JPH0792302A - Optical member with hardened coating film - Google Patents

Abstract

PURPOSE:To obtain an optical member excellent in the adhesion of the substrate to the hardened coating film and the adhesion of the coating film to the inorg. vapor-deposited film by applying a specified coating compsn. on the surface of a substrate and hardening the compsn. CONSTITUTION:A coating compsn. contg. an organosilicon compd. represented by formula I and/or its hydrolyzate, an arom. ring-contg. organosilicon compd. represented by formula II and/or its hydrolyzate, a silicate compd. represented by formula III and fine silica particles having 1-100mum particle size is applied and hardened. In the formula I, R1 is 1-4C alkyl and R2 is 1-4C alkylene. In the formula II, R3 is 1-4C alkyl and n1 is an integer of 1-3. In the formula III, each of X and R4-R7 is a 1-4C org. group, Y is an epoxy group-contg. functional group, n2 is an integer of 1-3 and n3 is an integer of >=1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an optical member having a cured coating.

[0002]

2. Description of the Related Art It is well known that a cured coating is applied to the surface of a plastic molded article such as a plastic lens in order to improve scratch resistance. For example, Japanese Patent Publication Sho 5
JP-A-7-2735 discloses a compound containing an epoxy group and / or a silanol and / or a siloxane group on the surface of a plastic lens, silica fine particles having a particle size of 1 to 100 millimicrons, and an aluminum chelate compound. A method of applying and curing the coating composition to form a cured coating film is disclosed.

However, the Japanese Patent Publication No. 57-2735
When the coating composition disclosed in the publication is applied to a plastic lens and cured to form a cured coating, the adhesion between the plastic lens and the cured coating is insufficient depending on the type of the plastic lens, and the cured coating peels off. It has the drawback of being easy to do. Therefore, it is also possible to perform pretreatment such as plasma treatment and primer treatment on the plastic lens in advance, and then apply and cure the coating composition. However, such pretreatment only complicates the process. Moreover, there is a drawback that the adhesion between the plastic lens and the cured coating is not always sufficient even if such pretreatment is performed.

As a coating composition for solving these problems, there is, for example, one described in JP-A-4-271301. In the publication, an organosilicon compound containing an epoxy group, silica fine particles having a particle size of 1 to 100 millimicrons, an aluminum chelate compound, zinc dialkyldithiocarbamate and / or sodium dialkyldithiocarbamate are provided on the surface of a plastic lens. There is disclosed an optical member having a cured film obtained by applying and curing a coating composition containing

[0005]

[Patent Document 1] Japanese Unexamined Patent Application Publication No.
The coating composition disclosed in Japanese Patent No. 271301 has an unfavorable manufacturing problem that zinc dialkyldithiocarbamate and sodium dialkyldithiocarbamate are hardly dissolved during preparation. Further, an optical member having a cured film obtained by using the coating composition has excellent adhesiveness between a substrate and a cured film, and further, an adhesiveness between the cured film and an inorganic vapor deposition film provided thereon if desired. There is a problem that variations are seen.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a coating composition which is easy to prepare by using a coating composition which does not impair the conventional film performance and which is used as a base material and a cured film. An object of the present invention is to provide an optical member in which the adhesion, and further the adhesion between the cured film and the inorganic vapor-deposited film have little variation.

[0007]

The above-mentioned object is to provide the following (A), (B), (C) and (D) on the surface of a substrate.
It is achieved by an optical member having a cured coating, which is obtained by applying and curing a coating composition containing

(A) General formula

[Chemical 4] (In the formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, and R _{2 is}
Is an alkylene group having 1 to 4 carbon atoms) and / or a hydrolyzate thereof, (B) a general formula

[Chemical 5] (In the formula, R ₃ is an alkyl group having 1 to 4 carbon atoms, and n ₁
Is an integer of 1 to 3), an aromatic ring-containing organosilicon compound and / or a hydrolyzate thereof, (C) a general formula.

[Chemical 6] (In the formula, X and R _{4 to} R ₇ are organic groups having 1 to 4 carbon atoms,
Y is a functional group containing an epoxy group, n ₂ is an integer of 1 to ₃ , n ₃ is an integer of 1 or more), and (D) silica fine particles having a particle size of 1 to 100 millimicrons.

The present invention will be described in detail below.

As the organosilicon compound represented by the above general formula (I) used as the component (A) in the present invention, R _{1 in} the formula is a methyl group, an ethyl group, a propyl group or a butyl group, and R It is preferable that ₂ is a methylene group, an ethylene group, a propylene group or a butylene group. The propyl group, butyl group, propylene group and butylene group may have a branch.

As the component (A), a hydrolyzate of an organosilicon compound may be used. Such a hydrolyzate of an organosilicon compound partially or completely hydrolyzes the above organosilicon compound. Obtained. This hydrolysis is preferably carried out in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid. The organosilicon compound or its hydrolyzate as the component (A) may be used alone or in combination. As the component (A), the organosilicon compound and its hydrolyzate may be used in combination.

The above-mentioned general formula used as the component (B) in the present invention

[Chemical 7] (In the formula, R ₃ is an alkyl group having 1 to 4 carbon atoms, and n ₁
Is an integer of 1 to 3), as the aromatic ring-containing organosilicon compound, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Examples thereof include diphenyldipropoxysilane, diphenyldibutoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylpropoxysilane, and triphenylbutoxysilane. The “propoxy” group and the “butoxy” group in the above-exemplified compounds may be branched.

As the component (B), a hydrolyzate of an organosilicon compound can be used as in the above-mentioned component (A).

In the general formula showing the silicate compound as the component (C), X and R _{4 to} R ₇ are organic groups having 1 to 4 carbon atoms, for example, an alkyl group or an alkoxy group, and Y is a functional group containing an epoxy group. , For example, a glycidoxyalkyl group. That is, the silicate compound as the component (C) is obtained by adding an organosilicon compound having a glycidoxy group to the silicate, and its desirable characteristic range is as follows.

Epoxy content: 1.5-1.7 me
q / g Alkoxy content: 35-45 wt% (as MeOH) SiO ₂ content: 40-50 wt% Viscosity (25 ° C): 70 cps or less Specific gravity (25 ° C): 1.1-1.3 (C) of component Examples of the silicate compound are as follows.

(1)

[Chemical 8] 1,3-Bis [(tri-γ-glycidoxypropyldimethoxysiloxy) -siloxy] -1,3-tetramethoxydisiloxane (2)

[Chemical 9] 1,7-Bis [(tri-γ-glycidoxypropyldimethoxysiloxy) -siloxy] -1,3,5,7-octamethoxytetrasiloxane (3)

[Chemical 10] 1,3-Bis [(di-γ-glycidoxypropyldimethoxysiloxy) -methoxysiloxy] -1,3-tetramethoxydisiloxane (4)

[Chemical 11] 1,7-Bis [(di-γ-glycidoxypropyldimethoxysiloxy) -methoxysiloxy] -1,3,5,7
-Octamethoxytetrasiloxane (5)

[Chemical 12] 1,3-Bis [(γ-glycidoxypropyldimethoxysiloxy) -dimethoxysiloxy] -1,3-tetramethoxydisiloxane (6)

[Chemical 13] 1,7-Bis [(γ-glycidoxypropyldimethoxysiloxy) -dimethoxysiloxy] -1,3,5,7-
Octamethoxytetrasiloxane (7)

[Chemical 14] 1,3-Bis [(tri-γ-glycidoxypropyldimethoxysiloxy) -siloxy] -1,3-tetraethoxydisiloxane (8)

[Chemical 15] 1,3-Bis [(di-γ-glycidoxypropyldimethoxysiloxy) -methoxysiloxy] -1,3-tetraethoxydisiloxane (9)

[Chemical 16] 1,3-bis [(γ-glycidoxypropyldimethoxysiloxy) -dimethoxysiloxy] -1,3-tetraethoxydisiloxane (D) The silica fine particles having a particle size of 1 to 100 millimicrons are silica fine particles. Is used in the form of a colloidal solution in which water is dispersed in water, an organic solvent or a mixed solvent thereof. The silica fine particles mainly enhance the scratch resistance of the cured film. Examples of the organic solvent used for dispersing the silica fine particles include alcohols such as methanol and ethanol. The particle size of silica fine particles is 1 to 100
It is limited to millimicrons, particularly preferably 5 to 20 millimicrons. The reason for this is that if the particle size is less than 1 millimicron, the stability of the fine particles is lacking and the cured coating is inferior in durability, and if the particle size exceeds 100 millimicron, the cured coating is lacking in transparency, which is not preferable. .

The present inventor has added a conventionally known composition comprising the above-mentioned components (A) and (D) to the aromatic ring-containing organosilicon compound (B) and the silicate compound (C). By including the following, there is no variation in the adhesion between the base material and the cured film and the adhesion between the cured film and the inorganic vapor-deposited film regardless of the type of plastic lens without lowering the film hardness of the conventional cured film. Further, it has been found that the component (B) and the component (C) have good compatibility with solvents such as alcohols, ketones, cellosolves, and carboxylic acids, so that the compounding work can be facilitated and the present invention is completed. I arrived.

According to the study by the present inventor, (A),
A cured coating made of a coating composition composed of components (C) and (D) and lacking component (B) has insufficient adhesion depending on the type of plastic lens, and (A), (B) and It has been clarified that the cured film made of the coating composition comprising the component (C) and lacking the component (D) has insufficient adhesion to the inorganic vapor deposition film.

Next, the mixing ratio of each component will be described.

The amount of the component (B) added is preferably 0.01 to 0.5 part by weight, more preferably 0.1 to 0.3 part by weight, relative to 1 part by weight of the component (A). The reason is that if the amount is less than 0.01 parts by weight, it is difficult to obtain the effect of improving the adhesion to the cured film depending on the type of the plastic lens, and if it exceeds 0.5 parts by weight, the scratch resistance of the cured film is impaired. Because it is easy.

The amount of component (C) added is preferably 0.01 to 1.5 parts by weight, more preferably 0.2 to 0.7 parts by weight, based on 1 part by weight of component (A). The reason is that if it is less than 0.01 parts by weight, the adhesion with the inorganic vapor deposition film provided on the cured coating tends to be insufficient, and if it exceeds 1.5 parts by weight, the cured coating tends to crack. Is.

The amount of the component (D) added is 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 1 part by weight of the component (A).
It is preferably 1.5 parts by weight. The reason is 0.0
This is because if the amount is less than 1 part by weight, the scratch resistance of the cured film is insufficient, and if it exceeds 5 parts by weight, cracks are likely to occur in the cured film and the risk of lowering the transparency of the cured film increases. .

The coating composition used in the present invention may use a curing agent to accelerate the reaction and cure at a low temperature. Examples of the curing agent include amines such as allylamine and ethylamine, or various acids and bases including Lewis acids and Lewis bases such as organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, bromic acid, and selenium selenite. Examples thereof include acids, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminic acid, carbonic acid, perchloric acid, and other metal salts, and aluminum, zirconium, titanium, and other alkoxides, or complex compounds thereof.

Further, the coating composition used in the present invention contains aluminum, antimony, zirconium, tin, tungsten in order to match the refractive index with the optical member serving as the substrate and to further improve the scratch resistance. Alternatively, a fine-particle inorganic material composed of a metal oxide such as silicon may be added.

The coating composition used in the present invention may contain various surfactants for the purpose of improving the wettability at the time of application and improving the smoothness of the cured film. Further, an ultraviolet absorber, an antioxidant and the like can be used as long as they do not affect the physical properties of the cured film. In order to improve the coating property of the coating composition, the above-mentioned essential components and optional components are usually dissolved or dispersed in a solvent such as alcohols, ketones, cellosolves, and carboxylic acids. As a method for applying the coating composition to the surface of the base material, a commonly used method such as a dipping method, a spin method or a spray method can be applied, but the dipping method and the spin method are particularly preferable in terms of surface accuracy and the like.

As the substrate to which the coating composition is applied, a copolymer containing methyl methacrylate and one or more other monomers as monomer components, a diethylene glycol bisallyl carbonate homopolymer, and a copolymer containing sulfur. , Copolymers containing diethylene glycol bisallyl carbonate and one or more other monomers as monomer components, acrylonitrile-styrene copolymers, polystyrene, halogen-containing copolymers, polyvinyl chloride, unsaturated polyester resins, polyethylene Examples of the substrate include plastic lenses such as terephthalate and polyurethane, or inorganic glass lenses.
Particularly excellent adhesion and scratch resistance are obtained when an acrylic copolymer plastic lens is used. Examples of the acrylic copolymer plastic lens include a diethylene glycol bisallyl carbonate / benzyl methacrylate / diallyl phthalate terpolymer plastic lens. Further, a diethylene glycol bisallyl carbonate / benzyl methacrylate / diallyl phthalate / alkyl methacrylate quaternary copolymer may be mentioned. These acrylic copolymers are disclosed in JP-A Nos. 51-125487, 54-41965 and 59.
-191708 and WO89 / 09418
It is disclosed in the publication.

Curing of the coating composition is carried out by hot air drying and irradiation with active energy rays, preferably 70
It is preferable to carry out in hot air of up to 200 ° C., particularly preferably in hot air of 90 to 150 ° C. Far-infrared rays and the like are used as active energy rays, and damage due to heat can be suppressed to a low level.

Before coating and curing the coating composition on the substrate, chemical treatment with acid, alkali, various organic solvents, physical treatment with plasma, ultraviolet rays, etc., washing treatment with various detergents, and further various treatments It is also possible to perform a primer treatment using a resin.

The optical member of the present invention may have an antireflection film formed of an inorganic vapor deposition film on the surface of the above-mentioned cured film.

The optical member of the present invention includes an eyeglass lens,
It can be used for camera lenses, optical filters attached to word processor displays, and automobile window glasses.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the plastic lenses having a cured coating obtained in the present examples and comparative examples were measured by the following measuring methods.

(1) Scratch resistance test The surface of a plastic lens was rubbed with steel wool # 0000 to visually judge the scratch resistance. The judgment criteria were as follows.

A: Almost no scratch even if strongly rubbed B: Very scratched if strongly rubbed C: Scratch equivalent to the lens substrate (2) Adhesion test Cross cut tape test according to JIS D-0202 Was done. That is, after cross-cutting 100 stitches at 1 mm intervals and strongly adhering an adhesive tape (product name "Cellotape" manufactured by Nichiban Co., Ltd.), it was rapidly peeled off in 90 ° direction from the surface, leaving a cured film or a vapor deposition film. I checked the cells.

(3) Appearance The transparency, the colored state, the surface state, and the like were visually inspected.

Example 1 (Preparation of coating liquid) In a glass container equipped with a magnetic stirrer, 112.5 parts by weight of (A) component γ-glycidoxypropyltrimethoxysilane,
Phenyltriethoxysilane 22.5 as component (B)
By weight, a silicate compound to which γ-glycidoxypropyltrimethoxysilane as the component (C) is added (trade name: MKC silicate MSEP2, Mitsubishi Kasei Co., Ltd.)
(Manufactured by Mitsui Chemicals, Inc.) 42.5 parts by weight, and 3.75 parts by weight of 0.6N hydrochloric acid was added dropwise with stirring. After completion of dropping, the mixture was stirred for 24 hours to obtain a hydrolyzate. Then, the colloidal silica having a SiO ₂ concentration of 40% as the component (D) (trade name: Snowtex 40, water-dispersed silica, manufactured by Nissan Chemical Co., Ltd .: S
250 parts by weight of iO ₂ particle size of 10 to 20 millimicron),
300 parts by weight of isopropyl alcohol as a solvent, n-
100 parts by weight of butanol, 100 parts by weight of propylene glycol monomethyl ether, 15 parts by weight of aluminum acetylacetonate as a curing agent, and 0.6 parts by weight of a surfactant as a lubricant were added, and after sufficiently stirring, filtration was performed to obtain a coating liquid. Obtained. The coating liquid was easy to prepare, and the coating liquid was visually free from precipitates.

(Formation of Hardened Film) 50 acrylic resin plastic lenses (refractive index n _d 1.56) consisting of diethylene glycol bisallyl carbonate, benzyl methacrylate and diallyl isophthalate (45 ° C.)
After immersing in 10% NaOH aqueous solution for 5 minutes to perform sufficient washing, coating is performed by the dipping method (withdrawing speed 14 cm / min) using the coating liquid prepared by the above method, and at 130 ° C. for 2 hours. A cured coating was formed by heating and various evaluations were performed.

As shown in Table 1, all 50 plastic lenses having a cured coating obtained by the above method showed excellent results such as scratch resistance A, adhesion 100/100, and good appearance. .

(Formation of Antireflection Film) A laminated structure of SiO ₂ and ZrO ₂ (λ / 4−λ / 2−) is formed on the cured film of the optical member having the cured film obtained by the above method by vacuum deposition.
An antireflection film of λ / 4) was formed. As shown in Table 1, all the 50 plastic lenses having the cured film having the antireflection film thus obtained showed excellent results of scratch resistance of A and adhesion of 100/100. .

Example 2 As component (B), 22.5 parts by weight of diphenyldimethoxysilane was used in place of 22.5 parts by weight of phenyltriethoxysilane of Example 1, and pretreatment with an alkali was not carried out. Except for this, the same procedure as in Example 1 was performed. As shown in Table 1, the evaluation results were excellent as in Example 1.

Example 3 As the component (D), 250 parts by weight of the water-dispersed silica fine particles (solid content 40%) of Example 1 were used, and the SiO ₂ concentration was 20.
% Water-dispersed silica fine particles (trade name: Snowtex O, manufactured by Nissan Kagaku Co., Ltd .: SiO ₂ particle size 10 to ₂ )
The same procedure as in Example 1 was carried out except that 0 millimicron) was used and no pretreatment with alkali was performed. As shown in Table 1, the evaluation results were excellent as in Example 1.

[0041]

[Table 1]

Example 4 As the component (B), 12.5 parts by weight of phenyltriethoxysilane and 10 parts of diphenyldimethoxysilane were used instead of 22.5 parts by weight of phenyltriethoxysilane of Example 1.
The same procedure as in Example 1 was performed, except that parts by weight and no pretreatment with alkali were performed. As shown in Table 2, the evaluation results were excellent as in Example 1.

Examples 5 to 6 As shown in Table 2, diethylene glycol bisallyl carbonate resin (Example 5) and xylene diisocyanate-pentaerythritol tetrakispropionate type polyurethane resin were used as the base materials, and the same procedure as in Example 1 was carried out. It was As shown in Table 2, the evaluation results were excellent as in Example 1.

[0044]

[Table 2]

Comparative Examples 1 to 4 As shown in Tables 3 and 4, a composition lacking at least one of the components (A) to (D) was used to obtain a plastic lens having a cured film, which was further coated on the surface thereof. A plastic lens having the same antireflection film as in Example 1 was obtained. The evaluation results are shown in Tables 3 and 4. As shown in Tables 3 and 4, none of these plastic lenses satisfied the characteristics.

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

As described above, according to the present invention, by using a coating composition which is easy to prepare, the adhesion between the substrate and the cured film and the adhesion between the cured film and the inorganic vapor deposition film are excellent. Optical member can be obtained.

Claims (1)

[Claims] 1. On the surface of a substrate, (A) a general formula: (In the formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, and R _{2 is}
Is an alkylene group having 1 to 4 carbon atoms) and / or a hydrolyzate thereof, (B)
General formula: (In the formula, R ₃ is an alkyl group having 1 to 4 carbon atoms, and n ₁
Is an integer of 1 to 3), an aromatic ring-containing organosilicon compound and / or a hydrolyzate thereof, and (C) the general formula: (In the formula, X and R _{4 to} R ₇ are organic groups having 1 to 4 carbon atoms,
Y is a functional group containing an epoxy group, n ₂ is an integer of 1 to ₃ , n ₃ is an integer of 1 or more), and (D) silica fine particles having a particle size of 1 to 100 millimicrons. An optical member having a cured coating, which is obtained by applying and curing a coating composition containing: