JPH08311391A - Coating composition and its laminate - Google Patents

Abstract

PURPOSE: To obtain a coating composition by blending silica fine particles having specific particle diameters with a disilane compound, a silane compound, a polyfunctional epoxy compound and a curing catalyst, excellent in dyeability and durability of a coating film itself and durability of a laminate such as a reflection reducing film, etc. CONSTITUTION: This coating composition is obtained by blending (A) silica fine particles having 1-100 micron particle diameters with (B) an organosilicon compound of formula I (R<1> and R<2> are each a 1-6C hydrocarbon; X<1> and X<2> are each a hydrolyzable group; Y is an organic group containing a carbonate group or an epoxy group; (m) is 0 or 1), (C) an organosilicon compound of formula II (R<3> is a polymerizable reactive group-containing organic group; R<4> is a 1-6C hydrocarbon; X<3> is a hydrolyzable group; (n) is 0 or 1) (e.g. a vinyltrialkoxysilane, etc.), (D) a polyfunctional epoxy compound (e.g. 1,6- hexanediol diglycidyl ether, etc.) and (E) a curing catalyst (e.g. ammonium perchlorate, etc.), excellent in durability and is useful for lenses for glasses, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface of a transparent plastic material having abrasion resistance, chemical resistance, warm water resistance, heat resistance,
It provides a transparent film with excellent durability such as weather resistance and dyeability, and it is possible to provide an antireflection film made of an inorganic substance (hereinafter referred to as an inorganic vapor deposition film) on the film, further improving the yield and pot. The present invention relates to a coating composition which contributes to productivity improvement such as prolongation of life.

[0002]

2. Description of the Related Art Among currently used plastic materials, acrylic, methacrylic, vinyl, and polycarbonate materials are used.
Compared to glass, transparent plastic materials such as bone-based, urethane-based and allyl-based plastic materials have excellent properties such as impact resistance, light weight, processability, and colorability. It is used in large quantities as an industrial material in place of inorganic glass. However, these have the drawback of being inferior in scratch resistance and chemical resistance to inorganic glass. As a means for improving these drawbacks of plastic materials, for example, in Japanese Patent Publication No. 57-2735, a non-dye type thermosetting coating consisting of colloidal silica and an alkoxysilane containing an epoxy group, and Japanese Patent Publication No. 56-34033. No. 55-29102, a non-dye type thermosetting coating containing epoxy group-containing alkoxysilane and tetraalkoxysilane as main components is also disclosed in JP-B-63-6198.
In No. 1 public information, etc., a dyeable type thermosetting coating containing a partial condensate of colloidal silica and silanol and a cross-linking agent as main components, and in Japanese Kokai No. 59-231501 public relation, etc., colloidal silica A dyeable type thermosetting coating comprising an epoxy group-containing alkoxysilane and a polyfunctional epoxy compound is also disclosed in JP-A-59-102964 and JP-A-58-102964.
A thermosetting coating material containing disilane as a main component is also used in the public relations of No. 222160, and Japanese Patent Publications Nos. 57-43578 and 57-1.
No. 5,608,57-20968, etc. disclose photopolymerizable coatings, respectively, which are intended to improve chemical resistance and scratch resistance. On the other hand, JP-A-3-14
A publicly-known publication such as No. 5602 proposes a dyeable type curable coating which is excellent in adhesion to a plastic substrate by using both of these thermosetting and photocuring.

[0003]

Some of the above-mentioned coating compositions satisfy various durability of the coating film and various durability when the inorganic vapor deposition film is provided on the surface of the coating film, but the coating film itself. When the dyeing property is sufficient, the productivity such as yield and curing conditions tends to decrease.

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve these problems, and found that they are silica fine particles, a disilane compound having a carbonate group or an epoxy group in the middle, a polymerizable reactive group. A coating film obtained by heat-curing a composition containing a silane compound, a polyfunctional epoxy compound, and a curing catalyst as main components is transparent, dyeable, and adheres to an inorganic vapor deposition film (durability).
It has been found that excellent performance can be obtained, and further improved productivity such as long pot life, shortened curing time and drastic reduction of defective defects.

That is, the present invention is a coating composition characterized by containing at least the following components (A), (B), (C), (D) and (E) as main components, and a coating composition therefor. The present invention relates to a laminated body having an antireflection film made of an inorganic material provided on the surface of a film made of a material.

(A). Silica fine particles having a particle size of 1 to 100 millimicrons (B). General formula

[0007]

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An organosilicon compound represented by the formula (in the formula, R
¹ and R ² are hydrocarbon groups having 1 to 6 carbon atoms. X ¹ , X
² is a hydrolyzable group. Y is an organic group containing a carbonate group or an epoxy group, and m is 0 or 1.)

(C). General formula

[0010]

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An organosilicon compound represented by the formula (in the formula, R ³
Is an organic group having a polymerizable reactive group, R ⁴ is a carbon number of 1 to
6 hydrocarbon groups. X ³ is a hydrolyzable group, and n
Is 0 or 1.)

(D). Polyfunctional epoxy compound (E). Curing Catalyst As a specific example of the silica fine particles of the component (A) used in the present invention, inorganic oxide fine particles of SiO ₂ are colloidally dispersed in a dispersion medium such as water, alcohol or other organic solvent. is there. For the purpose of this invention, those having an average particle diameter of 1 to 100 millimicrons are used, but those having an average particle diameter of 5 to 30 microns are preferable, and the species to be applied to the coating composition of the present invention is suitable. The amount used and the amount used are determined depending on the intended film performance, but the amount used is preferably 10 to 50% by weight of the solid content. That is, if it is less than 10% by weight, the adhesion to the inorganic vapor deposition film becomes insufficient, or the scratch resistance of the coating film becomes insufficient. On the other hand, if it exceeds 50% by weight, the coating film is cracked and the dyeability becomes insufficient.

Next, in the general formula of the component (B), R ¹ ,
R ² is a hydrocarbon group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group and a phenyl group. Also, X ¹ and X ² are
It is a hydrolyzable functional group, and specific examples thereof include an alkoxy group such as a methoxy group, an ethoxy group and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group. Y is an organic group containing a carbonate group or an epoxy group, and specific examples include:

[0014]

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[0015]

[Chemical 4]

[0016]

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[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

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[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

And the like.

These disilane compounds can be synthesized by various conventionally known methods.

For example, it can be obtained by subjecting diallyl carbonate to an addition reaction of trichlorosilane or the like and then alkoxylation. Alternatively, it can be obtained by subjecting a compound having a substituent that can be added at both ends and further having an epoxy group or an epoxidizable functional group to the inside thereof to addition reaction of trichlorosilane or the like and then alkoxylation.

It is more effective that the component (B) is used after being hydrolyzed, or the coating film after curing is subjected to an acid treatment, whichever method is used. In addition, the addition of the component (B) improves the yield and makes it possible to extend the pot life.

The amount used is preferably 3 to 40% by weight of the solid content. That is, if it is less than 3% by weight, both the dyeability and the various durability of the inorganic vapor deposition film cannot be satisfied at the same time. If it exceeds 40% by weight, the water resistance of the coating film becomes poor.

Subsequently, in the component (C), R ³ is an organic group having a polymerizable reactive group, and is vinyl group, allyl group, acryl group, methacryl group, epoxy group, mercapto group, cyano group, isocyano group. , A silane compound having a polymerizable reactive group such as amino group, wherein R ⁴ has 1 carbon atom
Specific examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group and a phenyl group. X ³ is a hydrolyzable functional group, and specific examples thereof include alkoxy groups such as methoxy group, ethoxy group, and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy group.

Specific examples of the silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane and methacryl. Oxypropyl dialkoxymethyl silane, γ-glycidoxy propyl trialkoxy silane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxy silane, mercapto propyl trialkoxy silane, γ-amino propyl trialkoxy silane, N-β (Aminoethyl) -γ-aminopropylmethyldialkoxysilane and the like.

The component (C) may be used as a mixture of two or more kinds.

As with the component (B), it is more effective to use it after hydrolysis.

The amount of component (C) used is 20 to 20% of the total composition.
It is preferably 60% by weight. That is, if it is less than 20% by weight, the adhesiveness to the inorganic vapor deposition film tends to be insufficient. On the other hand, if it exceeds 60% by weight, it causes cracks in the cured film, which is not preferable.

Next, the polyfunctional epoxy compound as the component (D) is widely used for paints, adhesives, casting, etc. For example, a polyolefin-based epoxy resin synthesized by the peroxide method, cyclo Aliphatic epoxy resins such as pentadiene oxide, cyclohexene oxide or polyglycidyl ester obtained from hexahydrophthalic acid and epichlorohydrin, polyhydric phenols such as bisphenol A, catechol and resorcinol, or (poly) ethylene glycol, (poly) propylene glycol, Polyglycidyl ethers, epoxidized vegetable oils and novolaks obtained from epichlorohydrin and polyhydric alcohols such as neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol and sorbitol Epoxy novolac derived from phenol resin and epichlorohydrin, phenolphthalein and epoxy resins obtained from epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene,
Further, an epoxy acrylate obtained by a ring-opening reaction of a glycidyl group of the above-mentioned epoxy compound and a monocarboxylic acid-containing (meth) acrylic acid may be mentioned.

Specific examples of the polyfunctional epoxy compound include 1,6-hexanediol diglycidyl ether,
Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether ether,
Tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol hydroxyglyberic acid ester diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether Ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, Aliphatic epoxy compounds such as rubitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, isophoronediol diglycidyl ether, bis-2 Alicyclic epoxy compounds such as 2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ester Examples thereof include aromatic epoxy compounds such as ether and cresol novolac polyglycidyl ether.

In the present invention, the component (D), when only the component (B) is used to secure sufficient dyeing properties, the water resistance and warm water resistance are significantly lowered. Used to improve hot water. Therefore, among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxy) Aliphatic epoxy compounds such as triglycidyl ether of ethyl) isocyanurate are particularly preferred.

The amount of component (D) used is 5 to 4 of the total composition.
It is necessary to be 0% by weight. That is, if it is less than 5% by weight, the water resistance of the coating film becomes insufficient. On the other hand, if it exceeds 40% by weight, the adhesion to the inorganic vapor deposition film tends to be insufficient, which is not preferable.

The coating composition thus obtained can be used by diluting it with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.

The component (E) is added as a curing catalyst for silanol or an epoxy compound, and preferred are perchloric acids such as perchloric acid, ammonium perchlorate and magnesium perchlorate, Cu (II) and Zn. (II), Co
(II), Ni (II), Be (II), Ce (III), Ta
(III), Ti (III), Mn (III), La (III
), Cr (III), V (III), Co (III), Fe
(III), Al (III), Ce (IV), Zr (IV), V
Acetylacetonate having (IV) or the like as a central metal atom,
Examples thereof include amino acids such as amine and glycine, Lewis acids, and organic acid metal salts. Among them, in the composition of the present invention, magnesium perchlorate, Al (III), and Fe (III) acetylacetonate are more preferable in terms of curing conditions, pot life of the coating liquid, and the like. The addition amount is preferably within the range of 0.01 to 5.0% of the solid content concentration. Further, in order to improve the durability of the coating film such as scratch resistance, the general formula is S
It is also possible to add a hydrolyzate and / or a partial condensate of organosilicon represented by i (OR) ₄ (wherein R represents an alkyl group having 1 to 8 carbon atoms). The general formula is S
The tetrafunctional silane coupling agent compound represented by i (OR) ₄ is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxy. Silane, tetrakis (2-methoxyethoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2
-Ethylhexyloxy) silane, and the like. These may be used alone or in combination of two or more. Further, it is preferable to hydrolyze these in the presence of an acid in the absence of solvent or in an organic solvent such as alcohol before use.

In addition to the above components, the coating composition of the present invention may contain a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye / oil soluble dye /
It is also possible to add a fluorescent dye / pigment, a photochromic compound, a light-resistant heat-resistant stabilizer such as a hindered amine / hindered phenol system, etc. to improve the coatability of the coating solution and the film performance after curing. In particular, it is possible to impart excellent weather resistance to the coating film by adding one kind or two or more kinds selected from an ultraviolet absorber, an antioxidant, a light resistance and heat resistance stabilizer such as a hindered amine and a hindered phenol. In addition, in applying the coating composition of the present invention, the surface of the substrate is previously treated with an alkali, an acid, a surfactant, or inorganic or organic fine particles for the purpose of improving the adhesion between the substrate lens and the coating. It is effective to perform polishing treatment, primer treatment or plasma treatment.

As a coating / curing method, a coating solution is applied by a dipping method, a spinner method, a spray method or a flow method, and then dried by heating at a temperature of 40 to 200 ° C. for several hours to form a film. be able to. In particular, for a base material having a heat distortion temperature of less than 100 ° C., a spinner method that does not require fixing the lens base material with a jig is suitable.

The film thickness of the cured film is 0.05.
It is preferably ˜30 μ. That is, 0.05μ
If it is less than 30 μm, the basic performance does not appear, and if it exceeds 30 μ,
The surface smoothness is impaired and optical distortion occurs, which is not preferable.

As the coating method, a dipping method or a spray method is used.
Method, roll coat method, spin coat method, flow coat method and the like.

As a coating method for forming an antireflection film made of an inorganic substance on the surface of the coating film thus obtained, a vacuum deposition method, an ion plating method, a sputtering method and the like can be mentioned. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used. In addition, as the film configuration,
Either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic material used include Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti
₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , Mg
O, Y ₂ O _3, etc. SnO _2, MgF _2, WO ₃ and the like. These inorganic substances may be used alone or as a mixture of two or more.

Further, when forming the antireflection film, it is desirable to perform surface treatment of the hard coat film. Specific examples of the surface treatment include acid treatment, alkali treatment, ultraviolet irradiation treatment, plasma treatment by high frequency discharge in an argon or oxygen atmosphere, and ion beam irradiation treatment of argon, oxygen or nitrogen.

Hereinafter, further details will be described with reference to examples.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of coating liquid 1535.8 g of butyl cellosolve 1614.3 g, methanol-dispersed colloidal silica (Catalyst Kasei Co., Ltd., trade name "Oscar 1132", solid content concentration 30% by weight)
Was mixed, and 604.1 g of γ-glycidoxypropyltrimethoxysilane and disilane of the following structural formula (DS
-1) 601.5 g was mixed. 0.05 in this mixture
331.7 g of an aqueous N hydrochloric acid solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and aged overnight. To this liquid was added 1,6-hexanediol diglycidyl ether (manufactured by Nagase Kasei Co., Ltd., trade name "Denacol EX-212") 29.
After adding 4.4 g, magnesium perchlorate 18.1 g,
1.5 g of a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-7001") and a hindered amine-based light stabilizer (manufactured by Sankyo Co., Ltd., trade name [Sanol LS-77
0 ") 7.5 g was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid.

* DS-1

[0051]

[Chemical 13]

(2) Coating and Curing The coating liquid thus obtained was subjected to alkali treatment and had a refractive index of 1.50 and spectacle lenses (Seiko Epson Corporation).
(Manufactured by Seiko Plax Co., Ltd.) and applied by the dipping method. The pulling rate was 23 cm / min. After coating, air-dry at 80 ° C for 20 minutes and then at 135 ° C for 40 minutes.
Baking was performed for a minute. The cured film thus obtained had a thickness of about 2 μm and was excellent in both appearance and dyeability.

Example-2 An antireflection coating thin film made of an inorganic material was formed on each of the lenses obtained in Example-1 by the following method.

(1) Formation of Antireflection Thin Film After the lens obtained by the above method was subjected to plasma treatment (400 W of argon plasma for 60 seconds), SiO ₂ , ZrO ₂ and SiO were sequentially turned from the substrate to the atmosphere. ₂ , Z
An antireflection multilayer film consisting of 5 layers of rO ₂ and SiO ₂ was formed by a vacuum deposition method (manufactured by Vacuum Instrument Co., Ltd .; BMC-1000). The optical thickness of each layer is
₂ layers, the following equivalent film layer of ZrO ₂ and SiO ₂ and the following Z
The rO ₂ layer and the uppermost SiO ₂ layer were formed to have λ / 4, respectively. The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green and the total light transmittance was 98%.

(2) Test and Evaluation Results The lenses obtained in Example-1 (hereinafter referred to as hard coat lenses) and the lenses obtained in Example-2 (hereinafter referred to as hard multicoat lenses) are respectively tested as follows. Tests were conducted by the method described, and the results are shown in Table 1.

(A) Abrasion resistance: 1 kg of Bonster # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.)
Then, the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated in the following stages.

A: No scratches were found in the area of 1 cm * 3 cm. B: 1 to 10 scratches are formed within the above range. C: 10 to 100 scratches are formed within the above range. D: Countless scratches are attached, but a smooth surface remains. E: No smooth surface remained due to scratches on the surface.

(B) Water resistance / chemical resistance: water, alcohol,
It was soaked in kerosene for 48 hours, and those having no change in surface condition were regarded as good.

(C) Acid resistance / detergent resistance: 0.1N hydrochloric acid and 1% Mama lemon (manufactured by Lion Oil and Fat Co., Ltd.) aqueous solution 12
Immersion for a period of time was evaluated as good if the surface condition was not changed.

(D) Adhesion: The adhesion between the substrate and the hard coat film and between the hard coat film and the multi coat film is JI.
A cross-cut tape test was performed according to SD-0202. That is, cuts are made at intervals of 1 mm on the surface of the substrate using a knife to form 100 squares of 1 mm 2. Then, after strongly pressing the cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) on top of it, it was pulled by 90 degrees from the surface and peeled off rapidly. It was used as an index.

(E) Weather resistance: The one having no change in surface condition after being exposed to a sunshine weather meter by a xenon lamp for 400 hours was regarded as good.

(F) Heat resistance (cooling cycle property): 70 ° C.
After storing in warm air for 1 hour, the surface condition was examined. Furthermore-
The cycle of 5 minutes at 5 ° C. and 15 minutes at 60 ° C. was repeated 5 times, and those having no change in surface condition were regarded as good.

(G) Durability: Considering that durability is essentially an adhesive connection, the above-mentioned cross-cut tape test was carried out on the coat films subjected to the tests of (a) to (f). Those without peeling were considered good.

(H) Dyeability (hard coat lens only): 2 g of Seiko Plax Diamond Coat dye Amber D was dispersed in 1 liter of pure water at 92 ° C. to prepare a dye solution.

Dyeing was carried out by immersing in this dyeing solution for 5 minutes, and there was no dyeing unevenness and the total light transmittance was 30% or more before and after dyeing.

Example-3 (1) Preparation of coating liquid Methyl cellosolve 1913.9 g and isopropyl alcohol-dispersed colloidal silica (Catalyst Kasei Kogyo KK)
Manufactured, trade name "Oscar 1432", solid content concentration 30% by weight) 1177.4 g, and then γ-glycidoxypropyltrimethoxysilane 555.7 g, γ-glycidoxypropylmethyldiethoxysilane 291.9 g
And 482.7 g of disilane (DS-2) having the following structural formula
Was mixed. 0.05N hydrochloric acid aqueous solution 30
5.8 g was added dropwise with stirring, and the mixture was stirred for 4 hours and aged overnight. After adding 324.5 g of glycerol triglycidyl ether (manufactured by Nagase Kasei Co., Ltd., trade name "Denacol EX-314") to this liquid, Fe (II
I) Acetylacetonate 32.9 g, silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “FZ-211”)
0 ") 1.5 g and phenolic antioxidant (Kawaguchi Chemical Co., Ltd., trade name" ANTAGE CRYSTAL ")
7.5 g was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid.

* DS-2

[0069]

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(2) Coating and curing With the coating liquid thus obtained, a spectacle lens having a refractive index of 1.56 (manufactured by Seiko Epson Corporation, Seiko Plax)
It was applied to a IIGX lens cloth) by a spinner method.

The coating conditions are as follows.

The rotation speed was 500 rpm for 10 seconds (the coating liquid was applied during this time) The rotation speed was 2000 rpm for 1 second The rotation speed was 500 rpm for 5 seconds After coating, air drying was performed at 80 ° C. for 20 minutes, and then baking was performed at 130 ° C. for 60 minutes. The cured film thus obtained had a thickness of about 2.2 μm and was excellent in both appearance and dyeability.

(3) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Example-4 (1) Formation of Antireflection Thin Film After subjecting the lens obtained by the method of Example-3 to plasma treatment (argon plasma 400 W × 60 seconds), the substrate was exposed to the atmosphere, and then sequentially. ZrO ₂ , SiO ₂ , ZrO ₂
An antireflection multilayer film composed of four layers of SiO ₂ was formed by a vacuum vapor deposition method (manufactured by Vacuum Instrument Co., Ltd .; BMC-1000). The optical film thickness of each layer is as follows: the equivalent film layer of the first ZrO ₂ and SiO ₂ and the second ZrO ₂ layer, the S layer of the uppermost layer.
The iO ₂ layers were formed so as to have λ / 4. In addition,
The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green and the total light transmittance was 98%.

(2) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-2, and the results are shown in Table 1.

Example-5 (1) Preparation of coating liquid Isopropyl cellosolve 1552.2 g and isopropyl alcohol-dispersed colloidal silica (Catalyst Chemical Co., Ltd., trade name "Oscar 1432", solid content concentration 3)
0 wt%) 1597.5 g, and then γ-methacryloxypropyltrimethoxysilane 389.0 g, DS
-58.65 and tetramethoxysilane 95.-2.
5g were mixed. 0.05N hydrochloric acid aqueous solution 3
03.5 g was added dropwise with stirring, and the mixture was stirred for 4 hours and aged overnight. After adding 334.5 g of glycerol diglycidyl ether (manufactured by Nagase Kasei Co., Ltd., trade name "Denacol EX-313") to this liquid, Al (II
I) acetylacetonate 22.8 g, silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-760
4 ") 1.5 g was added, and the mixture was stirred for 4 hours and aged overnight to give a coating solution.

(2) Coating and curing The coating liquid thus obtained was applied to a polycarbonate injection molded spectacle lens having a refractive index of 1.58 by a spray method.

The spraying was carried out using an Iwata Wider 61 (manufactured by Iwata Co., Ltd .; nozzle diameter 1 mm) at a spray pressure of 3 kg / square cm and a paint discharge rate of 100 ml / min. After coating, it was air dried at 80 ° C. for 10 minutes and then baked at 100 ° C. for 90 minutes. The cured coating thus obtained had a thickness of about 3 μm and was excellent in both appearance and dyeability.

(3) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Example-6 (1) Formation of Antireflection Thin Film After subjecting the lens obtained in Example-5 to ion beam irradiation treatment (accelerating voltage 500 V × 60 seconds) with oxygen gas, the substrate was exposed to the atmosphere. In order of SiO ₂ , ZrO
_An antireflection multilayer film consisting of 5 layers of ₂ , SiO ₂ , TiO ₂ , and SiO ₂ is formed by a vacuum deposition method (manufactured by Vacuum Instrument Co., Ltd .; BM
C-1000). At that time, T of the fourth layer
A film of iO ₂ was formed by ion beam assisted vapor deposition. The optical film thickness of each vapor-deposited layer is as follows: first SiO ₂ , second Z
The equivalent film layer of rO ₂ and SiO ₂ is λ / 4, and the TiO ₂ layer is λ / 4.
/ 2, and the uppermost SiO ₂ layer was formed to be λ / 4. The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%.

(2) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-2, and the results are shown in Table 1.

Comparative Example-1 A lens was coated in the same manner as in Example-1, except that DS-1 was not added.

The lens thus obtained was tested by the same method, and the results are shown in Table 1.

Comparative Example-2 In Example-1, DS-1, was added with the amount of 1,6-hexanediol diglycidyl ether added to 747.8 g.
The lens thus obtained was applied to the lens in the same manner except that was not added.
A test was conducted in the same manner as in No. 1 and the results are shown in Table 1.

Comparative Example-3 An antireflection film was formed on the lens obtained in Comparative Example-2 by the same method as in Example-2.

The lens thus obtained was used as an example-
A test was conducted in the same manner as in 2, and the results are shown in Table 1.

Comparative Example-4 In Example-1, the addition amount of DS-1 was 1470.8.
g, and 540.0 g of 0.05N hydrochloric acid aqueous solution,
The lens thus obtained was coated in the same manner except that 1,6-hexanediol diglycidyl ether was not added. The thus obtained lens was tested in the same manner as in Example-1, and the results were obtained. Is shown in Table 1.

Comparative Example-5 An antireflection film was formed on the lens obtained in Comparative Example-4 by the same method as in Example-2.

The lens thus obtained was used as an example-
A test was conducted in the same manner as in 2, and the results are shown in Table 1.

[0092]

[Table 1]

[0093]

As described above in detail, according to the present invention, the coating film itself has sufficient dyeability, various durability, and the adhesion and various durability when the inorganic vapor deposition film is provided on the surface of the coating film are sufficiently satisfied. As a result, a coating composition having a high yield and a long pot life and having high productivity could be obtained.

A plastic material having excellent scratch resistance, good dyeability, and good adhesion (durability) with an antireflection film made of an inorganic material is a spectacle lens, a camera lens, a light beam condensing lens or a light beam. It can be widely applied as a diffusion lens for consumer use or industrial use. Further, the effects of the present invention can be applied to transparent glasses such as watch glasses and cover glasses for displays, and transparent plastics for optical applications such as cover glasses, and the obtained effects are great.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 183/06 PMT C09D 183/06 PMT C23C 14/08 C23C 14/08 N G02B 1/10 G02B 1/10 Z

Claims (2)

[Claims] 1. At least the following components (A), (B),
A coating composition comprising (C), (D) and (E) as a main component. (A). Silica fine particles having a particle size of 1 to 100 millimicrons (B). General formula: (Wherein R ¹ and R ² are hydrocarbon groups having 1 to 6 carbon atoms. X ¹ and X ² are hydrolyzable groups. Y is a carbonate group or an epoxy group) Is an organic group containing m, and m is 0 or 1.) (C). General formula: (Wherein R ³ is an organic group having a polymerizable reactive group, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, X ³ is a hydrolyzable group, and n is Is 0 or 1
Is. ) (D). Polyfunctional epoxy compound (E). Curing catalyst 2. A laminate, wherein an antireflection film made of an inorganic substance is provided on the surface of a coat film made of the coating composition according to claim 1.