JP2003238845A - Coating material composition, molded product using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material composition for automobile head lamp lens coating with favorable abrasion and weather resistances without causing bluish white cloud on the coated surface of the automobile head lamp lenses by irradiation with an H.I.D. bulb light, and the molded products having cured coated layer formed with the coating material composition. <P>SOLUTION: The coating material composition curable by active energy ray contains a monomer and/or an oligomer having one or more radical polymerizable unsaturated double bond in one molecule (component A). The coating material compositions composed of 60% or over of the radically polymerizable component (A) used for the automobile head lamp lenses under irradiation with an active energy ray of 10 mW/cm<SP>2</SP>at 30°C cause no blueish white cloud by irradiation with the H.I.D. bulb light and exhibit favorable abrasion and weather resistances. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray-curable coating material composition and a molded article using the same.

[0002]

2. Description of the Related Art Generally, a polycarbonate resin is widely used as an engineering plastic having excellent transparency, moldability, heat resistance, and impact resistance. Widely used in automotive applications such as lenses, side cover lamp lenses, and glazing materials.
Among them, for the headlamp lens, a polycarbonate resin is particularly preferably used because of its weight reduction for improving the fuel efficiency of automobiles and variety of designs.

However, since the polycarbonate resin lacks in abrasion resistance, the surface thereof is easily damaged by scratches and the like. Further, it has a drawback that it has insufficient weather resistance as compared with other engineering plastics.

Particularly in automobiles used for outdoor applications, the headlamp lens, etc., has scratches due to dust or washing, deterioration of transparency due to light rays such as ultraviolet rays contained in sunlight etc., cracks, crazing, yellow bands. Since the problem of appearance deterioration such as increase in color is likely to occur, high abrasion resistance and weather resistance are required. Therefore, it is indispensable to form a coating that imparts wear resistance and weather resistance on the surface of the polycarbonate resin headlamp lens.

As a method of forming a coating film which compensates for such a drawback of the polycarbonate resin, Japanese Patent Laid-Open No. 56-12284.
No. 0, a coating composition prepared by mixing an ultraviolet absorber with an acrylic resin, a melamine resin, a urethane resin, a silicon resin, etc. is applied to the surface of a polycarbonate resin molded product to activate heat, ultraviolet rays, electron beams, or the like. A method of curing by using energy rays to form a film is disclosed. In particular, the active energy ray curing system has advantages such as superior productivity as compared with other methods, and so far, as a method capable of imparting excellent abrasion resistance and weather resistance to a polycarbonate resin molded product. Many coating agent compositions have been disclosed (Japanese Patent Laid-Open No. 5-179157 and Japanese Patent Laid-Open No. 5-230).
397, JP-A-5-17706, JP-A-5
-275769).

On the other hand, headlamp lenses are undergoing changes that have never been seen before. It is the change of light source. That is, a halogen bulb has been conventionally used as a light source for a headlamp, but in recent years, the amount of light is large and bright, and HID (High Intensitity Discharge)
It is changing to valves (or xenon valves). The HID bulb has a large amount of light, a low heat generation, and a long life as compared with a halogen bulb, and since a visual sensation similar to that during the daytime can be obtained at night, the driver's feeling of fatigue can be reduced.

[0007]

However, a headlamp lens having a coating film formed using a conventional coating composition which is cured by active energy rays or heat,
When the HID bulb is turned on, there is a problem that the coating on the surface of the headlamp lens becomes pale and cloudy. The present invention has been made in view of the above circumstances, and even in a headlamp lens of a headlamp using an HID bulb as a light source, a phenomenon in which the coating on the surface of the headlamp lens does not become pale is generated, Also provided are a coating material composition that forms a coating film having excellent performance such as abrasion resistance and weather resistance, and a molded article having a cured coating layer formed from the coating material composition.

[0008]

The coating material composition of the present invention comprises an active energy ray containing a monomer and / or oligomer (A) having at least one radically polymerizable unsaturated double bond in one molecule. In the curable coating material composition,
A monomer having a radically polymerizable unsaturated double bond and / or
Or, the oligomer (A) is 10 mW /
It is characterized in that, after irradiation with an active energy ray of cm ² , 60% or more thereof undergoes a radical polymerization reaction in less than 1 minute.
In addition, the coating material composition comprises a monomer having at least one radically polymerizable unsaturated double bond in one molecule and /
Alternatively, a coating material composition containing 0.1 to 10 parts by mass of the photopolymerization initiator (B) with respect to 100 parts by mass of the oligomer (A), wherein the photopolymerization initiator (B) is a methanol solution. Medium absorption coefficient at 405 nm is 100 ml / g · cm
The radical-polymerizable photopolymerization initiator (b1) is 1 to
It is preferable to contain 100% by mass. Further, it is preferable that the coating material composition further contains an ultraviolet absorber (C) and / or a hindered amine light stabilizer (D).
The molded article of the present invention is characterized by having a cured coating layer formed from the coating composition. In addition, a molded product having the above-mentioned cured coating layer is manufactured by H.264. I. D. A headlamp lens for an automobile headlamp having a bulb as a light source is preferable. Further, the headlamp lens is preferably made of polycarbonate resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The coating material composition of the present invention comprises a monomer and / or oligomer (A) having one or more radically polymerizable unsaturated double bonds in one molecule (hereinafter referred to as component (A)). (Abbreviated) is an active energy ray-curable coating material composition, wherein the component (A) is 10 m under conditions of 30 ° C.
Less than 1 minute after irradiation with W / cm ² of active energy rays,
60% or more of the radical polymerization reaction occurs. The coating material composition of the present invention is not particularly limited as long as it contains such component (A). Hereinafter, an example of the constitution of the coating material composition of the present invention will be described.

As the component (A) used in the present invention,
There is no particular limitation as long as it can be cured with active energy rays. Usable monomers and oligomers include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloylalkoxysilane. Examples thereof include monofunctional (meth) acrylates having a polymerizable unsaturated bond, polyfunctional (meth) acrylates, and the like, which may be appropriately selected depending on the required performance of the coating.

Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl. (Meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate,
Morphoryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, tricyclodecane (meth) acrylate, polyethylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl ( (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl Addition of (meth) acrylate, mono (meth) acrylate such as phenyl (meth) acrylate, phthalic anhydride and 2-hydroxyethyl (meth) acrylate Include mono (meth) acrylate compounds such as.

Specific examples of polyfunctional (meth) acrylates include 1,4-butanediol-di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,9-nonanedioldi (meth) acrylate. ,
Neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (n = 2 to 15) di (meth) acrylate,
Polypropylene glycol (n = 2-15) di (meth)
Acrylate, polybutylene glycol (n = 2-1
5) Di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2
-Bis (4- (meth) acryloxydiethoxyphenyl) propane, trimethylolpropane diacrylate, bis (2- (meth) acryloxyethyl) -hydroxyethyl-isocyanurate, trimethylolpropane tri (meth) acrylate, Tris (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol-
Rutetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type diepoxy and epoxy di ( Epoxy poly (meth) acrylate such as (meth) acrylate, urethane tri (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with a trimer of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 2-hydroxypropyl Urethane di (meth) acrylate reacted with (meth) acrylate, urethane hexa (meth) reacted with isophorone diisocyanate and pentaerythritol tri (meth) acrylate Acrylate, di cycloalkyl diisocyanate and 2-hydroxyethyl (meth) urethane di obtained by reacting acrylate (meth) acrylate, di cycloalkyl diisocyanate and poly (n =. 6 to
15) Urethane poly (meth) acrylate such as urethane di (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with a urethanization reaction product with tetramethylene glycol, trimethylolethane, succinic acid and (meth) acrylic Polyester (meth) acrylate such as polyester (meth) acrylate reacted with acid, trimethylolpropane and succinic acid, ethylene glycol, and polyester (meth) acrylate reacted with (meth) acrylic acid Can be mentioned.

Other than the above, an organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloylalkoxysilane is also used for increasing the hardness of the coating. Specifically, colloidal silica and vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 2 -(Meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, etc. And an organic-inorganic hybrid vinyl compound and an organic-inorganic hybrid (meth) acrylate compound.

The above-mentioned component (A) may be used alone, but it is preferable to use a plurality of them in combination if necessary. In particular, 1-2 kinds of monofunctional acrylates and 1-
A combination of two polyfunctional acrylates and a urethane poly (meth) acrylate compound having at least two or more radically polymerizable unsaturated double bonds in one molecule covers the surface of an automobile headlamp. Suitable for More specifically, poly (meth) acrylates of mono or polypentaerythritol 10 to 40
5 to 40 parts by mass of a urethane poly (meth) acrylate compound having at least two radically polymerizable unsaturated double bonds in one molecule, and poly [(meth) acryloyloxyalkyl] (iso) cyanurate 20 to 20 parts by mass. 70
A combination of parts by mass is preferable, and a coating film having excellent heat resistance, chemical resistance, durability, and adhesion to a substrate can be obtained. When the poly (meth) acrylate of mono- or polypentaerythritol is 10 parts by mass, a cured coating having sufficient abrasion resistance cannot be obtained, and when it exceeds 40 parts by mass, abrasion resistance tends to decrease. Furthermore, if it is blended in a large excess, cracks are likely to occur in the cured film,
Cracks may occur in the cured film after the durability test or the weather resistance test. In addition, the heat resistance of the cured coating tends to decrease. If the amount of the urethane poly (meth) acrylate compound is less than 5 parts by mass, a cured coating having sufficient toughness and weather resistance cannot be obtained, and the curability in an air atmosphere tends to be poor. If it exceeds 40 parts by mass, the abrasion resistance tends to decrease. If the poly [(meth) acryloyloxyalkyl] (iso) cyanurate is less than 20 parts by mass, a cured coating having sufficient abrasion resistance and heat resistance cannot be obtained, and if it exceeds 70 parts by mass, the curability tends to decrease. It is in.

The coating composition of the present invention has the above-mentioned (A).
405n in a methanol solution based on 100 parts by mass of the component
Radical polymerizable photopolymerization initiator (b1) having an extinction coefficient in m of 100 ml / g · cm or more 1 to 100% by mass
It is preferable to include 0.1 to 10 parts by mass of the photopolymerization initiator (B) (hereinafter abbreviated as component (B)) to be contained.

The above radical-polymerizable photopolymerization initiator (b1)
Examples thereof include an acylphosphine oxide system. As a specific example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“lucirin TPO
, Manufactured by BASF), 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide (“lucirin
TPO-L ", manufactured by BASF) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (" Irg.819 "manufactured by Chiba Specialty Chemicals). , Bis (2,6-dimethoxybenzoyl) -2,
Examples thereof include bisacylphosphine oxide represented by 4,4-trimethyl-pentylphosphine oxide (“CGI403”, manufactured by Chiba specialty Chemicals).

Other usable radically polymerizable photopolymerization initiators (b1) include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-
1 (“Irg.369”, manufactured by Chiba specialty Chemicals) and aminoketones and camphorquinones. The radical polymerizable photopolymerization initiator (b1) is
When the content is 1 to 100% by mass in the component (B), it is easy to obtain a sufficient curing rate. As will be described in detail later, a cured coating layer formed from a coating material composition having a sufficient curing rate is described in H.264. I. When formed in a headlamp lens of a vehicle headlamp having a D bulb as a light source, the headlamp lens has an effect of improving the phenomenon of bluish whitish without impairing performance such as abrasion resistance and weather resistance.

The component (B) is a radical-polymerizable photopolymerization initiator (b) which does not impair the above effects.
A photopolymerization initiator other than 1) may be contained. Examples of the photopolymerization initiator component used in combination with the radical polymerizable photopolymerization initiator (b1) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether,
Acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, methylphenylglyoxylate, 2-hydroxy-2-
Carbonyl compounds such as methyl-1-phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide and the like can be mentioned.

The component (B) is 0.1 to 10 parts by mass, more preferably 2 to 4 parts by mass, relative to 100 parts by mass of the component (A). If the amount of component (B) is less than 0.1 parts by mass, the curability of the coating film may be insufficient, and sufficient abrasion resistance, adhesion and weather resistance may not be obtained. On the contrary, when the amount of the component (B) exceeds 10 parts by mass, the coating may be colored and the weather resistance may be deteriorated.

The coating material composition of the present invention may further contain an ultraviolet absorber (C) and / or a hindered amine light stabilizer (D). The above ultraviolet absorber (C)
The ((C) component) is not particularly limited. Any material can be used as long as it can be uniformly dissolved in the coating material composition and can impart necessary weather resistance. In particular, benzophenone series,
A compound derived from benzotriazole type, phenyl salicylate type, and phenyl benzoate type, ultraviolet absorbers (C) having a maximum absorption wavelength in the range of 240 to 380 nm are preferable, and particularly benzophenone type and benzotriazole type ultraviolet rays. The absorbent (C) is preferable, and it is most preferable to use the above two kinds in combination.

Specific examples of the ultraviolet absorber (C) include 2
-Hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-octyloxybenzophenone, 4
-Dodecyloxy-2-hydroxybenzophenone, 2-
Hydroxy-4-octadecyloxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, phenyl salicylate, p-tert-
Butylphenyl salicylate, p- (1,1,3,3,
-Tetramethylbutyl) phenyl salicylate, 3-hydroxyphenylbenzoate, phenylene-1,3-
Dibenzoate, 2- (2-hydroxy-5'-methylphenyl) benzotriazole, 2- (2-hydroxy-
5-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy3,5-tert-
Butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryl Roxyethylphenyl) -2H-benzotriazole, 2- (2,4-dihydroxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -2H-benzotriazole, 2- (2,4-dihydroxyphenyl) -4,6
-Reaction products of bis (2,4-dimethylphenyl) -1,3,5-triazine and glycidyl alkyl (C12-C13) ether are mentioned. Among them, benzophenone-based 2-hydroxy 4-oct Xybenzophenone, 2,4-dihydroxybenzophenone, and benzotriazole-based 2- (2-hydroxy-tert)
-Butylphenyl) benzotriazole is particularly preferable, and it is more preferable to use a combination of two or more thereof.

The ratio of the ultraviolet absorber (C) used is (A)
It is 2 to 30 parts by mass, more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the component. UV absorber (C) is 2
If it is less than 10 parts by mass, the weather resistance of the cured coating tends to be insufficient, and if it exceeds 30 parts by mass, the curing of the coating itself becomes insufficient and the toughness, heat resistance, and abrasion resistance of the cured coating tend to decrease. is there.

Hindered amine light stabilizer (D)
Examples of the component (D) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,
2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2) , 2,6,6-Tetramethyl-4-piperidyl) sebacate, bis (1-propoxy-2,2,6,
6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, bis (1-pentyloxy-
2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-
Heptyloxy-2,2,6,6-tetramethyl-4-piperidi-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, bis (1-nonyloxy-2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis (1
-Decanyloxy-2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, bis (1-dodecyloxy-
2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like can be mentioned, and among these, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate is particularly preferable. .

The proportion of the hindered amine light stabilizer (D) used is 0.1 to 5 relative to 100 parts by weight of the component (A).
Parts by mass, more preferably 0.5 to 2 parts by mass. When the hindered amine light stabilizer (D) is less than 0.1 parts by mass, the weather resistance and durability of the cured film are insufficient, and when it exceeds 5 parts by mass, the curing of the film itself becomes insufficient and the toughness of the cured film is high. , The heat resistance and wear resistance tend to decrease.

The coating material composition of the present invention, if necessary,
Organic solvent, antioxidant, yellowing agent, blueing agent,
Ingredients such as various additives such as pigments, leveling agents, defoaming agents, thickeners, anti-settling agents, antistatic agents, antifogging agents and the like may be contained. The organic solvent is preferably selected and used according to the type of base material to which the coating composition is applied. For example, when polycarbonate is used as the base material, it is preferable to use an alcohol solvent such as isobutanol, an ester solvent such as n-butyl acetate or diethylene glycol acetate, in combination. The amount of the organic solvent used is preferably 20 to 800 parts by mass with respect to 100 parts by mass of the coating material composition.

In the coating material composition having the above-mentioned constitution, 60% or more of the radical polymerization reaction occurs in less than 1 minute after irradiation with an active energy ray of 10 mW / cm ² at 30 ° C. (A ) Component.

0.003 g (sample) of the coating material composition was sampled in an aluminum dish having a diameter of 6 mm, and at 30 ° C.
The coating material composition is cured by irradiating the sample with ultraviolet light having an intensity of 10 mW / cm ² using a high pressure mercury lamp. The amount of heat generated by polymerization during curing is determined by the Dupont 930 Differential Photocalori
meter (made by Dupont) and Dupont 910 Differential Scan
Ning Calorimeter (manufactured by Dupont) is used for measurement, and the time required for 60% reaction of radical polymerization of the coating material composition is calculated from the measurement result.

As a method for controlling the curing rate to a predetermined value (a method for increasing the curing rate), (1) a method of increasing the irradiation amount of active energy rays, (2) a radical-polymerizable photopolymerization initiator (b1) is used. However, other methods such as increasing the concentration of the initiator and (3) increasing the temperature of the atmosphere can be mentioned. Among these, wear resistance and weather resistance are not impaired, and headlamp lenses for automobile headlamps H. I.
Even if the light of the D bulb is irradiated, the phenomenon that it becomes cloudy white is improved,
From the viewpoint of obtaining more preferable light, 0.1 to 10 parts by mass of the component (B) containing 1 to 100% by mass of the radically polymerizable photopolymerization initiator (b1) as described above is used as the component 10 of the component (A).
The method used for 0 part by mass is preferred.

The coating material composition of the present invention is applied to a substrate and then crosslinked by irradiation with active energy rays to form a cured coating layer. As a method for applying the coating composition, known methods such as a spray coating method, a spin coating method, a shower flow coating method, a curtain flow coating method, and a dipping method can be applied. Further, the coating amount is preferably within a range such that the thickness of the obtained cured coating layer is 3 to 12 μm.

When curing by irradiation with active energy rays, the organic solvent is volatilized, and then ultraviolet rays or the like are irradiated using a high pressure mercury lamp, a metal halide lamp or the like. The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon.

The coating material composition of the present invention can be used for modifying the surface of various synthetic resin molded articles which are base materials.
Examples of synthetic resin molded products include various thermoplastic resins and thermosetting resins that have been conventionally demanded to have improved wear resistance and weather resistance. Specifically, polymethylmethacryl resin, polycarbonate resin, polyester resin, poly (polyester) carbonate resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, polymethacrylimide resin, polyallyl diglycol carbonate resin. And so on. In particular,
Since polymethylmethacryl resin, polycarbonate resin, polystyrene resin, and polymethacrylimide resin have excellent transparency and strong demands for improvement in abrasion resistance, it is particularly effective to apply the coating material composition of the present invention. A synthetic resin molded product is an automobile headlamp lens made of these resins.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. All "parts" in the examples mean "parts by mass". (Examples 1 to 6) A coating material composition was prepared at a compounding ratio shown in Table 1, and a coating film after curing was applied to a polycarbonate resin plate having a thickness of 3 mm (trade name "Lexan LS-II", manufactured by GE). Was 8 μm. The organic solvent was volatilized by heating for 90 seconds in a heating furnace at 60 ° C., and then a high pressure mercury lamp was used in the air to measure wavelengths of 340 to 38.
A test piece was obtained by irradiating with energy having an integrated light amount of 0 nm of 3000 mJ / cm ² and curing. At this time, the time required for the radical polymerization reaction of the component (A) to be 60% or more is 1
Was less than a minute. In particular, in Example 4, it was less than 30 seconds. The curing time was obtained as described above.

[0033]

[Table 1]

(Comparative Examples 1 to 12) A coating material composition was prepared at the compounding ratio shown in Table 2, and a polycarbonate resin plate (trade name "Lexan LS-II", manufactured by GE) having a thickness of 3 mm was prepared.
Spray coating was applied so that the cured coating film had a thickness of 8 μm.
After the organic solvent is volatilized by heating for 90 seconds in a heating furnace at 60 ° C., a high pressure mercury lamp is used in the air, and the cumulative light amount at a wavelength of 340 to 380 nm is 3000 mJ / cm ²
Was irradiated with the above energy to be cured to obtain a test piece. At this time, the time required for the radical polymerization reaction of 60% or more of the component (A) was 1 minute or more. The curing time was obtained as described above.

[0035]

[Table 2]

The evaluation methods for each example and comparative example are as follows. (1) Appearance of cured film The appearance of a test piece obtained by applying and curing the coating composition was visually evaluated. The criteria for judging the result are as follows. ○: The surface is smooth and transparent. △: Partly cloudy. ×: Whitening, yellowing, and cloudiness.

(2) Presence or absence of a phenomenon in which the cured film becomes pale and cloudy when the HID bulb is turned on. From the back side of the test piece, the HID bulb (trade name "HID Handy"
Light Pro. ", Manufactured by Koito Manufacturing Co., Ltd.) was turned on to determine whether or not there was a phenomenon in which the cured coating became cloudy in white. The criteria for judging the result are as follows. ○: It is colorless and transparent. X: A phenomenon of bluish white clouding and whitening are observed.

(3) Wear resistance Using a Taber wear tester, wear wheels CS-10,500
After 300 rotations of wear under a g load, the diffuse transmittance (haze value) was measured to determine the wear resistance. The criteria for abrasion resistance are as follows. ○: increased haze value = 0 to 15 Δ: increased haze value = 16 to 20 x: increased haze value = 20 or more

(4) Adhesiveness Cross-cuts reaching the substrate at 1 mm intervals were placed in the cured coating on the test piece to make 100 1 mm ² squares, and an adhesive tape was affixed to it and peeled off rapidly. I counted the number of crosses. The criteria for judging the result are as follows. ○: There is no peeling at all. Δ: The number of peelings is 1 to 50. X: The number of peeled pieces is 51 to 100.

(5) The heat resistance test piece was put in a hot air dryer at 120 ° C. for 24 hours, and the appearance change of the cured film on the test piece was visually observed. The criteria for judging the result are as follows. ○: No change. △: Small cracks occurred. ×: Cracks were generated on the entire surface of the coated plate.

(6) The weather resistance test piece was tested with a sunshine carbon weatherometer ("W
EL-SUN-HC-B type ", manufactured by Suga Test Instruments Co., Ltd.) and tested using a weather resistance tester (black panel temperature 63 ± 3 ° C., rainfall 12 minutes, irradiation 48 minutes cycle). Changes in the cured film after exposure for 2000 hours and 2500 hours were observed, and the appearance, adhesiveness, occurrence of cracks, and peeling of the film were examined. The criteria for judging the result are as follows. As for the appearance, those with almost no discoloration compared to the initial stage are marked with ◎,
The case where there was a slight yellowing was marked with ◯, and the case where the yellowing was large was marked with x. The adhesion was evaluated by the same method as the above (4) Adhesion. Regarding the occurrence of cracks and peeling of the film, those that did not exist were marked with ◯, and those that did exist were marked with x.

The evaluation results of Examples 1 to 6 are shown in Table 3 and Comparative Example 1
Table 4 shows the evaluation results of ~ 12. The symbols in the table are as follows. DPHA: dipentaerythritol hexaacrylate UA1: urethane acrylate having a molecular weight of 2500 synthesized from 2 mol of dicyclohexylmethanediol, 1 mol of nonabutylene glycol and 2 mol of 2-hydroxyethyl acrylate TAIC: tris (2-acryloyloxyethyl) isocyanurate PA1: polyester acrylate ( "Aronix M-8030 manufactured by Toagosei") HBPB: 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole BOTS: bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl ) Sebacate BNP: benzophenone MPG: methylphenylglyoxylate MAPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BAP Bis (2,4,6-trimethylbenzoyl)
-Phenylphosphine oxide Irg.184: 1-hydroxycyclohexyl phenyl ketone Irg.654: benzyl dimethyl ketal Irg.369: 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) butanone-1

[0043]

[Table 3]

[0044]

[Table 4]

As is apparent from Table 3, the molded articles having the cured coating layer formed from the coating material compositions produced in Examples 1 to 6 were excellent in that they did not cause the phenomenon of bluish white when the HID bulb was turned on. Have performance. On the other hand, Comparative Examples 1 to 3
Since the curing rate of the coating material composition produced in (1) was 1 minute or more, a molded article having a cured coating layer formed from the coating material composition was not preferable because the phenomenon of bluish white clouding was observed. The coating material compositions produced in Comparative Examples 4 and 5 had a curing rate of 1 minute or more, and molded articles having a cured coating layer formed from the coating material compositions not only showed a phenomenon of bluish white clouding,
Since the compounding amount of DPHA as the component (A) was not appropriate, abrasion resistance, heat resistance and weather resistance were deteriorated. The coating material compositions produced in Comparative Examples 6 and 7 had a curing rate of 1 minute or more, and molded articles having a cured coating layer formed therefrom were
Not only the phenomenon of bluish-white clouding was observed, but also the abrasion resistance and weather resistance were deteriorated because the compounding amount of UA1 as the component (A) was not appropriate. The coating material composition produced in Comparative Example 8 was
A molded article having a curing rate of 1 minute or more, and having a cured coating layer formed therefrom not only has a phenomenon of becoming cloudy in white, but also contains a large amount of TAIC as the component (A).
Abrasion was reduced. The coating material compositions prepared in Comparative Examples 9 and 10 have a curing rate of 1 minute or more, and molded articles having a cured coating layer formed from the coating material compositions show not only a phenomenon of bluish whiteness, but also the component (C). Since the compounding amount of HBPB was not appropriate, abrasion resistance, adhesion, heat resistance, and weather resistance deteriorated. The coating material compositions produced in Comparative Examples 11 and 12 had a curing rate of 1 minute or more, and molded articles having a cured coating layer formed from the coating material compositions exhibited not only a phenomenon of bluish white clouding, but also a component (D). Since the compounding amount of BOTS is not appropriate, abrasion resistance, heat resistance, and weather resistance were deteriorated.

[0046]

EFFECTS OF THE INVENTION According to the coating material composition of the present invention, when it is used for a headlamp lens of an automobile headlamp, the H. I. Even if the light from the D bulb is irradiated, it has the effect of not causing a bluish-white clouding phenomenon, and has excellent performance such as abrasion resistance and weather resistance. Therefore, the headlamp lens using the coating material composition of the present invention has a clearer visual field for the driver and is advantageous in terms of safety, as compared with the headlamp lens having the coating film of the conventional coating material composition. .

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) F21S 8/10 C08L 69:00 F21V 5/00 F21M 3/02 R 17/00 // C08L 69:00 (72) Invention Koji Furukawa 4-1-1, Sunadabashi, Higashi-ku, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Laboratory F-term (reference) 3K042 AA08 AB01 AB04 BC00 4F006 AA36 AB43 BA02 CA05 DA04 EA03 4J011 QA03 QA07 QA13 QA23 QA24 QA27 QA34 QA34 QA34 QA34 QB14 QB16 QB19 QB24 QB29 QC10 SA06 SA22 SA26 SA32. CA29 CA32 CA34 CB10 CC03 CC05 CD04 4J038 FA111 PA17 PB07 PB08

Claims (6)

[Claims] 1. An active energy ray-curable coating material composition containing a monomer and / or oligomer (A) having one or more radically polymerizable unsaturated double bonds in one molecule, wherein the radically polymerizable The monomer and / or oligomer (A) having an unsaturated double bond is 10 m under the condition of 30 ° C.
Less than 1 minute after irradiation with W / cm ² of active energy rays,
A coating material composition, characterized in that 60% or more thereof undergoes a radical polymerization reaction. 2. 100 parts by mass of the monomer and / or oligomer (A) having at least one radical-polymerizable unsaturated double bond in one molecule, to the photopolymerization initiator (B) 0.
A coating material composition containing 1 to 10 parts by mass, wherein the photopolymerization initiator (B) is 405 nm in a methanol solution.
1 to 100% by mass of the radical-polymerizable photopolymerization initiator (b1) having an extinction coefficient of 100 ml / g · cm or more
The coating material composition according to claim 1, comprising: 3. The coating material composition according to claim 1, further comprising an ultraviolet absorber (C) and / or a hindered amine-based light stabilizer (D). 4. A molded article having a cured coating layer formed from the coating material composition according to claim 1. 5. A molded article having the cured coating layer is made of H.264.
I. D. The molded article according to claim 4, which is a headlamp lens for an automobile headlamp having a bulb as a light source. 6. The molded product according to claim 5, wherein the headlamp lens is made of a polycarbonate resin.