JP2509391B2 - Optical member having cured coating - Google Patents

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, JP-A-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.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
When the coating composition disclosed in Japanese Patent Laid-Open No. 35-35 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 is It has the drawback of being easy to peel off. 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. Therefore, an object of the present invention is to improve the above-mentioned drawbacks of the prior art and provide an optical member having a cured coating film having excellent adhesion on the surface of a plastic molded article such as a plastic lens.

[0004]

The present invention has been made in order to achieve the above-mentioned object, and is provided on the surface of a substrate.
(A) General formula (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (wherein R ¹ is an organic group containing an epoxy group and having 4 to 14 carbon atoms, and R ² is Alkyl group having 1 to 4 carbon atoms or 1 carbon atom
To 4 acyl groups, R ³ is an alkyl group having 1 to 6 carbon atoms, a
And b is an integer of 0 or 1), and / or a hydrolyzate thereof, and (B) silica fine particles having a particle size of 1 to 100 mm, (C) a general formula Al.X _m Y _3-m (where X is OL (L is an alkyl group having 1 to 4 carbon atoms),
Y is a ligand derived from a compound represented by the general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are both alkyl groups having 1 to 4 carbon atoms) and the general formula M ³ COCH ₂ COOM
⁴ (M ³ and M ⁴ are both alkyl groups having 1 to 4 carbon atoms)
Is at least one selected from the ligands derived from the compounds represented by the formula (1), and m is 0, 1 or 2, and (D ₁ ) a general formula [(C _n H _{2n + 1} ) ₂ NCS ₂ ] ₂ Zn (where n is an integer of 1 to 6) and zinc dialkyldithiocarbamate and /
Or (D ₂₎ (here p a is an integer from 1 to 6) the general formula _{(C p H 2p + 1)} 2 NCS 2 Na coating cure Kotin'ngu composition comprising a dialkyl sodium dithiocarbamate represented by The gist is an optical member having a cured coating formed by

The present invention will be described in detail below. The optical member of the present invention is characterized by having a cured film obtained by applying and curing a coating composition on the surface of a substrate,
The coating composition contains the above-mentioned component (A), component (B), component (C), component (D ₁ ) and / or component (D ₂ ).

As the organosilicon compound represented by the general formula (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} used as the component (A), known compounds are used, Examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, (3,4- Examples thereof include epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyldimethylmonomethoxysilane, and methyltrimethoxysilane. As the component (A), a hydrolyzate of an organosilicon compound may be used, and such a partial hydrolyzate of the organosilicon compound is obtained by partially or completely hydrolyzing the above organosilicon compound. . 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.

Particle size 1 to 10 used as component (B)
0 millimicron silica microparticles
It is used in the form of a colloidal solution dispersed in an organic solvent or a mixed solvent thereof. The silica fine particles are mainly used for enhancing 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 the silica fine particles is limited to 1 to 100 millimicrons, and particularly preferably 5 to 20 millimicrons. The reason is that when the particle size is less than 1 millimicron, the stability of fine particles is lacking, the durability of the cured film is poor, and 100
This is because a particle size exceeding millimicrons is not preferable because the cured film may lack transparency.

The general formula Al · used as the component (C)
Examples of the aluminum chelate compound represented by X _m Y _3-m include known compounds, and examples thereof include aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum-di-n-butoxide-mono. Examples thereof include ethyl acetoacetonate and aluminum-di-iso-propoxide-monomethylacetoacetate. In addition, these (C) components can be used in combination of two or more kinds.
The component (C) is a curing agent used to accelerate the curing reaction and cure at low temperature.

However, the curing reaction accelerating effect of the component (C) is not yet sufficient. Therefore, in the present invention, in addition to the component (C) as the curing agent, the component (D ₁ ) and / or the component (D ₁ )
₂ ) It uses the component. Examples of the zinc dialkyldithiocarbamate represented by the general formula [(C _n H _{2n + 1} ) ₂ NCS ₂ ] ₂ Zn used as the component (D ₁ ) include, for example, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, and dipropyldithiocarbamine. Examples thereof include zinc acid salt, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, and zinc dihexyldithiocarbamate. Two or more of these zinc dialkyldithiocarbamates can be used in combination.

Examples of the sodium dialkyldithiocarbamate represented by the general formula (C _p H _{2p + 1} ) ₂ NCS ₂ Na used as the component (D ₂ ) include sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate and dipropyldithiocarbamine. Examples thereof include sodium acid salt, sodium dibutyldithiocarbamate, sodium dipentyldithiocarbamate, and sodium dihexyldithiocarbamate. In addition, these sodium dialkyldithiocarbamate compounds can be used in combination of two or more kinds.

As the curing agent, the component (D ₁ ) and / or
Alternatively, by using the component (D ₂ ) together with the component (C), the curing reaction is further promoted as compared with the case where only the component (C) is used as a curing agent, and the adhesion to the substrate is excellent, and A cured coating excellent in scratch resistance can be obtained.

In the case of using nickel dialkyldithiocarbamate, iron dialkyldithiocarbamate, copper dialkyldithiocarbamate, etc., which are different from the zinc dialkyldithiocarbamate as the component (D ₁ ) and sodium dialkyldithiocarbamate as the component (D ₂ ) only in the metal species. However, it has been confirmed that these cause problems such as coloring of the cured film and insolubility in the coating composition. The same was true for zinc dibenzyldithiocarbamate.

Next, the mixing ratio of each component will be described.
The amount of the component (B) added is 0.
It is preferably from 0.1 to 5 parts by weight, particularly preferably from 0.1 to 1.5 parts by weight. The reason is that if the amount is less than 0.01 parts 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 transparency of the cured film may decrease. ⊚ The amount of the component (C) added is preferably 0.01 to 0.2 parts by weight per 1 part by weight of the component (A). The reason is that if the amount is less than 0.01 parts by weight, the curing is insufficient, and if the amount exceeds 0.2 parts by weight, the transparency of the cured coating is likely to decrease. The amount of the component (D ₁ ) and / or the component (D ₂ ) added is 0.0001 to 0.1 part by weight, and particularly preferably 0.0, per 1 part by weight of the component (A).
It is preferably from 0.05 to 0.02 parts by weight. 0.000
This is because if the amount is less than 1 part by weight, the adhesion of the cured film is insufficient, and if it exceeds 0.1 parts by weight, the transparency of the cured film is likely to decrease.

Furthermore, the coating composition used in the present invention is made of aluminum in order to match the refractive index with various substrates (plastic molded articles such as plastic lenses) together with the above-mentioned essential components, and to further improve scratch resistance. It is possible to contain a fine-particle inorganic substance composed of an oxide of a metal such as titanium, antimony, zirconium, or cerium. Furthermore, various surfactants can be added for the purpose of improving the flowability during coating and improving the smoothness of the cured film. Further, an ultraviolet absorber, an antioxidant, etc. can be added 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 at least one other monomer as a monomer component, 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
No. 6,086,045.

The coating composition is cured 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 resins are used. It is also possible to carry out the primer treatment.

The optical member of the present invention may be provided with a functional film as an antireflection film on the surface thereof. The optical member of the present invention can be used for a lens for a camera, an optical filter attached to a display of a word processor, a window glass of an automobile, as well as a spectacle lens.

[0018]

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 the 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: Scratch is considerably caused when strongly rubbed C: Scratch equivalent to that of the lens substrate is provided (2) Adhesion test A cross-cut tape test was performed according to JIS D-0202. . In other words, after 100 cross-cuts at 1 mm intervals and strong adhesion of adhesive tape (product name "Cellotape" manufactured by Nichiban Co., Ltd.), it was rapidly peeled in the direction of 90 ° from the surface, leaving a cured coating I checked.

(3) Appearance test The cured plastic film-coated plastic lens was visually inspected in a dark room, under fluorescent light, or the like for cloudiness or coloration. The criteria are as follows. A: Almost no cloudiness or coloring is visible. B ... I can see it a little. C ... quite visible.

(4) Dyeability test The obtained cured coated plastic lens was immersed in a solution for dyeing a plastic lens (a dyeing agent for HI-LUX manufactured by Hoya Co., Ltd. Maron) at 80 ° C. for 10 minutes to measure the dyeing density. did. The dyeing density was measured using light having a wavelength of λ = 550 nm. Dyeing concentration (%) = 100-transmittance (%) [Example 1] (Preparation of coating liquid) γ-glycidoxypropyltrimethoxysilane, which is the component (A), in a glass container equipped with a magnetic stirrer. 100 parts by weight was added, and 16 parts by weight of 0.1 N hydrochloric acid was added dropwise with stirring. After completion of dropping, the mixture was stirred for 24 hours to obtain a hydrolyzate. Then, water-dispersed silica fine particles (solid content 20%, average particle size 15
100 parts by weight, 80 parts by weight of isopropyl alcohol as a solvent, 80 parts by weight of ethyl cellosolve,
Further, 1 part by weight of a silicone-based surfactant as a lubricant, 4 parts by weight of aluminum acetylacetonate as the component (C) and 1 part by weight of zinc dimethyldithiocarbamate as the component (D ₁ ) were added as a curing agent, and after sufficiently stirring, Filtration was performed to obtain a coating liquid.

(Formation of Hardened Film) An acrylic copolymer plastic lens (refractive index n _d 1.56) consisting of diethylene glycol bisallyl carbonate, benzyl methacrylate and diallyl isophthalate was placed at 45 ° C. at 10 ° C.
% Aqueous solution of NaOH for 5 minutes for thorough washing, and then coating with the coating solution prepared by the above method by the dipping method (pulling speed 14 cm / min) and heating at 130 ° C. for 2 hours. A cured film was formed and various evaluations were performed.

As shown in Table 1, the plastic lens having a cured film obtained by the above method was confirmed to be a lens having good scratch resistance, appearance, dyeability, and excellent adhesion. It was

[Example 2] Using 50 parts by weight of water-dispersed antimony particles (solid content 20%, average particle size 20 mm) together with 100 parts by weight of water-dispersed silica particles (B), and pretreatment with alkali The same procedure as in Example 1 was carried out except that the above procedure was not performed. As shown in Table 1, the evaluation results have excellent physical properties as in Example 1.

[0025]

[Table 1]

[Examples 3 to 9] As shown in Tables 2 and 3, (A) component, (B) component, (C) component and (D)
₁₎ component or (D ₂₎ applying a component of the coating composition obtained by a predetermined amount to the substrate to obtain an optical member having a cured coating film was cured. Various physical properties of the obtained optical members with cured coatings of Examples 3 to 9 were evaluated in the same manner as in Example 1. As the results, as shown in Tables 2 and 3, the same results as in Example 1 were obtained.

[0027]

[Table 2]

[0028]

[Table 3]

[Comparative Example 1] The same procedure as in Example 1 was carried out except that the component (D ₁ ), zinc dimethyldithiocarbamate, was not used. As a result, as shown in Table 4, adhesion and dyeability were insufficient.

[0030]

[Table 4]

[Comparative Examples 2 to 5] (D ₁ ), instead of zinc dimethyldithiocarbamate as the component (D ₁ ),
Zinc dibenzyldithiocarbamate (Comparative Example 2), nickel dimethyldithiocarbamate (Comparative Example 3), iron dimethyldithiocarbamate (Comparative Example 4), and copper dimethyldithiocarbamate (Comparative Example 5), which are curing agents other than the component (D ₂ ). ) Was performed in the same manner as in Example 1. As a result, as shown in Table-5, the cured film was clouded, colored, and enthusiastic, and could not be used as an eyeglass lens.

[0032]

[Table 5]

[Comparative Examples 6 to 7] (C) used in Example 1
Except that only aluminum acetylacetonate was not used as the curing agent, and only zinc dimethyldithiocarbamate (Comparative Example 6) as the component (D ₁ ) and sodium dimethyldithiocarbamate (Comparative Example 7) as the component (D ₂ ) were used. The same procedure as in Example 1 was performed. As a result, as shown in Table-6, the scratch resistance was low.

[0034]

[Table 6]

[0035]

As described above, the optical member having the cured coating of the present invention has the remarkable advantages that it has excellent adhesion between the substrate and the cured coating and is excellent in scratch resistance, appearance and dyeability. .

Claims (3)

(57) [Claims] 1. On the surface of a substrate, (A) a general formula (R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (wherein R ¹ contains an epoxy group, carbon An organic group having 4 to 14 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms or 1 carbon atom
To 4 acyl groups, R ³ is an alkyl group having 1 to 6 carbon atoms, a
And b is an integer of 0 or 1), and / or a hydrolyzate thereof, and (B) silica fine particles having a particle size of 1 to 100 mm, (C) a general formula Al.X _m Y _3-m (where X is OL (L is an alkyl group having 1 to 4 carbon atoms),
Y is a ligand derived from a compound represented by the general formula M ¹ COCH ₂ COM ² (M ¹ and M ² are both alkyl groups having 1 to 4 carbon atoms) and the general formula M ³ COCH ₂ COOM
⁴ (M ³ and M ⁴ are both alkyl groups having 1 to 4 carbon atoms)
Is at least one selected from the ligands derived from the compounds represented by the formula ( ₁ ) and m is 0, 1 or 2, and (D ₁ ) a general formula [(C _n H _{2n + 1} ) ₂ NCS ₂ ] ₂ Zn (where n is an integer of 1 to 6) and zinc dialkyldithiocarbamate and /
Or (D ₂₎ (here p a is an integer from 1 to 6) the general formula _{(C p H 2p + 1)} 2 NCS 2 Na coating cure Kotin'ngu composition comprising a dialkyl sodium dithiocarbamate represented by An optical member having a cured coating formed by 2. The optical member according to claim 1, wherein the base material is a plastic molded product. 3. The optical member according to claim 2, wherein the plastic molded product is a plastic lens.