photopolymerization initiator (however, the total of components (A) to (C) is 100 parts by weight). 2. A synthetic resin molded article having a cured coating film of the coating material composition according to claim 1 on its surface. 3. A method for producing a synthetic resin molded article having a cured coating on the surface, which comprises applying the coating material composition according to claim 1 to the surface of the synthetic resin molded article and irradiating with active energy rays.