JP2006010799A - Hard coat composition and plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide hard coat composition which can suppress the occurrence of interference fringes when it is applied to a high refractive index lens, and which can be dyed and is excellent in weather resistance and a hard coat composite good which can be obtained by curing the composition after an application of the composition. <P>SOLUTION: The hard coat composition of this invention is characterized by including components, such as (A): composite metal oxide constituted of tin oxide, zirconium oxide and antimony pentoxide and whose outermost surface is modified composite metal oxide covered with the antimony pentoxide and/or silicon dioxide, and (B): an epoxy group-containing silicon compound or its partially hydrolyzed substance and (C): an organic compound which has only one OH group or SH group in a molecule and includes at least one or more functional groups in the main chain of the molecule and also has at least one or more unsaturated groups in the molecule, and which is soluble to water or to alcohol having 1 to 4 of the number of carbons and (D): the cured catalyst of the epoxy group-containing silicon compound or the the partially hydrolyzed substance. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hard coat composition and a plastic lens using the same.

  Plastic lenses have the advantages of being lighter, safer, and rich in color variations than conventional glass lenses. Lens resin materials are rapidly increasing in refractive index, and lenses having a refractive index of 1.60 or higher are also on the market. However, on the other hand, since there is a drawback that scratches are extremely easily caused, a method of providing a silicone hard coat layer on the surface of a plastic lens is generally performed. Furthermore, in recent years, it has become possible to suppress surface reflection by the development of a low antireflection technology, and a lens provided with both a hard coat layer and antireflection has also been provided.

  Here, the silicone-based hard coat layer is composed mainly of a colloidal sol of metal oxide and a silane coupling agent which is an organosilicon compound. Conventionally, a silicon dioxide sol has been used exclusively as a metal oxide sol. However, the refractive index of the hard coat film is about 1.50.

  As described above, in recent years, the refractive index of plastic lenses has been increased, and lens materials having a refractive index of 1.67 or more have become mainstream, but such high refractive index lenses have a refractive index of about 1.50. When a hard coat film is applied, interference fringes due to a difference in refractive index between the lens material and the hard coat film are conspicuous, which is not preferable in appearance. As a technical means for solving this problem, silicon dioxide sol used in a silicone-based coating composition, such as JP-B-61-54331 and JP-B-63-37142, is made of Al having a high refractive index. , Ti, Zr, Sn, Sb, and the coating technology of replacing with a sol of inorganic oxide fine particles is disclosed. JP-A-2-264902 discloses a composite inorganic oxide sol of Ti and Ce, and JP-A-3-68901 discloses a sol obtained by treating a composite inorganic oxide sol of Ti, Ce and Si with organosilicon. Techniques used for the above are disclosed. JP-A-10-324846, JP-A-11-116843, and JP-A-11-310755 disclose a technique of using a composite inorganic oxide sol of Sn, Ti, and Zr as a coating composition. Japanese Patent Application Laid-Open No. 2001-122621 and Japanese Patent Application Laid-Open No. 2001-123115 disclose a technique in which a stable sol made of a modified composite metal oxide in which metal oxide fine particles such as Ti are coated with antimony pentoxide is used as a coating composition. It is disclosed.

Thus, the high refractive index of the hard coat film is generally a method using an inorganic oxide sol having a high refractive index. Specifically, one kind or two or more kinds of single fine particles and / or composite fine particles made of an oxide selected from Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. Many used sols are used. Among these, Ti oxide sol has a refractive index higher than that of other metal oxides, and therefore can be applied to a hard coat film having a higher refractive index. Also, the amount added can be small. As a result, it is possible to suppress the occurrence of film cracks due to a decrease in toughness due to the addition amount of the metal oxide sol in the hard coat film being too large. Thus, it can be said that titanium oxide is extremely effective as a high refractive index metal oxide.
Japanese Patent Publication No. 61-54331 Japanese Patent Publication No. 63-37142 JP-A-2-264902 Japanese Patent Laid-Open No. 3-68901 Japanese Patent Laid-Open No. 10-324846 JP 11-116843 A JP-A-11-310755 JP 2001-122621 A JP 2001-123115 A

  However, when titanium oxide is used as a hard coating material, it has been pointed out that there are the following problems. That is, titanium oxide is active when it receives ultraviolet energy (light), and has a characteristic of decomposing organic substances by a strong oxidative degradation power. As a result, the weather-resistant adhesion of the hard coat film became insufficient, and when an antireflection film was applied to the upper layer, it was easily bluish by ultraviolet rays. Further, in the case of a lens dyed with a hard coat film, there is also a disadvantage that the stain impregnated in the coat film is decomposed by the photoactive action of titanium oxide, resulting in poor weather fading.

  The present invention has been made in view of the above circumstances, and in a hard coating film mainly composed of a silane compound having a reactive group capable of being polymerized with a metal oxide sol, it has excellent transparency, dyeability and various durability, It is an object of the present invention to provide a hard coating agent that is excellent in various durability when an upper inorganic vapor deposition film is provided on the surface of the coating, and a plastic lens on which the hard coating agent is formed.

  In order to achieve the above object, the coating composition of the present invention comprises the following components (A) and (B) as main components and the following components (C) and (D) as essential addition components. It is characterized by that.

  Component (A) used in the present invention is a particle obtained by coating the surface of a metal oxide colloidal particle having an average particle diameter of 1 to 60 nm with a coating made of colloidal particles of acidic oxide. It is. As a specific example, a stable modified complex metal oxide in which the core complex metal oxide is composed of tin oxide, zirconium oxide and antimony pentoxide, and the outermost surface thereof is coated with antimony pentoxide and / or silicon dioxide. It is a thing. Here, the coating includes not only a completely covered state but also a scattered (scattered) state coating. A modified composite metal oxide sol in which this modified composite metal oxide is uniformly dispersed in a dispersion medium such as water, alcohols, or other organic solvents is used. Thereby, the above-mentioned problem of weather resistance and fading due to the photoactive action of titanium oxide can be improved. As the modified composite metal oxide, it is also possible to use a material obtained by treating the surface of the fine particles with an organosilicon compound or an amine compound in order to enhance dispersion stability in the coating liquid.

  Examples of the organosilicon compound used in this case include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. Further, after the treatment, it is preferable that the hydrolyzable group reacts with the —OH group of the fine particles, but there is no problem in stability even if a part of the hydrolyzable group remains. As amine compounds, alkylamines such as ammonium or ethylamine, triethylamine, diisopropylpropylamine, n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as pyridine, monoethanolamine, triethanolamine, etc. There are alkanolamines.

Subsequently, the component (B) is represented by the following general formula (1)
_{^{R 1 a R 2 b Si (}} OR 3) 4-a-b ... (1)
Or an hydrolyzate thereof.
Where the substituents R ¹ in the formula is an organic group containing an epoxy group having 2 to 8 carbon atoms, having for example glycidoxypropyl methyl group, an alkylene group having 1 to 4 carbon atoms such as glycidoxypropyl group Examples thereof include a glycidoxyalkyl group and an epoxycyclohexylalkyl group. R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkoxyalkyl group, or an acyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, and a phenyl group. R ³ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkoxyalkyl group or an acyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a methoxyethyl group, an ethoxyethyl group. , Butoxyethyl group, acetyl group, propionyl group and the like. a and b are integers satisfying 0 <a <2 and 0 ≦ b <2, respectively. The most preferable specific examples of the silicon compound satisfying the above formula (1) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane. Is mentioned.

  This (B) component may be used individually by 1 type, or may be used in mixture of 2 or more types. Moreover, although it can be used as it is, the partial hydrolyzate can also be used.

On the other hand, as a silane compound other than the above, a tetrafunctional silane represented by the following general formula (2) may be used in combination.
Si (OR ¹ ) ₄ (2)
The substituent R ¹ in the formula is an alkyl group or an alkoxyl group. As the most preferable specific examples of the silicon compound satisfying the above formula (2), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxymethylsilane, tetraethoxyethylsilane, tetrapropoxypropylsilane And tetrabutoxybutylsilane.

  In the present invention, the component (C) is used as a staining component for imparting dyeability to the film. The component (C) has only one OH group or SH group in the molecule, and -O-, -CO-O-, -S-, -CO-S-, and -CS in the molecular main chain. A compound that is soluble in water or an alcohol having 1 to 4 carbon atoms, which contains at least one or more functional groups selected from -S- and further has at least one unsaturated group in the molecule. is there. Examples of such compounds include diethylene glycol monoacrylate, tetraethylene glycol monoacrylate, tripropylene glycol monoacrylate, diethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, polyethylene glycol monomethacrylate, tripropylene glycol monomethacrylate, and polypropylene glycol monomethacrylate. .

  In addition, component (D) is added as a curing catalyst. The curing catalyst is used as needed for the purpose of shortening the time when forming a three-dimensional network structure of silanol or epoxy compound. Preferred curing catalysts include perchloric acid, ammonium perchlorate, magnesium perchlorate. Perchloric acids such as Li (I), Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Mn (III) Acetylacetonate, amine, glycine, etc. having a central metal atom such as La (III), Cr (III), Fe (III), Al (III), Ce (IV), Zr (IV), V (IV), etc. Amino acid, Lewis acid organic acid metal salt and the like. Although these can be arbitrarily used from these alone or in combination of two or more, the most preferred curing catalyst includes magnesium perchlorate and Al (III), Fe (III) acetylacetonate. .

  The solvent that can be included in the coating agent of the present invention includes lower alcohols such as methanol, ethanol, isopanol, butanol, isobutanol and diacetone alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve, cellosolve acetate, and butyl cellosolve. A mixture of these with a solvent such as esters, ketones, amides and aromatic compounds is also preferably used.

  Further, for the purpose of improving the coating property, each silicone surfactant and fluorine-based surfactant can be blended. Other anti-static agents, UV absorbers, antioxidants, disperse dyes, oil-soluble dyes, fluorescent dyes, pigments, photochromic compounds, light-resistant and heat-resistant stabilizers such as hindered amines and hindered phenols, etc. are added as necessary. It is also possible to improve the coating properties of the liquid and the coating performance after curing.

  The coating agent of the present invention is applied to various plastics. The applied plastic is not particularly limited, but polymethyl methacrylate, polycarbonate, polystyrene, polyester, polyurethane, polythiourethane, dimethacrylate polymer of halogenated bisphenol A and its polymer, urethane modified dimethacrylate polymer of halogenated bisphenol A And polymers thereof.

  In this case, the coating agent of the present invention can be applied to an optical product such as a plastic lens, and a protective coating layer can be provided by heat treatment. As a coating method, a normal coating method such as brush coating, roll coating, spray coating, flow coating, dip coating, or spin coating can be employed. Furthermore, although the curing conditions vary depending on the blending amount of the curing catalyst, etc., a desired cured film can be obtained by performing heat treatment at 80 to 150 ° C. for 0.1 to 10 hours.

  In general, the lens substrate is pretreated before coating. Examples of the pretreatment method include degreasing cleaning with acid alkali, surfactant processing, peeling / polishing processing with inorganic or organic fine particles, primer processing, plasma processing, ultrasonic cleaning, and the like. By performing the pretreatment, it is possible to improve adhesion and the like. As a film thickness of a cured film, 0.5-4 micrometers is suitable. That is, if the thickness is less than 0.5 μm, the hardness is lowered, and if it exceeds 4 μm, the surface smoothness may be impaired or cracks may easily occur.

Examples of the method for forming an antireflection film made of an inorganic substance in the present invention include a vacuum deposition method, an ion plating method, and a sputtering method. 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. 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 SiO 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 , MgO, and Y _2. Examples include O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like. These inorganic substances are used alone or in a mixture of two or more.

  The film obtained by applying and curing the hard coat composition obtained by the present invention on a high refractive index substrate suppresses the generation of interference fringes and has very high weather resistance and scratch resistance. In addition, it has good dyeability and excellent weather fading.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the following Example.

(1) Preparation of hard coat solution Weigh out 200 parts of γ-glycidoxypropyltrimethoxysilane in a beaker, add 50 parts of distilled water with stirring, and then hydrolyze to obtain hydrolyzate of organoalkoxysilane. It was adjusted.
The hydrolyzate is a modified composite metal oxide sol having a composite metal oxide composed of SnO ₂ —ZrO ₂ —Sb ₂ O ₅ as a nucleus (solid content 30%, methanol dispersion sol, manufactured by Nissan Chemical Co., Ltd., trade name) HX-305M5) 655 parts, ethanol 25 parts and diacetone alcohol 25 parts were gradually added. Next, 10 parts of acetylacetone aluminum (III) was added as a catalyst and stirred for 2 hours. Thereafter, 30 parts of polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd., trade name: Blenmer PE200) was added while stirring the mixed solution. Furthermore, 0.3 parts and 0.2 parts of silicone surfactants (trade names Paintad 32 and Paintad 57, manufactured by Dow Corning Asia Co., Ltd.) were added as leveling agents and stirred for 1 hour. The above mixture was aged for 24 hours and filtered to prepare a hard coat composition.
(2) Application and curing of hard coat film The coating solution thus obtained was applied by a dipping method (pulling speed 200 mm / min) and cured under conditions of 120 ° C. × 2 hours. For the substrate, plastic lenses made using MR8 and MR6 (both manufactured by Mitsui Chemicals) monomers having a refractive index of 1.60 were used, and pre-immersed in an alkaline aqueous solution (30 wt% KOH) for 3 minutes. Application was performed later.
(3) Formation of anti-reflection film On the lens with hard coat obtained by the operation of (2), an anti-reflection film composed of silicon oxide and zirconium oxide, which are inorganic substances, is coated in a multilayer by vacuum deposition method, and with an anti-reflection film A lens was produced.
(4) Evaluation Each of the obtained lens with hard coat and lens with antireflection film was evaluated as follows. The results are shown in Table 1.
a) Appearance (interference fringes)
The appearance of interference fringes was visually confirmed under a fluorescent lamp.
b) Dyeability A BPI Gray of Brain Power Inc (USA) diluted to 10 wt% with distilled water is heated to 90 ° C., and a lens with a hard coat layer is immersed in this aqueous solution for 5 minutes. Thereafter, the lens was taken out, washed with water and dried, and the total light transmittance of the obtained dyed lens was measured.
c) After cross-cutting 100 squares at 1 mm intervals on the adhesive coating layer, and sticking adhesive tape (Nichiban Co., Ltd., trade name cello tape CT-24) on the cross-cut part, the adhesive tape is rapidly applied. Repeat the process of peeling 5 times. Thereafter, the presence or absence of peeling of the cured film was examined.
○: No peeling △: Partial peeling ×: Whole peeling d) Scratch-resistant bonster steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.) was used to rub 10 reciprocating lens surfaces while applying a load of 500 g to the lens surface. Then, the difficulty of scratching was visually determined.
A: No scratches B: Some scratches C: Scratches D: Severe scratches E: Scratches to the substrate e) Impact resistant hard sphere (16 g) from a height of 127 cm It was judged whether it was dropped in the center of the slab and cracked.
○: not cracked △: cracked ×: penetrated (cracked)
f) 20 hours of irradiation (irradiation distance 70 mm) was performed with a fading mercury lamp (Toshiba H400-E), and the color change before and after the test was visually confirmed. Judgment criteria are represented by rank A for the small change stage and rank B for the larger stage.
g) Weather-resistant adhesion Using a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.), confirming adhesion for each 60-hour irradiation up to 300 hours for lenses with a hard coat, up to 420 hours for lenses with an antireflection coating did. The confirmation of the adhesion was performed in the same manner as the c) adhesion evaluation method.
○: No peeling Δ: Partial peeling ×: Full peeling [Comparative Example 1]

(1) Preparation of hard coat solution Weigh out 200 parts of γ-glycidoxypropyltrimethoxysilane in a beaker, add 50 parts of distilled water with stirring, and then hydrolyze to obtain hydrolyzate of organoalkoxysilane. It was adjusted.
In the hydrolyzate, 520 parts of a composite metal oxide sol composed of SnO ₂ —TiO ₂ —ZrO ₂ (solid content 30%, methanol dispersion sol, manufactured by Nissan Chemical Co., Ltd., trade name: HIT-30M) and ethanol 92.5 And 92.5 parts of diacetone alcohol were gradually added. Next, 10 parts of acetylacetone aluminum (III) was added as a catalyst and stirred for 2 hours. Thereafter, 30 parts of polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd., trade name: Blenmer PE200) was added while stirring the mixed solution. Furthermore, 0.3 parts and 0.2 parts of silicone surfactants (trade names Paintad 32 and Paintad 57, manufactured by Dow Corning Asia Co., Ltd.) were added as leveling agents and stirred for 1 hour. The above mixture was aged for 24 hours and filtered to prepare a hard coat composition.
(2) Hereinafter, the formation method and evaluation method of the hard coat film and the antireflection film were carried out in the same manner as in Example 1. The results are shown in Table 1.
[Comparative Example 2]

(1) Use a hard coat composition (trade name: C-410, manufactured by Nippon ALC Co., Ltd.) to which a composite metal oxide sol composed of TiO ₂ —Fe ₂ O ₃ —SiO ₂ is added as component (A). .
(2) Hereinafter, the formation method and evaluation method of the hard coat film and the antireflection film were carried out in the same manner as in Example 1. The results are shown in Table 1.

Claims (4)

A hard coat composition comprising the following component (A) and component (B) as main components and the following component (C) and component (D) as essential addition components.
Component (A): a modified composite metal oxide composed of a composite metal oxide composed of tin oxide, zirconium oxide, and antimony pentoxide, and having the outermost surface covered with antimony pentoxide and / or silicon dioxide.
Component (B): Epoxy group-containing silicon compound or a partial hydrolyzate thereof.
Component (C): having only one OH group or SH group in the molecule, and -O-, -CO-O-, -S-, -CO-S-, and -CS-S in the molecular main chain An organic compound soluble in water or an alcohol having 1 to 4 carbon atoms, containing at least one or more functional groups selected from-and having at least one unsaturated group in the molecule.
Component (D): a curing catalyst for an epoxy group-containing silicon compound or a partial hydrolyzate thereof. A plastic lens comprising a coating film formed on the surface of the hard coat composition according to claim 1. A plastic lens obtained by dyeing the coating film according to claim 2. 4. The plastic lens according to claim 2, wherein an antireflection film is formed on the hard coat film.