JPH05320289A - Actinic radiation curing coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. capable of forming a coating film excellent in weatherability, adhesion and cracking resistance by blending a partial condensate of colloidal silica and a hydrolyzate of a specific silane compd. with specific polyfunctional monomers and a photopolymn. initiator. CONSTITUTION:The compsn. comprises (A) 5-49wt.% partial condensate of colloidal silica comprising silica particles of 1 to 200mmu in prim. particle size and a hydrolyzate of a silane compd. of formula I [R<1> is a single bond or a bivalent (substd.) hydrocarbon group; R<2> is a monovalent hydrocarbon group or H; R<3> is a monovalend (substd.) hydrocarbon group; a is 1 to 3; b is 0 to 2; and a+b is 1 to 3], (B) 51-95wt.% polyfunctional monomers having at least 2 (meth)acryloyloxy groups per molecule and comprising at least 30wt.% polyfunctional monomer of formula II [R<4>, R<5> and R<6> are each a bivalent (substd.) hydrocarbon group; and X is a group of formula III or IV], and (C) a photopolymn. initiator in an amt. of 0.1 to 5 pts.wt. per 100 pts.wt. total of the components A and B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray curable coating composition capable of forming a weather resistant, abrasion resistant and scratch resistant cured coating film.

[0002]

2. Description of the Related Art Synthetic resin moldings such as polymethylmethacrylate resin, polycarbonate resin and polyarylate resin are not only lighter in weight and superior in impact resistance than glass, but also inexpensive. It has various advantages such as easy molding and is widely used in many fields by taking advantage of these advantages. For example, it is used in glazing of automobiles, buses, airplanes and other public transportation vehicles or lenses such as headlamp lenses and corner lenses, and lenses for spectacles and optical devices.

However, since the surface hardness of these synthetic resin molded products is insufficient, the surface is damaged by the action of contact with other objects, impact, scratching, etc. during transportation of the molded product, attachment of parts or use. And the aesthetics are damaged,
The product value will decrease and the product yield will decrease.

Therefore, there is a strong demand for improving the surface hardness of the surfaces of these synthetic resin molded products, and many methods for improving the surface hardness have been proposed. For example,
A coating composed of a partial condensation reaction product of a silane mixture containing an alkyltrialkoxysilane as a main component and colloidal silica is applied to the surface of a molded article, and then this is heat-treated to form a cured film and improve wear resistance. Method, or a coating mainly composed of a polyfunctional acrylate having two or more (meth) acryloyloxy groups in one molecule is applied to the surface of a molded product, and then ultraviolet rays are irradiated to form a cured film. Methods for improving wear resistance have been proposed.

Of these methods, the former is an excellent method because it has a large effect of improving the wear resistance, but since the adhesion to the molded product is poor, a primer coat treatment is required, resulting in high cost. However, the heat treatment becomes complicated, and the heat treatment is long, so that there is a problem in productivity. In addition, the latter is excellent in productivity because the curing time is extremely short as several seconds to ten and several seconds due to the ultraviolet curing method, and in recent years a method capable of curing even in air has been proposed, which is an economically extremely useful method. However, this latter UV curing method tends to have a lower level of wear resistance than the former heat curing method, and the fact that the wear resistance level is obviously low for the latter especially when the abrasive material is abrasive grains Is recognized.

Therefore, a method utilizing the former method and the latter method has also been proposed. That is, JP-A-1-18
Japanese Patent No. 8509 discloses a UV-curable silicone coating composition in which a polyfunctional acrylate is mixed with a partial condensate of colloidal silica and vinyl-functional silane. The advantage of using ultraviolet rays for curing is that the curing time, which was a fundamental problem with silicon-based coating materials, can be greatly shortened, and curing can be performed in a few seconds to a few minutes, which is advantageous in terms of productivity. Is recognized.

[0007]

However, the silicon coating material composition disclosed in JP-A-1-188509 has a problem that the weather resistance is insufficient. In other words, the performance required of the coating material composition is not only improved in wear resistance of the synthetic resin molded product but also improved in weather resistance, and particularly in outdoor applications, high weather resistance is required. However, the abrasion-resistant synthetic resin molded article obtained by using the silicon coating material composition of the above-mentioned publication does not have sufficient weather resistance, and the cured film is cracked in the accelerated exposure test such as sunshine and weather meter. Occurrence was observed, an increase in haze value, an increase in yellowness, and a decrease in adhesion were observed,
There remains the issue of weather resistance. An object of the present invention is to provide an active energy ray curable coating material composition that solves the above problems.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies on improving the weather resistance of a silicon coating material composition. As a result, a partial condensation reaction product of a colloidal silica component and a vinylsilane compound and a specific polyfunctional (metafunctional ) The active energy ray-curable coating material composition containing acrylate in a specific ratio has been found to have good weather resistance and to solve the above problems, and has completed the present invention.

The present invention comprises (a) colloidal silica composed of silica particles having a primary particle size of 1 to 200 millimicrons and the following formula:

[0010]

[Chemical 3]

(Wherein R ¹ is a single bond or a substituted or unsubstituted divalent hydrocarbon group, R ² is a monovalent hydrocarbon group or a hydrogen atom, and R ³ is a substituted or unsubstituted monovalent hydrocarbon group. Yes,
a is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is 1 to 3.
5 to 49% by weight of a partial condensation reaction product with a hydrolyzate of a silane compound represented by the formula:

[0012]

[Chemical 4]

[Wherein R ⁴ , R ⁵ and R ⁶ are the same or different, substituted or unsubstituted divalent hydrocarbon groups, and X is CH ₂ ═C
H-COO- group or a CH ₂ = C (CH ₃₎ containing 30 wt% or more of polyfunctional monomer represented by -COO group], 2 or more acryloyloxy groups and / or meta in one molecule Acryloyloxy group-containing polyfunctional monomer 51-
95% by weight, (c) a photopolymerization initiator as a component (a) and (b)
The active energy ray curable coating material composition comprises 0.1 to 5 parts by weight based on 100 parts by weight in total of the components.
The present invention will be described in detail. First, each component will be described.

Regarding the component (a), the component (a) is a partial condensation reaction product of colloidal silica and a hydrolyzate of the silane compound represented by the general formula (I). The colloidal silica used here is composed of silica particles having a primary particle size of 1 to 200 millimicrons, and ultrafine particles of silicic acid anhydride are used as a colloidal solution. Also, powdery colloidal silica containing no dispersion medium can be used in the present invention.
As the dispersion medium of colloidal silica, water, methanol,
Ethanol, iso-propanol, n-butanol, n
-Alcohols such as propanol, ethylene glycol
Polyhydric alcohols such as alcohols, polyhydric alcohol derivatives such as ethyl cellosolve and butyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol
2-hydroxyethyl acrylate
, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, etc., and general organic solvents. In the present invention, particularly, an alkyl group having 1 to 4 carbon atoms in the alkyl group is used. -Groups are preferred.

As these colloidal silicas, commercially available ones manufactured by a known method can be used. For example, a water-dispersed colloidal silica (trade name: SNO-TEX), a methanol-dispersed colloidal silica (trade name: methanol-silica sol), an iso-propanol-dispersed colloidal silica (trade name) marketed by Nissan Kagaku Co., Ltd. IPA-ST), a methanol-dispersed colloidal silica (trade name OSCA) commercially available from Catalyst Kasei Co., Ltd.
L1132), iso-propanol-dispersed colloidal silica (trade name OSCAL1432), and the like. As the powdery colloidal silica, there may be mentioned the trade name OSCAP available from Catalyst Kasei Co., Ltd. The colloidal silica of the present invention is available in acidic or basic form, but it is more preferred to use the acidic form in the method of making the coating composition of the present invention.

It is preferable to use a particle having a particle diameter of 1 to 200 mm, particularly preferably 5 to 80 mm. If the particle size is less than 1 millimicron, the stability of the dispersed state is poor and it is difficult to obtain a uniform quality, and if the particle size exceeds 200 millimicrons, the transparency of the coating becomes poor and turbidity You can only get big ones.

The hydrolysis product of the vinylsilane compound represented by the general formula (I) is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy). ) Silane, vinyltriacetoxysilane, vinyltetramethylenetrimethoxysilane, vinyloctamethylenetrimethoxysilane, vinyltriisopropoxysilane, vinyltris-t-butoxysilane, vinyldimethylethoxysilane, etc.
It can be obtained by a conventional method such as stirring with water in the presence of an effective amount of a hydrolysis catalyst, for example, hydrochloric acid, at a temperature lower than normal temperature to a reflux temperature for about 1 to 10 hours. Among the vinylsilane compounds, vinyltrimethoxysilane is
It is particularly preferable because it has excellent polymerization activity upon irradiation with active energy rays, especially ultraviolet rays, and has a large effect of exhibiting wear resistance of the cured film.

Next, preparation of a partial condensation reaction product obtained by reacting colloidal silica and a hydrolyzate of vinylsilane, that is, the component (a) will be described. This preparation is performed, for example, by the method shown below. The vinylsilane compound is stirred in the presence of an effective amount of a hydrolysis catalyst, for example, hydrochloric acid, at a temperature from a temperature lower than room temperature to a reflux temperature for several hours to sufficiently hydrolyze, and then a colloidal silica is added, and the mixture is mixed. A method of obtaining a partial condensation reaction product by stirring the system at a temperature from normal temperature to reflux temperature. A method of obtaining a partial condensation reaction product by mixing a vinylsilane compound, an effective amount of a hydrolysis catalyst and colloidal silica, and stirring the mixed system at a temperature from normal temperature to reflux temperature.

A vinylsilane compound, an effective amount of a hydrolysis catalyst and colloidal silica are blended, and volatile components such as alcohols are distilled from the mixed system under atmospheric pressure or reduced pressure to a maximum of 100% of distillate components. And then reacting at a temperature from room temperature to about 120 ° C. to obtain a partial condensation reaction product. A vinylsilane compound, an effective amount of a hydrolysis catalyst and colloidal silica are blended, and after thoroughly stirring this mixed system,
The volatile component of the mixed system is replaced with a monomer of the component (b) of the present invention, a monomer other than the component (b), a mixture thereof, or an organic solvent, and then the temperature is changed from room temperature to about 12
A method of obtaining a partial condensation reaction product by reacting at a temperature of 0 ° C. And so on. Among the above reaction methods, the method (1) is particularly useful in the present invention because it is advantageous in terms of durability of the coating film such as curability and weather resistance.

The mixing ratio of the colloidal silica and the hydrolyzate of the vinylsilane compound is 95/5 to 30/70% by weight when calculated as (silica component in colloidal silica) / (100% hydrolyzate of vinylsilane compound). %, Preferably 90/10 to 40/60% by weight. If the silica component exceeds 95% by weight, the effect of preventing crack formation is small, and if it is less than 30% by weight, sufficient abrasion resistance is not exhibited. The partial condensation reaction product (a) component is an essential component of the present invention in order to prevent wear resistance and weather resistance of the cured film, especially to prevent deterioration of wear resistance after accelerated exposure.

The proportion of the component (a) in the curable coating material composition of the present invention is 5 to 49% by weight, preferably 1 of 100% by weight of the total of the components (a) and (b).
It is 0 to 45% by weight. If the blending ratio is less than 5% by weight, the wear resistance of the hardened coating, particularly the wear resistance due to the abrasive grains, becomes insufficient. On the contrary, if it exceeds 49% by weight, cracks occur in the hardened coating, especially accelerated exposure. The occurrence of cracks later becomes noticeable, and the deterioration of weather resistance becomes large.

As for the component (b), the component (b) contains two or more acryloyloxy groups in one molecule and contains 30% by weight or more of the polyfunctional monomer represented by the general formula (II), and / Alternatively, it is a polyfunctional monomer having a methacryloyloxy group. The polyfunctional monomer represented by the general formula (II) is
It is manufactured by a well-known method and is commercially available. In particular,
The following structural formula

[0023]

[Chemical 5]

The monomer represented by the following can be mentioned as an example. As a commercially available product, there is Aronix M-215 under the trade name of Toagosei Co., Ltd.

Since the polyfunctional monomer represented by the general formula (II) has excellent polymerization activity in an air atmosphere, it can be cured in normal air without using an inert gas such as nitrogen gas. And has a great advantage in terms of economy. Further, the cured film formed from the above-mentioned monomer has excellent weather resistance, and does not cause an increase in haze value, an increase in yellowness, or generation of cracks in accelerated exposure or natural exposure. Still another advantage is that the compatibility with the above-mentioned partial condensation reaction product (a) component is excellent, so that the transparency, adhesion, and weather resistance of the cured film are not deteriorated without decreasing the wear resistance of the cured film. Can be improved. Therefore, in order to achieve both abrasion resistance and weather resistance, the polyfunctional monomer represented by the general formula (II) is an essential component in the present invention.

The polyfunctional monomer as the component (b) must contain 30% by weight or more of the polyfunctional monomer represented by the general formula (II). In other words, in the polyfunctional monomer of the general formula (II), a polyfunctional monomer having two or more acryloyloxy groups and / or methacryloyloxy groups in one molecule other than the general formula (II) is used. You may use together in the ratio of less than 70 weight%. When the compounding ratio of the polyfunctional monomer of the general formula (II) is less than 30% by weight, the transparency and weather resistance of the cured film are deteriorated. Further, other than the polyfunctional monomer of the general formula (II), a polyfunctional monomer having two or more acryloyloxy groups and / or methacryloyloxy groups in one molecule has a wear resistance of a cured film. Although it is used for the purpose of improvement or adhesion improvement, if the amount used exceeds 70% by weight, the weather resistance will be decreased, which is not preferable.

Other than these polyfunctional monomers of general formula (II), two or more acryloyloxy groups and // in one molecule
Further, specific examples of the polyfunctional monomer having a methacryloyloxy group include, for example, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate,
Bifunctional monomers such as 1,9-nonanediodiol diacrylate, neopentyl glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, urethane acrylate, trimethylolpropane triacrylate -To, pentaerythritol-lutriacryle-
G, tris (acryloxyethyl) isocyanurate,
A trifunctional or higher polyfunctional monomer such as ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
Other examples include those described in UV / EB Curing Handbook-Raw Materials (Polymer Society).

Among these monomers, the 1,6-hexanediol diacrylate combination system is a preferable monomer because it has a large effect of improving adhesion and a small decrease in weather resistance. (B) in the curable coating material composition of the present invention
The mixing ratio of the components is 10 in total of the components (a) and (b).
51-95% by weight of 0% by weight, preferably 55-95%
90% by weight. When the blending ratio is less than 51% by weight, the transparency of the cured film is deteriorated and cracks due to accelerated exposure are observed. On the contrary, when it is used in excess of 95% by weight, the wear resistance, especially the wear resistance due to abrasive grains It is not preferable because it deteriorates the property.

Regarding the component (c). When ultraviolet rays are used as the active energy rays, it is preferable to incorporate a slight amount of the photopolymerization initiator (c) into the coating material composition in consideration of practical curing. Specific examples of the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, ptyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, Diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate,
4,4'-bis (dimethylaminobenzophenone), 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, 1-hydroxycyclohexylphenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1-
[4- (Methyldio) phenyl] -2-morpholino-
Carbonyl compounds such as propan-1-one; sulfur compounds such as tetramethylthiuram disulfide and tetramethylthiuram monosulfide; azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile; Peroxide compounds such as benzoylper-oxide and di-salt-butyl-peroxide; and the like. These may be used alone or in combination of two or more.

The amount of the photopolymerization initiator added to the coating composition is 0.1 to 5 parts by weight based on 100 parts by weight of the total of the components (a) and (b). If the amount of the photopolymerization initiator is too large, the weather resistance of the cured film will be deteriorated and coloring will be likely to occur.

The active energy ray-curable coating material composition of the present invention comprises the above-mentioned components (a), (b) and (c), and if necessary, further contains an ultraviolet absorber, a light stabilizer and an antioxidant. Agents, stabilizers such as thermal polymerization inhibitors; leveling agents, defoamers, thickeners, antisettling agents, pigment dispersants, antistatic agents,
Surfactants such as antifogging agents; curing catalysts selected from acids, alkalis, salts and the like may be used in an appropriate amount.

Further, from the viewpoints of uniform solubility, dispersion stability, adhesion to a substrate, smoothness and uniformity of the coating material composition, an organic solvent is used by being blended in the coating material composition. May be. The organic solvent is not particularly limited, and one that can satisfy the desired performance as described above may be used. Further, two or more kinds of organic solvents may be used in combination. The use ratio of this organic solvent is 0 to 2000 parts by weight with respect to 100 parts by weight of the coating material composition. If the amount used exceeds 2000 parts by weight, only a thin film is obtained, so that the wear resistance and the scratch resistance are not sufficient.

Further, by incorporating a mono (meth) acrylate having one (meth) acryloyloxy group in one molecule into the coating material composition, the desired performance as described above can be obtained similarly to the organic solvent. You can also satisfy the face.
Examples of such a mono (meth) acrylate include:
Methyl methacrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, glycidyl acrylate, 2
Examples thereof include low-viscosity mono (meth) acrylates such as -hydroxyethyl acrylate and tetrahydrofurfuryl acrylate.

For the purpose of further improving the weather resistance of the cured film, benzophenone type, benzotriazole type, phenyl salicylate type, phenyl benzoate type,
It is also possible to add an ultraviolet absorber having a maximum absorption wavelength in the range of 240 to 380 nm derived from a cyanoacrylate compound, or a hindered amine light stabilizer. Further, it is more preferable to add both components together. With this addition, the weather resistance of the coating is further improved, for example, yellowing resistance of the coating due to exposure, retention of gloss and transparency, crack resistance, or retention of adhesion to synthetic resin substrates.

Next, a method of using the active energy ray-curable coating material composition will be described. The coating material composition of the present invention can be used in various applications conventionally known as a field of use of the coating material, in particular, by forming a coating excellent in wear resistance on the surface of the synthetic resin molded article, It is very effective for producing wear resistant synthetic resin molded products. That is, a step of applying the coating material composition of the present invention to the surface of a synthetic resin molded article and curing the composition by irradiation with active energy rays to form a coating film having a thickness of 1 to 30 μm on the surface is adopted. By doing so, it is possible to easily form a practically effective coating film having various properties on the surface of the synthetic resin molded product.

As a method for applying the coating material composition of the present invention to the surface of a synthetic resin molded article, there are coating methods such as dip coating, brush coating, flow coating, spray coating and spin coating. Among these, the dip coating method is preferable from the viewpoint of coating workability of the coating material composition, the smoothness and uniformity of the coating film, and the spray coating method is preferable from the viewpoint of adaptability to the shape of the molded product. The amount of the coating material composition to be supplied may be appropriately adjusted and supplied so that the film thickness of the cured film is in the range of 1 to 30 μm, preferably 3 to 15 μm.

As a method for curing the coating material composition of the present invention, active energy rays such as electron rays, α rays, γ rays, β rays and ultraviolet rays extracted from an electron beam accelerator of 20 to 2000 kV are irradiated. Adopt the method. It is preferable to use ultraviolet rays having a wavelength of 100 to 400 nm from the viewpoint of being easily and economically cured. When ultraviolet rays are used, it is desirable to add a photopolymerization initiator to the coating material composition as described above. As a source of ultraviolet rays, a wavelength of 100 to 400n is used by using an ultraviolet lamp from the viewpoint of practicality and economy.
The method of irradiating ultraviolet rays of m is preferable, and specific examples of this ultraviolet lamp include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, and a metal halide lamp. The atmosphere at the time of irradiating and curing with ultraviolet rays may be ordinary air or may be an inert gas such as nitrogen or argon. Further, for the purpose of improving the adhesion of the coating, etc., before irradiation with ultraviolet rays, an infrared ray or a hot air drying oven is used for 20 to 1
You may heat-process for 1 to 60 minutes in a temperature range of 20 degreeC.

In this way, the film thickness on the surface of the molded product is from 1 to
A cured film having a thickness of 30 μm, preferably 3 to 10 μm can be formed. If the film thickness is less than 1 μm, sufficient abrasion resistance and scratch resistance cannot be obtained, and conversely, if it exceeds 30 μm, the adhesion to the molded product is deteriorated or the coating film is cracked.

The synthetic resin molded articles to which the active energy ray-curable coating material composition of the present invention is applied are various thermoplastic resin molded articles and heat-resistant articles which have conventionally been required to have improved abrasion resistance and the like. It is a curable resin molded product. Examples of such a resin include polymethylmethacryl resin, polycarbonate resin, polyallyl diglycol carbonate resin,
Examples thereof include polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin, and polymethacrylimide resin. Further, the molded product is a sheet-shaped molded product, a film-shaped molded product, various injection molded products and the like made of such a resin. Among these molded products, molded products such as methylmethacrylate resin, polycarbonate resin, and polymethacrylimide resin are often used as transparent materials because they are excellent in transparency, and have improved wear resistance. Since the demand is strong, the coating composition of the present invention can be used particularly effectively.

[0040]

EXAMPLES The present invention will now be described in more detail with reference to examples. Example 1. In a 1-liter four-necked flask reaction vessel equipped with a stirrer and a cooling tube, 200 g of iso-propyl alcohol-dispersed colloidal silica [trade name IPA-ST, manufactured by Nissan Kagaku Co., Ltd., SiO ₂ concentration 30% by weight]. 30g of vinyltrimethoxysilane with stirring
(Weight at 100% hydrolysis 21.5g) and 0.001
11 g of a normal hydrochloric acid aqueous solution was added, and the mixture was stirred at room temperature for 1 hour. Next, bis- (acryloxyethyl) hydroxyethyl isocyanurate [trade name Aronix M-
215, manufactured by Toagosei Co., Ltd.] and a mixed solution of 133 g and 57 g of 1,6-hexanediol diacrylate were added, and the mixture was stirred at room temperature for 1 hour. Next, the reaction system was depressurized, the volatile matter was distilled out in the temperature range of 40 ° C. to 60 ° C., and the temperature of the reaction system was raised to normal pressure with a filter when almost no distillation was observed. After reacting for 2 hours at an internal temperature of about 80 ° C. under normal pressure, 100 g of toluene was added and water was removed azeotropically with toluene under reduced pressure. As a result, a highly viscous and almost colorless transparent reaction liquid was obtained.

The following coating material composition was prepared using this reaction solution. The above reaction solution 50 g Iso-butyl alcohol 25 g Acetate-butyl 20 g Methoxybutanol 5 g Methylphenylglyoxylate 0.5 g Benzophenone 0.5 g 2- (2-Hydroxy-5-tert-butylphenyl) benzotriazole ( Product name: TINUVIN-PS, CHIBA, Gaigi Co., Ltd.) 2.5g

Next, using this coating composition, a thickness of 3 m
m, 100 mm × 100 mm polycarbonate resin (trade name: Lexan LS-2111, color tone clear, manufactured by General Electric Co.) spray-coated on an injection-molded plate to form a film, which was then dried in a dryer at 80 ° C. Let stand for a minute. Next, this was irradiated with ultraviolet rays of 2,000 mj / cm ² (ultraviolet integrated energy amount in the wavelength range of 320 to 380 nm) in an air atmosphere using a high pressure mercury lamp to form a cured coating film having a thickness of 7 mm.

Example 2. 30 g of vinyltrimethoxysilane of Example 1 was added to 30 g (10 g) of vinyltriethoxysilane.
A reaction solution was prepared according to Example 1 except that the weight at the time of 0% hydrolysis was changed to 23.4 g). The obtained reaction liquid had a high viscosity and was almost colorless and transparent. Using this reaction solution, the same coating material composition as in Example 1 was treated under the same treatment conditions.
The thickness of the obtained cured coating was 7 μm.

Example 3. Into the reaction vessel of Example 1, 200 g of iso-propyl alcohol-dispersed colloidal silica was charged, and 40 g of vinyltrimethoxysilane (1
A weight of 28.6 g at the time of 00% hydrolysis) and 14 g of a 0.01 N hydrochloric acid aqueous solution were added, and the mixture was stirred at room temperature for 1 hour. Next, the temperature of this reaction system was raised and the reaction was carried out for 8 hours while refluxing the volatile components.

The following coating material composition was prepared using this reaction solution. The above reaction solution 100 g Bis- (acryloxyethyl) hydroxy ethyl isocyanurate 42 g 1,6-hexanediol diacrylate 10 g Iso-butyl alcohol 69 g N-butyl acetate 55 g Methoxybutanol 14 g Methylphenylglyoxylate 0.6 g benzoin-iso-propyl ether 0.6 g 2,4-dihydroxybenzophenone (trade name Ubinal # 400 manufactured by BASF) 4.3 g Treatment with the above coating composition in accordance with Example 1 A cured coating having a film thickness of 8 μm was formed.

Example 4. Using the coating material composition of Example 1, a methyl methacrylate resin having a thickness of 3 mm and a size of 100 mm × 100 mm [registered trade name Acrypet VH, color tone 0
01 clear, manufactured by Mitsubishi Rayon Co., Ltd.] Spray-coated on an injection-molded plate to form a film, and the film was allowed to stand at 70 ° C. for 20 minutes. Then, this was irradiated with 2,400 mj / cm ² of ultraviolet rays in an air atmosphere using a high pressure mercury lamp to form a cured film having a film thickness of 6 μm.

Example 5. Instead of the 1,6-hexanediol diacrylate of Example 1, 1,9-nonanedio-
A cured film was formed in the same manner as in Example 1 except that ludia acrylate was used.

Example 6. A cured coating was formed in accordance with Example 1 except that trimethylolpropane triacrylate was used instead of 1,6-hexanediol diacrylate in Example 1.

Example 7. A cured coating was formed in the same manner as in Example 1 except that neopentyl glycol diacrylate dihydroxypivalate was used instead of 1,6-hexanediol diacrylate in Example 1.

Comparative Example 1. The following coating material composition was prepared using the reaction solution of Example 3. Reaction liquid of Example 3 100 g Bis- (acryloxyethyl) hydroxyethyl isocyanurate 12 g 1,6-hexanediol diacrylate 3 g Iso-butyl alcohol 25 g n-Butyl acetate 20 g Methoxybutanol 5 g Methylphenylglyoxy Rate 0.3 g Benzoin-iso-propyl ether 0.3 g 2,4-Dihydroxybenzophenone 2.5 g Treated according to Example 1 using the above coating composition to give a cured coating having a thickness of 7 microns. Formed.

Comparative Example 2. The following coating material composition was prepared using the reaction solution of Example 3. Reaction liquid of Example 3 100 g Dipentaerythritol hexaacrylate 52 g Iso-butyl alcohol 69 g n-Butyl acetate 55 g Methoxybutanol 14 g Methylphenylglyoxylate 0.6 g Benzophenone 0.6 g 2,4-dihydroxy Benzophenone 4.3 g The above coating material composition was treated in the same manner as in Example 1 to form a cured coating having a thickness of 7 μm.

Comparative Example 3. The following coating material composition was prepared using the reaction solution of Example 3. Reaction liquid of Example 3 100 g Iso-butyl alcohol 20 g n-Butyl acetate 16 g Methoxybutanol 4 g Methylphenylglyoxylate 0.35 g Benzophenone 0.35 g Treated according to Example 4 using the above coating composition. As a result, a cured film having a thickness of 6 μm was formed.

Comparative Example 4. The following coating composition was prepared. Iso-propyl alcohol-dispersed colloidal silica 133 g Bis (acryloxyethyl) hydroxyethyl isocyanurate 48 g 1,6-hexane diol diacrylate 12 g Iso-butyl alcohol 70 g n-Butyl acetate 56 g Methoxybutanol 14 g Methylphenyl Glyoxylate 1 g Benzophenone 1 g UV energy of Example 4 using the above coating composition.
Example 4 except that the amount was changed to 1,500 mg / cm ^2.
According to the procedure described above, a cured coating having a film thickness of 6 μm was formed.

Comparative Example 5. The following coating composition was prepared. Bis- (acryloxyethyl) hydroxyethyl isocyanurate 48g 1,6-hexanediol diacrylate 12g iso-butyl alcohol 70g n-butyl acetate 56g methoxybutanol 14g methylphenylglyoxylate 0.6g benzophenone 0.6 g The coating material composition was treated according to Comparative Example 4 to form a cured coating film having a thickness of 6 μm. Example 1 above
-7 and the physical properties of the cured coatings of Comparative Examples 1-5 were evaluated. The results are shown in Table 1.

[0055]

[Table 1]

The evaluation of each physical property was performed as follows. (1) Abrasion resistance and scratch resistance A Taber abrasion test was conducted in accordance with ASTM D-1044. Wear wheel CS-10F, load 500g, wear count 5
It was worn under the condition of 00 cycles. The sample was washed with a neutral detergent and the haze value was measured with a head meter.
Abrasion resistance is indicated by the Δhaze (%) value of (haze value after abrasion-haze value before abrasion). (2) Adhesion The surface of the sample was razored to scratch 11 scratches on each side of 1.5
100 cells were formed at intervals of mm, and then cellophane tape [width: 25 mm, manufactured by Nichiban Co., Ltd.] was crimped to the cells and rapidly peeled upward. The evaluation of the adhesiveness is shown by "the number of remaining squares / total number of squares".

(3) Appearance (a) Transparency: Shown in haze value (%) using a head meter. (B) Crack: visually determined. No cracks were evaluated as ◯, some cracks were evaluated as Δ, and innumerable cracks were evaluated as x. (4) Weather resistance Sunshine weather meter [Suga Test Instruments Co., Ltd. WE
L-SUN-DHC type] was used for the exposure test. The exposure conditions are an exposure time of 1,000 hours and a black panel temperature of 63.
℃, rainfall conditions 12 minutes water spray / 60 minutes cycle. The exposed samples were evaluated for the adhesiveness in the item (2) and the appearance in the item (3).

[0058]

The active energy ray-curable coating material composition of the present invention does not contain a partial condensation reaction product of colloidal silica and a specific silane compound having a vinyl group, and a specific polyfunctional monomer. Since the three components were used together in a ratio, the three components interact with each other, so that the coating composition was applied to the substrate,
When cured with active energy rays, it excels in wear resistance under severe conditions, adhesion to base materials, and crack resistance,
In particular, it is possible to obtain a cured coating having excellent weather resistance as compared with the conventional coating material composition of this type. Therefore, the coating material composition of the present invention is particularly useful for coating synthetic resin molded articles used for outdoor applications.

Claims (1)

[Claims] 1. A colloidal silica comprising (a) silica particles having a primary particle size of 1 to 200 millimicrons, and the following formula: (In the formula, R ¹ is a single bond or a substituted or unsubstituted divalent hydrocarbon group, R ² is a monovalent hydrocarbon group or a hydrogen atom, R ³ is a substituted or unsubstituted monovalent hydrocarbon group, a Is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is an integer of 1 to 3). Partial condensation reaction product 5 with a hydrolyzate of a silane compound.
49% by weight, (b) the following formula, [Wherein R ⁴ , R ⁵ and R ⁶ are the same or different substituted or unsubstituted divalent hydrocarbon groups, and X is CH ₂ ═CH—COO—
Group or CH ₂ ═C (CH ₃ ) —COO— group] in an amount of 30% by weight or more and 2 in one molecule.
51 to 95% by weight of a polyfunctional monomer having one or more acryloyloxy groups and / or methacryloyloxy groups, and (c) a photopolymerization initiator in a total of 1 of the component (a) and the component (b).
An active energy ray curable coating material composition comprising 0.1 to 5 parts by weight with respect to 00 parts by weight.