JPH06102776B2 - Cured film and optical member having the cured film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cured film and an optical member having a cured film.

[Conventional technology]

It is well known that a high-refractive-index synthetic resin is provided with a cured film of an organosilicon polymer in order to improve scratch resistance of the high-refractive-index synthetic resin such as a polyurethane resin or a halogen-containing resin. It is also known that in a high-refractive-index synthetic resin having a cured film made of an organosilicon polymer, the cured film contains fine particles of a high-refractive-index metal oxide in order to suppress the occurrence of interference fringes. As an example, Japanese Examined Japanese Patent Publication No. 63-37
No. 142 discloses a cured film of a coating composition containing tin oxide fine particles having an average particle diameter of 1 to 300 mμ and an organic silicon compound.

[Problems to be Solved by the Invention]

However, the coating composition containing the tin oxide fine particles and the organosilicon compound disclosed in JP-B-63-37142 is in a state where the tin oxide fine particles are positively charged, and the organosilicon compound is negatively charged. Since they are in a charged state, the tin oxide fine particles tend to agglomerate. Therefore, when this coating composition is used, for example, in an eyeglass lens that requires high transparency, the transparency of the applied cured film tends to be insufficient, and the coating composition has a problem that it is difficult to handle. . The present invention has been made to solve the above problems,
It is an object of the present invention to provide a cured film made of a coating composition that does not cause the tin oxide fine particles to agglomerate and does not impair the characteristics of the tin oxide fine particles, and an optical member having the cured film.

[Means for Solving the Problems]

 The above-mentioned objects have been solved by the invention described below.

A first invention thereof is a cured film obtained by curing a coating composition containing the following A component and B component.

Component A: general formula (R ¹ ) a (R ³ ) bSi (OR ² ) 4- (a + b) (wherein R ¹ is an organic group having 4 to 14 carbon atoms, including an epoxy group, R ² is carbon) Alkyl group of 1 to 4 or 1 to 4 carbon atoms
An acyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, a and b
Represents an integer of 0 or 1), and is an organosilicon compound or a hydrolyzate thereof.

Component B: Particle size 1 coated with tungsten oxide particles
100 millimicron tin oxide fine particles.

The second invention is an optical member characterized by comprising a cured film formed by curing a coating composition containing the following components A and B on an optical substrate.

Component A: general formula (R ¹ ) a (R ³ ) bSi (OR ² ) 4- (a + b) (wherein R ¹ is an organic group having 4 to 14 carbon atoms, including an epoxy group, R ² is carbon) Alkyl group of 1 to 4 or 1 to 4 carbon atoms
An acyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, a and b
Represents an integer of 0 or 1), and is an organosilicon compound or a hydrolyzate thereof.

Component B: Particle size 1 coated with tungsten oxide particles
100 millimicron tin oxide fine particles.

Hereinafter, the present invention will be described in detail.

Examples of the organosilicon compound represented by the general formula (R ¹ ) a (R ³ ) bSi (OR ² ) 4- (a + b) or its hydrolyzate used as the component A in the present invention and, for example, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane , Γ-glycidoxypropyldimethylmonomethoxysilane, methyltrimethoxysilane and the like, and hydrolysates thereof, but are not limited to these.

The tin oxide fine particles having a particle size of 1 to 100 millimicrons coated with the tungsten oxide fine particles used as the component B in the present invention are used in the form of a colloidal solution in which the fine particles are dispersed in water, an organic solvent or a mixed solvent thereof. It is used to improve the refractive index, scratch resistance and warm water resistance of the cured film, and to facilitate the handling of the coating composition.

The particle size of the tin oxide fine particles is limited to 1 to 100 millimicrons, particularly preferably 5 to 20 millimicrons. The reason is that if the particle size is less than 1 millimicron, the stability of fine particles is lacking and the durability of the cured film is poor, and if the particle size exceeds 100 millimicrons, the transparency of the cured film is poor, which is not preferable. .

The tin oxide fine particles coated with the tungsten oxide fine particles have a structure in which the tungsten oxide fine particles and the tin oxide fine particles are chemically or physically bonded to each other, and the tungsten oxide fine particles cover the tin oxide fine particles.
The reason for specifying the fine particles is as described below.

The tungsten oxide fine particles are in a negatively charged state. When the tin oxide particles are coated with the tungsten oxide particles, the entire surface of the particles becomes negatively charged without impairing the characteristics of the tin oxide particles. Therefore, when mixed with the organosilicon compound, the tin oxide fine particles coated with the tungsten oxide fine particles repel because the organosilicon compound is negatively charged, and it becomes possible to uniformly disperse without causing aggregation. The handling of the coating composition becomes easy. It should be noted that the surface of the tin oxide particles cannot be negatively charged by simply mixing the tungsten oxide particles and the tin oxide particles, which is not preferable.

The refractive index of tin oxide fine particles coated with tungsten oxide fine particles is 1.82 to 1.86, and the specific gravity is 1.095 to 1.1 at 25 ° C.
15, pH of 6.5 to 10.0 at room temperature and viscosity of 10 or less at 25 ° C. are particularly preferably used.

The amount of tin oxide fine particles coated with tungsten oxide fine particles is such that the ratio of the solid content of tin oxide coated with tungsten oxide fine particles / the amount of organic silicon compound or its hydrolyzate used is 1/50 to 5/1. Preferably. The reason is that when the ratio is 1/50, the refractive index of the cured film becomes low, and the range of application to the base material is significantly limited.If it exceeds 5/1, cracks and the like tend to occur between the cured film and the substrate. This is because the possibility of further deterioration of transparency is increased.

The coating composition for forming the cured film of the present invention contains a curing agent to accelerate the reaction, and a particulate metal oxide having a particle diameter of 1 to 300 mμ in order to match the refractive index with the lenses serving as various substrates. For the purpose of improving the wettability during coating and improving the smoothness of the cured film, various surfactants can be contained. Further, an ultraviolet absorber, an antioxidant and the like can be added as long as they do not affect the physical properties of the cured film.

Examples of the curing agent include amines such as allylamine and ethylamine, and various acids and bases including Lewis acids and Lewis bases such as organic carboxylic acids, chromic acid, hypozinc acid, boric acid, bromic acid, and selenium selenite. Examples thereof include a metal salt having an acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminic acid, carbonic acid, a metal alkoxide having aluminum, zirconium, titanium, or a metal chelate compound thereof.

Examples of the fine particle metal oxides include fine particles of aluminum oxide, titanium oxide, antimony oxide, zirconium oxide, silicon oxide, cerium oxide and the like.

The cured film of the present invention can be obtained by curing the coating composition. Curing of the coating composition is carried out by irradiation with hot air drying active energy rays, and the curing condition is preferably carried out in hot air of 70 to 200 ° C, particularly preferably 90 to 150 ° C.

The substrate used for applying the cured film of the present invention,
Methyl methacrylate homopolymer, copolymer containing methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate and one or more other monomers as monomer components And a plastic lens such as a copolymer, polycarbonate, polystyrene, polyvinyl chloride, polyethylene terephthalate, or polyurethane, or an inorganic glass lens.

Examples of the method of forming the cured film of the present invention on a substrate include a method of applying the coating composition described above to the substrate. As a coating means, a commonly used method such as a dipping method, a spin method or a spray method can be applied, but a dipping method or a spin method is particularly preferable from the viewpoint of surface accuracy.

Furthermore, before applying the above-mentioned coating composition to a 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. By performing the above-mentioned primer treatment, the adhesion between the base material and the cured film can be improved.

The cured film of the present invention can be used as an antireflection film as a high refractive index film, and can also be used as a multifunctional film by adding functional components such as antifogging, photochromic and antifouling.

Furthermore, the optical member having the cured film of the present invention can be formed with an antireflection film made of an inorganic material on the cured film, and can be used for an spectacle lens, a camera lens, an optical filter attached to a word processor, or the like. .

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition,
Various physical properties of the optical members having a cured film obtained in the present example and the comparative example were measured by the following measuring methods.

(1) Scratch resistance test The surface of the cured film was rubbed with steel wool # 0000 to visually determine the scratch resistance. The judgment criteria were as follows.

A: Almost no scratch even if it is rubbed strongly B: It is considerably scratched if it is rubbed strongly C: It has the same scratch as the optical substrate (2) Presence or absence of interference fringes Visually see the optical member with a cured film under fluorescent light It was judged.
The judgment criteria are as follows.

A: Almost no interference fringes are visible B: A little visible C: Quite visible (3) Adhesion test 100 pieces of 1-mm intervals are cross-cut on the cured film, and adhesive tape (product name "Cellotape" Nichiban ( (Product Co., Ltd.) was strongly adhered, the adhesive tape was rapidly peeled off, and the presence or absence of peeling of the cured film after peeling off the adhesive tape was examined.

(4) Impact resistance test A 16 g steel ball was dropped from a height of 127 cm to the center of an optical member having a center thickness of 2 mm to check for damage.

(5) Warm water resistance test The optical member was immersed in warm water at 50 ° C for 5 hours, and the same scratch resistance test and adhesion test as described above were performed.

(6) Transparency test (a) Visual test It was visually examined in a dark room under a fluorescent lamp whether the cured film had fog. The judgment criteria are as follows.

A: Almost no haze is visible B: Little visible C: Very visible (b) Haze value measurement A direct reading haze computer (manufactured by Suga Test Instruments Co., Ltd.) was used for measurement.

[Example 1] (Preparation of coating liquid) To a glass container equipped with a magnetic stirrer, 70 parts by weight of γ-glycidoxypropylmethoxysilane corresponding to the above-mentioned component A was added, and the mixture was stirred at 0.1%.
16 parts by weight of normal hydrochloric acid was added dropwise. After completion of dropping, the mixture was stirred for 24 hours to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, 105 parts by weight of water-dispersed tin oxide fine particles (solid content 20%, average particle diameter 15 mm) coated with the above-mentioned component B, tungsten oxide fine particles, 80 parts by weight of isopropyl alcohol as a solvent, 80 parts by weight of ethyl cellosolve. Parts, 1 part by weight of a silicone-based surfactant as a lubricant, and 4 parts by weight of aluminum acetylacetonate as a curing agent were added to the aforementioned hydrolyzate of γ-glycidoxypropyltrimethoxysilane, and the mixture was thoroughly stirred. Then, filtration was performed to prepare a coating liquid.

(Cured film formation) A plastic lens made of diethylene glycol bisallyl carbonate, benzyl methacrylate, and diallyl isophthalate (refractive index nd1.56) was immersed in a 10% NaOH aqueous solution at 45 ° C for 5 minutes to thoroughly wash it. The plastic lens is dipped in the coating liquid prepared by the method described above, and the dip method (pulling speed 14 cm /
Min), and after completion of the immersion, the plastic lens was heated at 130 ° C. for 2 hours to form a cured film, and the above-described various evaluations were performed.

As shown in Table 1, the plastic lens having the cured film obtained by the above-mentioned method showed almost no interference fringes, had a haze value of 0.1, and had excellent transparency by visual inspection. Further, it was confirmed that the fine metal particles of the coating composition were uniformly dispersed because of the excellent transparency.

Example 2 Instead of 70 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the component A used in Example 1, the same A was used.
Example 1 was repeated except that 70 parts by weight of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane corresponding to the component was used. As shown in Table 1, the evaluation results were as excellent as those in Example 1.

Example 3 Instead of 70 parts by weight of γ-glycidoxypropyltrimethoxysilane corresponding to the component A used in Example 1, the same A was used.
The same procedure as in Example 1 was carried out except that 70 parts by weight of methyltrimethoxysilane corresponding to the components and 4 parts by weight of sodium acetate were used as the curing agent instead of 4 parts by weight of aluminum acetylacetonate. As shown in Table 1, the evaluation results were as excellent as those in Example 1.

[Comparative Example 1] 78 parts by weight of methanol-dispersed antimony sol (solid content: 30%, average particle size: 15 mm) was used instead of 105 parts by weight of tungsten oxide particles-coated tin oxide particles corresponding to the component B used in Example 1. The same procedure as in Example 1 was carried out except that it was used. As shown in Table 1, the evaluation results were inferior in scratch resistance and hot water resistance to the lenses obtained in Example 1.

[Comparative Example 2] Tungsten oxide fine particle coating corresponding to the component B used in Example 1 was replaced with tin oxide fine particles, and water-dispersed colloidal silica (solid content 20%, average particle diameter 15 mm) was used. The procedure was as in Example 1. The results are shown in Table 1.
As shown in (4), interference fringes were generated, which was not preferable in appearance.

Comparative Example 3 Instead of 105 parts by weight of the tin oxide fine particles coated with tungsten oxide fine particles corresponding to the component B used in Example 1, water-dispersed tin oxide fine particles not coated with tungsten oxide fine particles (solid content 20%, average) The same procedure as in Example 1 was carried out except that 105 parts by weight (particle size: 10 mm) was used. As a result, as shown in Table 1, the haze value was 8.3, which was inferior in transparency as compared with the optical members of the examples, and clouding of the cured film was also observed in the visual test, and thus tin oxide fine particles were aggregated. It was confirmed.

[Effects of the Invention] As described above, according to the present invention, it is possible to provide a cured film made of a coating composition which does not impair the characteristics of tin oxide fine particles and in which the tin oxide fine particles are hard to aggregate, and an optical member having the cured film. did it. The cured film of the present invention has particularly good hot water resistance and transparency, and can be particularly preferably used as an eyeglass lens.

Claims (5)

[Claims] 1. A cured film obtained by curing a coating composition containing the following components A and B. Component A: general formula (R ¹ ) a (R ³ ) bSi (OR ² ) 4- (a + b) (wherein R ¹ is an organic group having 4 to 14 carbon atoms, including an epoxy group, R ² is carbon) Alkyl group of 1 to 4 or 1 to 4 carbon atoms
An acyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, a and b
Represents an integer of 0 or 1) or an organic silicon compound or a hydrolyzate thereof. Component B: Particle size 1 coated with tungsten oxide particles
100 millimicron tin oxide fine particles. 2. The cured film according to claim 1, wherein the surface of the tin oxide fine particles having a particle size of 1 to 100 mm and coated with the tungsten oxide fine particles as the component B is negatively charged. 3. The cured film according to claim 1, wherein the coating composition contains at least one curing catalyst selected from the group consisting of metal salts, metal alkoxides and metal chelate compounds. 4. An optical member having a cured film, comprising a cured film obtained by curing a coating composition containing the following components A and B of an optical substrate. Component A: general formula (R ¹ ) a (R ³ ) bSi (OR ² ) 4- (a + b) (wherein R ¹ is an organic group having 4 to 14 carbon atoms, including an epoxy group, R ² is carbon) Alkyl group of 1 to 4 or 1 to 4 carbon atoms
An acyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, a and b
Represents an integer of 0 or 1) or an organic silicon compound or a hydrolyzate thereof. Component B: Particle size 1 coated with tungsten oxide particles
100 millimicron tin oxide fine particles. 5. The optical member having a cured film according to claim 4, wherein the optical member is an eyeglass lens.