JP2007188103A - Plastic lens and method for manufacturing plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic lens and a method for manufacturing a plastic lens having excellent weather resistance while suppressing degradation of an antireflection film comprising an organic thin film as much as possible. <P>SOLUTION: The plastic lens comprises a plastic lens base, a hard coat layer on the plastic lens base, and an antireflection film comprising an organic thin film on the hard coat layer, wherein the hard coat layer is formed from a coating composition that contains titanium oxide having a rutile crystalline structure as inorganic oxide fine particles. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a plastic lens having an antireflection film composed of an organic thin film and a method for manufacturing the same.

  Plastic lenses are widely used in the field of spectacle lenses because they are lighter than glass lenses, have good moldability, processability, and dyeability, are hard to break and have high safety. However, since the plastic lens is soft and easily damaged, a hard coating layer having a high hardness is provided on the surface of the plastic lens to improve the scratch resistance. Furthermore, an antireflection film in which an inorganic substance is deposited on the surface of the hard coat layer may be provided for the purpose of preventing surface reflection. Due to the surface treatment layer of the plastic lens, the quality of the plastic lens is high.

  In recent years, high refractive index materials have been developed in order to reduce the thickness and weight of plastic lenses. Currently, urethane-based plastic lenses and episulfide-based plastic lenses are widely used as high refractive index plastic spectacle lens materials. In Patent Document 1 shown below, as an optical material excellent in the balance between a high refractive index and a high Abbe number, it has one or more disulfide bonds (SS) in the molecule, and an epoxy group and / or a thioepoxy group. Compounds have been proposed. In Patent Documents 2 and 3 shown below, a plastic lens having a thiourethane structure, which is obtained by a reaction between a polyisocyanate compound and a compound having an active hydrogen group such as a polythiol compound, is proposed. Patent Document 4 proposes a compound having two or more mercapto groups in the molecule.

  The hard coat layer formed on the plastic lens substrate having such a high refractive index is required to have the same high refractive index in order to suppress the generation of interference fringes. The hard coat layer is generally formed as a coating film by applying and curing a coating composition containing an organosilicon compound containing sol-like metal oxide fine particles. In order to make the hard coat layer have a high refractive index, as shown in Patent Document 5 and Patent Document 6, a method using metal oxide fine particles containing titanium dioxide having a high refractive index is employed. Furthermore, as shown in Patent Document 7 and Patent Document 8, a method of using a rutile-type titanium oxide sol as a coating composition, or a core particle of a composite solid solution oxide having a rutile-type structure containing oxides of titanium and tin. There has been proposed a method of using, on the surface, composite oxide fine particles formed by coating a composite oxide of silicon oxide and zirconium and / or aluminum oxide.

On the other hand, in recent years, as an antireflection film formed on such a high refractive index hard coat layer, a coating composition containing low refractive index silica fine particles as disclosed in Patent Document 9 is applied. A technique for forming an antireflection film composed of an organic thin film having a refractive index lower by 0.10 or more than the refractive index of the hard coat layer and a film thickness of 50 nm to 150 nm has been developed.
JP 11-322930 A Japanese Patent Publication No. 4-58489 JP-A-5-148340 JP 2001-342252 A JP-A-1-301517 JP-A-2-263902 JP-A-2-255532 JP 2000-204301 A JP 2003-222703 A

  However, such an antireflection film composed of an organic thin film is excellent in heat resistance because it has a thermal expansion coefficient close to that of the underlying hard coat layer, but is composed of an inorganic vapor deposition film because it is an organic thin film and very thin. Unlike the antireflection film, it is recognized that it is strongly influenced by the underlying hard coat layer. That is, if the hard coat layer is inferior in weather resistance and light resistance and deteriorates even slightly due to aging, the antireflection film composed of an organic thin film may be deteriorated.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a plastic lens excellent in weather resistance and light resistance in which deterioration of an antireflection film composed of an organic thin film is suppressed as much as possible. To do. Moreover, an object of this invention is to provide the manufacturing method of the plastic lens which can manufacture the plastic lens excellent in this weather resistance and light resistance.

In order to achieve the above object, first, the present invention provides a plastic lens substrate, a hard coat layer formed on the plastic lens substrate, and an antireflection film formed on the hard coat layer. The hard coat layer is a coating film formed from a coating composition containing at least the following components (A) and (B), and (A) an average particle diameter of 1 to 200 nm: Inorganic oxide fine particles containing titanium oxide having a rutile-type crystal structure of (B), an organosilicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ has a polymerizable reactive group) An organic group having 2 or more carbon atoms, and X ¹ represents a hydrolyzable group.), The antireflection film has a refractive index lower by 0.10 or more than the refractive index of the hard coat layer, and 50nm Providing a plastic lens, which is a film thickness organic thin of 150 nm.

  Secondly, in the first plastic lens according to the present invention, the inorganic oxide fine particles have an average particle diameter having a rutile crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. A plastic lens comprising a composite oxide having a thickness of 1 to 200 nm is provided.

  Thirdly, in the second plastic lens according to the present invention, the inorganic oxide fine particles have a rutile-type crystal structure (i) titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. There is provided a plastic lens comprising a core particle surface of a composite oxide coated with a coating layer of (ii) a composite oxide composed of silicon oxide and zirconium oxide and / or aluminum oxide.

Since the inorganic oxide fine particles blended in the hard coat layer contain titanium oxide, the refractive index of the hard coat layer can be increased. In addition, since titanium oxide has a rutile crystal structure, anatase-type titanium oxide is active when it receives light (ultraviolet) energy, and has a characteristic of decomposing organic matter by strong oxidative decomposition power. Unlike this, such photoactivity is low. This is because, when irradiated with light (ultraviolet rays), electrons in the valence band of titanium oxide are excited to form OH free radicals and HO ₂ free radicals, which decompose organic substances by this strong oxidizing power. This is because rutile titanium oxide is more stable in terms of thermal energy, and the amount of free radicals produced is extremely small. Therefore, since the hard coat layer containing titanium oxide having a rutile crystal structure is excellent in weather resistance and light resistance, there is no possibility that the anti-reflection film composed of the organic thin film is altered by the hard coat layer, and the weather resistance. It becomes a plastic lens with excellent properties and light resistance.

  The rutile type titanium oxide used in the present invention includes inorganic oxide fine particles containing a composite oxide having a rutile type crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. However, since the free radicals are also generated in this rutile type titanium oxide, the surface of the core particles made of the composite oxide is covered with a composite oxide coating layer made of silicon oxide and zirconium oxide and / or aluminum oxide. It is desirable to use a coated one. This is because the free radicals generated in the core particles have the same strong oxidizing power but are unstable, and therefore disappear due to the catalytic action of the coating layer while passing through the coating layer. It is. Thereby, since the hard coat layer in which such inorganic oxide fine particles are blended is excellent in weather resistance and light resistance, there is no possibility that the antireflection film composed of an organic thin film is altered by the hard coat layer, It becomes a plastic lens with excellent weather resistance and light resistance.

Fourth, the present invention provides the plastic lens according to any one of the first to third aspects, wherein the antireflection film has the following (F) component and (G) component (F) general formula: R ⁵ _r R ⁶ _q SiX ⁵ _An organosilicon compound represented by _4-q-r , wherein R ⁵ is an organic group having a polymerizable reactive group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, and X ⁵ is a hydrolyzable group. Q is 0 or 1, and r is 0 or 1.) (G) An organic thin film formed from a coating composition containing silica-based fine particles having an average particle diameter of 1 to 150 nm. Provide plastic lens. The organosilicon compound of the F component functions as a binder for the organic thin film, and the silica-based fine particles are components for adjusting the refractive index.

Fifth, the present invention provides the plastic lens according to the fourth plastic lens, wherein the silica-based fine particles have an internal cavity.
Since the refractive index of the antireflection film can be lowered by using silica-based fine particles having internal cavities, the antireflection effect can be enhanced by increasing the refractive index difference from the hard coat layer.

  Sixth, the present invention is characterized in that, in the fifth plastic lens, the silica-based fine particles have an average particle diameter of 20 to 150 nm and a refractive index is in the range of 1.16 to 1.39. Provide plastic lens.

Seventh, in the plastic lens according to any one of the first to sixth aspects, the coating composition for forming the hard coat layer further contains (C) a polyfunctional epoxy compound as the component (C). A plastic lens is provided.

  The polyfunctional epoxy compound can improve the adhesion of the hard coat layer to the plastic substrate, improve the water resistance of the hard coat layer, and further impart flexibility. The antireflection film composed of an inorganic vapor deposition film functions as a protective film for the hard coat layer. However, since the antireflection film composed of an organic thin film is extremely thin, the hard coat layer needs to have water resistance. Moreover, by giving a softness | flexibility, it can suppress that a hard-coat layer generate | occur | produces a crack and can improve a weather resistance combined with water resistance.

Eighthly, in the plastic lens according to any one of the first to seventh aspects of the present invention, the coating composition for forming the hard coat layer may further include (D) a component represented by the general formula: R ² _n SiX. ^{2 An} organosilicon compound represented by _4-n (wherein R ² represents a hydrocarbon group having 1 to 3 carbon atoms, X ² represents a hydrolyzable group, and n represents 0 or 1). A plastic lens is provided.
By blending this organosilicon compound, the hard coat layer can be further improved in durability, particularly scratch resistance.

Ninthly, in the plastic lens according to any one of the first to eighth aspects, the coating composition for forming the hard coat layer may further include (E) a component represented by the general formula: X ³ _{3− ^{m -Si (R 3 m) -Y}} -Si (R 4 m) -X 4 3-m represented by disilane compound (wherein, ^{R 3} and ^{R 4} are a hydrocarbon group having 1 to 6 carbon atoms X ³ and X ⁴ represent a hydrolyzable group, Y represents an organic group containing a carbonate group or an epoxy group, and m represents 0 or 1. Provide plastic lens.
By mix | blending this disilane compound, the cure rate at the time of forming a hard-coat layer from the composition for coating can be improved.

Tenthly, the present invention provides a hard coat layer forming step of forming a hard coat layer from a coating composition containing at least the following components (A) and (B) on a plastic lens substrate; ) Inorganic oxide fine particles containing titanium oxide having a rutile crystal structure with an average particle size of 1 to 200 nm, (B) an organosilicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ is An organic group having 2 or more carbon atoms having a polymerizable reactive group, and X ¹ represents a hydrolyzable group.), 0.10 or more lower than the refractive index of the hard coat layer on the hard coat layer An antireflection film forming step of forming an organic thin film having a refractive index and a film thickness of 50 nm to 150 nm is provided.

  In the eleventh aspect of the present invention, in the tenth method for producing a plastic lens, the inorganic oxide fine particles have a rutile crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. A method for producing a plastic lens comprising a composite oxide having an average particle diameter of 1 to 200 nm is provided.

The twelfth aspect of the invention relates to the eleventh plastic lens manufacturing method, wherein the inorganic oxide fine particles are (i) a rutile type crystal composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. It is characterized in that the surface of the core particle of the composite oxide having a structure is covered with (ii) a composite oxide coating layer composed of silicon oxide and zirconium oxide and / or aluminum oxide.
Thereby, there is no possibility that the antireflection film composed of the organic thin film is deteriorated by the hard coat layer, and a plastic lens excellent in weather resistance and light resistance can be manufactured.

In the thirteenth aspect of the present invention, in the method for producing a plastic lens according to any one of the tenth to twelfth aspects, the organic thin film formed in the antireflection film forming step comprises the following components (F) and (G): ) General formula: Organosilicon compound represented by R ⁵ _r R ⁶ _q SiX ⁵ _4-qr (wherein R ⁵ is an organic group having a polymerizable reactive group, R ⁶ is a C 1-6 carbon atom) A hydrocarbon group, X ⁵ is a hydrolyzable group, q is 0 or 1, and r is 0 or 1.),
(G) Provided is a method for producing a plastic lens, which is formed using a coating composition containing silica-based fine particles having an average particle diameter of 1 to 150 nm.

  The present invention provides, in a fourteenth aspect, the plastic lens manufacturing method according to the thirteenth plastic lens manufacturing method, wherein the silica-based fine particles have an internal cavity.

  The fifteenth aspect of the present invention is the method for producing a plastic lens according to any one of the thirteenth to fourteenth aspects, wherein the silica-based fine particles have an average particle diameter of 20 to 150 nm and a refractive index of 1.16 to 1.39. A method for producing a plastic lens is provided.

  Hereinafter, embodiments of the plastic lens and the plastic lens manufacturing method of the present invention will be described, but the present invention is not limited to the following embodiments.

  The plastic lens of the present invention has a structure having a plastic lens substrate, a hard coat layer formed on the plastic lens substrate, and an antireflection film formed on the hard coat layer. There is a feature in the combination of antireflection film. A primer layer may be provided between the plastic lens substrate and the hard coat layer.

  The plastic lens substrate may be either a high refractive index material that can be used at present or a high refractive index material that will be developed in the future. The refractive index of the material is preferably 1.60 or more. As a high refractive index material that can be used at present, as an optical material excellent in the balance between a high refractive index and a high Abbe number, it has one or more disulfide bonds (SS) in the molecule and has an epoxy group and / or a thioepoxy. There are compounds having groups. In addition, there is a plastic lens having a thiourethane structure obtained by a reaction between a poly (thio) isocyanate compound and a compound having an active hydrogen group such as a polythiol compound. In addition, there are compounds having two or more mercapto groups in the molecule.

  Examples of the compound having one or more disulfide bonds (SS) in the molecule and having an epoxy group and / or a thioepoxy group include bis (2,3-epoxypropyl) disulfide and bis (2,3 -(Thiothiopropyl) disulfide (thio) epoxy compound having one disulfide bond in the molecule, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, Bis (6,7-epithio-3,4-dithiaheptane) sulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epi Thiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethylthio) Examples include (thio) epoxy compounds having two or more disulfide bonds in the molecule, such as -4-thiahexane and 1,2,3-tris (2,3-epithiopropyldithio) propane. These 1 type can be used individually or in combination of 2 or more types.

  Examples of the compound having two or more iso (thio) cyanate groups in the molecule include aliphatic polyisocyanate compounds such as ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, An alicyclic polyisocyanate compound such as isophorone diisocyanate, an aromatic polyisocyanate compound such as xylylene diisocyanate, a sulfur-containing aliphatic polyisocyanate compound such as bis (isocyanate methyl) sulfide, and 2-isocyanate phenyl-4-isocyanate phenyl sulfide. Aromatic disulfide polyisocyanate compounds, aromatic disulfide polyisocyanate compounds such as bis (4-isocyanatophenyl) disulfide, 2,5 Sulfur-containing alicyclic polyisocyanate compounds such as diisocyanate tetrahydrothiophene, aromatic polyisothiocyanate compounds such as 1,2-diisothiocyanate benzene, aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanate ethane, thiobis ( Sulfur-containing aliphatic polyisothiocyanate compounds such as 3-isothiocyanate propane) can be exemplified.

  The polythiol having two or more thiol groups in one molecule that undergoes addition reaction with these epoxy groups, thioepoxy groups, and iso (thio) cyanate groups includes two or more mercapto groups in the molecule represented by the following general formula. A polythiol compound having a group can be preferably used. The resin obtained using this polythiol compound is excellent in high refractive index, impact resistance, and heat resistance.

R- (SCH ₂ SH) _t
In the above formula, R represents an organic residue excluding an aromatic ring. The organic residue is selected from linear or branched aliphatic, alicyclic, heterocyclic, or linear or branched aliphatic, alicyclic or heterocyclic having a sulfur atom in the chain. One or more of these may be mentioned. In the formula, t is an integer of 1 or more, and one or more, preferably two or more mercaptomethylthio groups are required in one molecule. Moreover, you may have mercapto groups other than a mercaptomethylthio group.

  Specific examples of the polythiol compound represented by the above general formula include 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3- Mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2,5 8-trithianonane, 3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3- Mercaptomethyl-1,6-dimercapto-2,5-dithiahexane, 3-mercaptomethylthio-1,5-dimercapto- -Thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,4,8,11-tetramercapto-2,6,10- Trithiaundecane, 1,4,9,12-tetramercapto-2,6,7,11-tetrathiadecane, 2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia- 1,7-heptanedithiol, 2,3,5,6,8,9-hexathia-1,10-decanedithiol, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis ( Mercaptomethylthio) -1,3-dithiane, 2-bis (mercaptomethylthio) methyl-1,3-dithietane, 2- (2,2-bis (mercaptomethylthio) ethyl) Include polythiol compounds such as 1,3-dithietane is, may be used each alone, or may be used in combination of two or more.

As other polythiols, for example, 4-mercaptomethyl-3,6-dithio-1,8-octanedithiol represented by the following formula (1), pentaerythritol tetrakis (3-mercaptopropio represented by the following formula (2) Nate), and tetrathiol represented by the following general formula (3).

Specific examples of the tetrathiol represented by the general formula (3) include compounds (A) to (G) having the following structural formula.

  Other polythiols include, for example, di (2-mercaptoethyl) ether, 1,2-ethanedithiol, 1,4-butanedithiol, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), penta Erythritol tetrakis (2-mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoacetate), 1,2-dimercaptobenzene, 4-methyl-1,2 -Dimercaptobenzene, 3,6-dichloro-1,2-dimercaptobenzene, 3,4,5,6-tetrachloro-1,2-dimercaptobenzene, O-xylylenedithiol, m-xylylenedithiol, p-xylylenedithiol, Beauty 1,3,5-tris (3-mercaptopropyl) isocyanurate and the like.

A polymerizable composition for producing a plastic lens substrate can be prepared by mixing a compound having a (thio) epoxy group or a poly (thio) isocyanate compound and a polythiol compound. It is preferable to mix a polymerization catalyst in the polymerizable composition. There are no particular restrictions on the polymerization catalyst for the (thio) epoxy group, but specific examples include tertiary amines such as dimethylbenzylamine, dimethylcyclohexylamine, diethylethanolamine, dibutylethanolamine, tridimethylaminomethylphenol, and ethyl. Examples include imidazoles such as methylimidazole. Specific examples of isocyanate and isothiocyanate polymerization catalysts include amine compounds such as ethylamine, ethylenediamine, triethylamine, and tributylamine, dibutyltin dichloride, dimethyltin dichloride, and the like.
Moreover, a light stabilizer, antioxidant, etc. can be mixed with a polymeric composition other than a polymerization catalyst as needed.

  When producing a plastic lens, casting polymerization is usually used. The side surfaces of two circular glass molds arranged opposite to each other are fixed with an adhesive tape or a gasket, and a mold in which a gap between the glass molds is sealed is assembled. The mold is filled with a polymerizable composition, and heat energy or light It can be polymerized and cured by energy to obtain a plastic lens substrate having a high refractive index.

The plastic lens of the present invention has a structure in which a hard coat layer is provided on such a high refractive index plastic lens substrate. The hard coat layer in the plastic lens of the present invention comprises at least the following (A) component and (B) component (A) inorganic oxide fine particles containing titanium oxide having a rutile crystal structure with an average particle size of 1 to 200 nm,
(B) an organic silicon compound represented by the general formula: R ¹ SiX ¹ ₃ ;
(In the formula, R ¹ represents an organic group having 2 or more carbon atoms having a polymerizable reactive group, and X ¹ represents a hydrolyzable group.)
It is the coating film formed from the composition for coating containing this.

More specifically, the hard coat layer in the plastic lens of the present invention comprises at least the following component (A) and component (B) (A) titanium oxide and tin oxide, or rutile comprising titanium oxide, tin oxide and silicon oxide. Inorganic oxide fine particles having an average particle diameter of 1 to 200 nm, including a composite oxide having a crystal structure of a type,
(B) the general formula: an organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein, R ¹ represents the number of carbon atoms having a polymerizable reactive group represents an organic group having two or more, X ¹ is a hydrolyzable group Represents)
It is the coating film formed from the composition for coating containing this.

  The hard coat layer preferably has a refractive index of about ± 0.03 of the refractive index of the plastic lens substrate having a high refractive index in order to suppress interference fringes. The method of using inorganic oxide fine particles having a high refractive index is generally used to increase the refractive index of the hard coat layer. Specifically, one or more metal oxides (including mixtures thereof) selected from Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti, In addition, colorless and transparent inorganic oxide fine particles made of a complex oxide containing two or more metals are often used. Among these, inorganic oxide fine particles containing titanium oxide have a relatively high refractive index and therefore have many advantages. First, since it has a high refractive index, it can cope with the design of a hard coat film that is expected to require a higher refractive index setting in the future. Further, when the target refractive index of the hard coat film is the same, the amount of addition is smaller than other metal oxide fine particles. As a result, the occurrence of a film crack failure during the curing reaction due to a decrease in toughness due to the large amount of metal oxide added to the hard coat film can be suppressed to a low level. Thus, it can be said that the inorganic oxide fine particle containing titanium oxide is extremely effective as a high refractive index metal oxide.

  However, when inorganic oxide fine particles containing titanium oxide are used as a metal oxide for a hard coat film, there are the following problems. Titanium oxide is active when it receives light (ultraviolet light) energy, and has a property of decomposing organic matter by a strong oxidative decomposition power (hereinafter referred to as photoactivity). As a result, when titanium oxide is contained as a constituent of the hard coat film, organic substances such as a silane coupling agent, which is another main constituent, are decomposed by photoactivity. Specifically, the hard coat film becomes cloudy after long-term use, and eventually proceeds to hard coat film cracks and film peeling, which is not preferable in terms of durability.

  As a measure to suppress the photoactivity of such inorganic oxide fine particles containing titanium oxide, absorption of ultraviolet rays with a metal oxide of Ce or Fe having an ultraviolet absorbing ability on the wavelength side higher than the ultraviolet absorption wavelength of titanium oxide. By using the inorganic oxide fine particles mixed and / or complex oxide metal oxide having a shielding effect that does not allow ultraviolet rays to reach titanium oxide, or trap the free radicals generated by ultraviolet irradiation There is a method using an oxide such as Al or Zr that can be formed and an oxide such as Si that can guard the free radical from coming out with a dense film. Thereby, organic substances, such as a silane coupling agent apply | coated on the said hard-coat layer, become difficult to decompose | disassemble. However, inorganic oxide fine particles containing titanium oxide, particularly composite oxide fine particles containing titanium oxide, have the advantage of increased weather resistance, but have the disadvantage of lowering the refractive index compared to the case of titanium oxide alone.

  There are three types of crystal forms of titanium oxide: anatase, rutile, and brookite. Among these, the anatase type and the rutile type are used industrially, and the brookite type is limited to academic research because of its unstable crystal structure.

  Titanium oxide most used industrially is of the rutile type, and the amount of anatase type titanium oxide used is about 1/10 that of rutile type titanium oxide. Anatase type titanium oxide is used where whiteness is the most important item and photoactivity can be ignored, and rutile type titanium oxide is used when low photoactivity is the most important item.

In the present invention, by using inorganic oxide fine particles containing titanium oxide selectively having a rutile crystal structure, various problems caused by titanium oxide photoactivity could be improved. By making the crystal structure a rutile type rather than an anatase type, the weather resistance is further improved, and the refractive index is higher in the rutile type crystal than in the anatase type crystal. There is an advantage that it can be obtained. Unlike photocatalytic activity, anatase-type titanium oxide is active when it receives light (ultraviolet light) energy, and has a characteristic of decomposing organic matter by a strong oxidative degradation power. Such photoactivity is low. This is because, when irradiated with light (ultraviolet rays), electrons in the valence band of titanium oxide are excited to form OH free radicals and HO ₂ free radicals, which decompose organic substances by this strong oxidizing power. This is because rutile titanium oxide is more stable in terms of thermal energy, and the amount of free radicals produced is extremely small. Therefore, since the hard coat layer containing titanium oxide having a rutile crystal structure is excellent in weather resistance and light resistance, there is no possibility that the anti-reflection film composed of the organic thin film is altered by the hard coat layer, and the weather resistance. It becomes a plastic lens with excellent properties and light resistance.

In order to obtain rutile-type titanium oxide, it is preferable to use a composite oxide with tin oxide and a composite oxide with silicon oxide added. These composite oxides containing titanium oxide have a rutile crystal structure. In this case, the amount of titanium oxide and tin oxide contained in the inorganic oxide fine particles, when converting the titanium oxide TiO _2, by converting the tin oxide SnO _2, the weight ratio of TiO 2 / SnO ₂ is 1 / It is desirable to be in the range of 3-20 / 1, preferably 1.5 / 1-13 / 1. Here, if the amount of SnO ₂ is made smaller than the above range, the crystal structure shifts from the rutile type to the anatase type, resulting in a mixed crystal containing the rutile type crystal and the anatase type crystal, Or it becomes an anatase type crystal. Further, when the amount of SnO ₂ is increased from the above range, a rutile crystal structure is present between the rutile crystal of titanium oxide and the rutile crystal of tin oxide. Show different crystal structures, and the refractive index of the resulting inorganic oxide fine particles also decreases.

Further, the titanium oxide contained in the inorganic oxide fine particles, the amount of tin oxide and silicon oxide are translated titanium oxide TiO _2, converting the tin oxide SnO _2, when converted to silicon oxide SiO ₂ The weight ratio of TiO ₂ / SnO _{2 is in} the range of 1/3 to 20/1, preferably 1.5 / 1 to 13/1, and the weight ratio of (TiO ₂ + SnO ₂ ) / SiO ₂ is 50 / It is desirable to be in the range of 45 to 99/1, preferably 70/30 to 98/2. The content of SnO ₂ is the same as in the above case, but the stability and dispersibility of the resulting inorganic oxide fine particles can be improved by including silicon oxide therein. Here, when the amount of SiO ₂ is made smaller than the above range, the stability and dispersibility are lowered, and when the amount of SiO ₂ is made larger than the above range, the stability and dispersion are reduced. However, it is not preferable because the refractive index of the resulting inorganic oxide fine particles is lowered.

  However, the free radicals are also generated in this rutile titanium oxide. The same applies to the case where inorganic oxide fine particles containing two or more composite oxides containing titanium oxide are used as the inorganic oxide fine particles containing titanium oxide.

Therefore, the hard coat layer in the plastic lens of the present invention has a rutile crystal structure composed of at least the following component (A) and component (B) (A) titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. Inorganic oxide fine particles having an average particle diameter of 1 to 200 nm, including those in which the surface of the core particles of the composite oxide is coated with a composite oxide coating layer composed of silicon oxide and zirconium oxide and / or aluminum oxide,
(B) the general formula: an organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein, R ¹ represents the number of carbon atoms having a polymerizable reactive group represents an organic group having two or more, X ¹ is a hydrolyzable group Represents.)
It is preferable to make it the coating film formed from the coating composition containing this.

As mentioned earlier, when titanium oxide is irradiated with light (ultraviolet rays), electrons in the valence band of titanium oxide are excited to produce OH free radicals and HO ₂ free radicals. Although it decomposes, rutile type titanium oxide is more stable in terms of thermal energy than anatase type titanium oxide, so that the amount of free radicals produced is extremely small. However, since the free radicals are also generated in this rutile type titanium oxide, the surface of the core particles made of the composite oxide is covered with a composite oxide coating layer made of silicon oxide and zirconium oxide and / or aluminum oxide. It is desirable to use a coated one. This is because the free radicals generated in the core particles have the same strong oxidizing power but are unstable, and therefore disappear due to the catalytic action of the coating layer while passing through the coating layer. It is.

  The contents of titanium oxide and tin oxide or titanium oxide, tin oxide and silicon oxide contained in the core particles are the same as in the above case, but the silicon oxide, zirconium oxide and oxide contained in the coating layer are the same. The aluminum content is preferably selected from the following range.

(A) When the coating layer is formed of a composite oxide of silicon oxide and zirconium oxide, the amount of silicon oxide and zirconium oxide contained in the coating layer is calculated by converting silicon oxide to SiO ₂ and converting zirconium oxide to ZrO. When converted to ₂ , it is desirable that the weight ratio of SiO ₂ / ZrO ₂ is in the range of 50/50 to 99/1, preferably 65/35 to 90/10. Here, when the amount of ZrO ₂ exceeds the above range, the number of Zr atoms capable of trapping free radicals increases. However, since the coating layer is distorted and a dense coating layer cannot be formed, it is generated by the nuclear particles. When free radicals come out on the surface of the inorganic oxide fine particles, leading to oxidation of organic substances, and when the amount of ZrO ₂ is less than the above range, a dense coating layer is easily formed, but traps free radicals. Since there are few Zr atoms to do, the free radical produced | generated by the said nucleus particle will come out on the surface of the said inorganic oxide fine particle, and will cause the oxidation of organic substance.
(B) When the coating layer is formed of a composite oxide of silicon oxide and aluminum oxide, the amount of silicon oxide and aluminum oxide contained in the coating layer is calculated by converting silicon oxide to SiO ₂ and converting aluminum oxide to Al. when converted to ₂ O _3, the weight ratio of 60 / 40-99 / 1 of SiO 2 / _Al 2 _{O 3,} preferably is desirably in the range of 68 / 32-95 / 5. Here, when the amount of Al ₂ O ₃ exceeds the above range, Al atoms capable of trapping free radicals increase, but since a dense coating layer cannot be formed, free radicals generated in the core particles are When it comes out on the surface of the oxide fine particles and causes oxidation of organic matter, and when the amount of Al ₂ O ₃ is less than the above range, a dense coating layer is easily formed, but for trapping free radicals. Since there are few Al atoms, the free radical produced | generated by the said nucleus particle will come out on the surface of the said inorganic oxide fine particle, and will cause the oxidation of organic substance.
(C) When the coating layer is formed of a composite oxide of silicon oxide, zirconium oxide and aluminum oxide, the amount of silicon oxide, zirconium oxide and aluminum oxide contained in the coating layer is calculated by converting silicon oxide to SiO ₂ and, converting the zirconium oxide ZrO _2, when converted to aluminum oxide _{Al 2 O 3, SiO 2 /} (ZrO 2 + Al 2 O 3) ratio by weight of 98 / 2-6 / 4, preferably 95 / It is desirable to be in the range of 5-7 / 3. Here, if the total amount of ZrO ₂ and Al ₂ O ₃ is larger than the above range, the total amount of Zr atoms and Al atoms that can trap free radicals increases, but a dense coating layer cannot be formed. When free radicals generated in the core particles come out on the surface of the inorganic oxide fine particles, leading to oxidation of organic matter, and when the total amount of ZrO ₂ and Al ₂ O ₃ is less than the above range, a dense coating is formed. Although the layer can be easily formed, since the total amount of Zr atoms and Al atoms for trapping free radicals is small, free radicals generated by the core particles come out on the surface of the inorganic oxide fine particles, and oxidize organic matter. Will be invited.
In addition, the thickness of the coating layer is desirably in the range of 0.02 to 2.27 nm, preferably 0.16 to 1.14 nm, from the above viewpoint.

  The composite oxide constituting the core particles referred to here is a composite solid solution oxide (including a doped composite oxide) and / or a composite oxide cluster comprising titanium oxide and tin oxide, or titanium oxide, oxidation. It means a complex solid solution oxide (including doped complex oxide) and / or complex oxide cluster composed of tin and silicon oxide. Furthermore, the composite oxide constituting the core particle and / or the coating layer may be a composite hydrous oxide having an OH group at the terminal, or may contain a part of the composite hydrous oxide. Good.

  The average particle size of the inorganic oxide fine particles containing titanium oxide is 1 to 200 nm, preferably 5 to 30 nm. Here, when the average particle size is less than 1 nm, the particles are bridged and do not shrink uniformly in the drying process for forming the hard coat layer on the plastic lens substrate, and the shrinkage rate is also reduced. The hard coat layer having a sufficient film hardness cannot be obtained. On the other hand, if the average particle size exceeds 200 nm, the hard coat layer turns white and becomes unsuitable for use as an optical component.

  The inorganic oxide fine particles containing titanium oxide having a rutile-type crystal structure may be used alone or in combination with other inorganic oxide particles. Other inorganic oxide particles include one or more metal oxides selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In (mixtures thereof) And / or inorganic oxide fine particles composed of a composite oxide containing two or more metals.

  Specific examples of the inorganic oxide fine particles include inorganic oxide fine particles containing titanium oxide having a rutile-type crystal structure with an average particle diameter of 1 to 200 nm, such as a dispersion medium such as water, alcohol-based, or others. In an organic solvent in a colloidal form. Examples of commercially available products include (i) titanium oxide and tin oxide, or the surface of a core particle of a composite oxide having a rutile-type crystal structure composed of titanium oxide, tin oxide and silicon oxide, and (ii) silicon oxide and zirconium oxide. And / or an op-trake manufactured by Catalyst Kasei Kogyo Co., Ltd., which is a dispersion sol for coating containing inorganic oxide fine particles having an average particle diameter of 8 to 10 nm coated with a composite oxide coating layer made of aluminum oxide. Can do.

  Furthermore, in order to increase the dispersion stability in the coating composition, it is also possible to use these inorganic oxide fine particle surfaces treated with an organosilicon compound or an amine compound, and further with a carboxylic acid such as tartaric acid or malic acid. It is.

  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. In addition, 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.

Amine compounds include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine. There is.
The addition amounts of these organosilicon compound and amine compound are preferably added within a range of about 1 to 15% with respect to the weight of the inorganic oxide fine particles.

  The type and blending amount of the inorganic oxide fine particles are determined by the target hardness, refractive index, etc., but the blending amount is 5 to 80% by weight, particularly 10 to 50% by weight of the solid content in the hard coat composition. It is desirable to be in the range of% by weight. If the amount is too small, the wear resistance of the coating film may be insufficient. Moreover, when there are too many compounding quantities, a crack will arise in a coating film and dyeing | staining property may become inadequate.

The organosilicon compound as component (B) that constitutes the coating composition for forming the hard coat layer is represented by the general formula: R ¹ SiX ¹ ₃ . This organosilicon compound functions as a binder for the hard coat layer.

In the formula, R ¹ has a polymerizable reactive group, preferably an organic group having 2 to 6 carbon atoms, vinyl group, allyl group, acrylic group, methacryl group, 1-methylvinyl group, epoxy group, mercapto group. , A cyano group, an isocyano group, an amino group, and other polymerizable reactive groups. X ¹ 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, or acyloxy groups. Etc. The number of hydrolyzable groups is 3, and it is necessary to be able to form a three-dimensional crosslinked structure. When the number of hydrolyzable groups is 2 or less, the abrasion resistance of the coating film is insufficient.

Specific examples of the organosilicon compound (B) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxy. Examples include silane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, and γ-aminopropyltrialkoxysilane.
Two or more organic silicon compounds as component (B) may be mixed and used. In addition, it is more effective to use the organosilicon compound as the component (B) after hydrolysis.

It is preferable to mix | blend a polyfunctional epoxy compound as (C) component with the coating composition which forms a hard-coat layer.
The polyfunctional epoxy compound can improve the adhesion of the hard coat layer to the plastic substrate, improve the water resistance of the hard coat layer, and can impart flexibility to the hard coat layer. The antireflection film composed of an inorganic vapor deposition film functions as a protective film for the hard coat layer. However, since the antireflection film composed of an organic thin film is extremely thin, the hard coat layer needs to have water resistance. In addition, the antireflection film composed of an organic thin film is cured by baking after applying the coating liquid, but the hard coat layer is baked twice together with its own baking during the baking, Cracks may occur in the hard coat layer. Furthermore, cracks may occur in the hard coat layer even when exposed to heat cycles or ultraviolet rays. It is considered that the polyfunctional epoxy compound can suppress the occurrence of such cracks by imparting flexibility to the hard coat layer, thereby improving yield and weather resistance.

  Specific examples of the polyfunctional epoxy compound include 1,6-hexanediol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and nonaethylene glycol. Diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol hydroxyhibarin Diglycidyl ether of acid ester, trimethylol propprop Diglycidyl ether, Trimerolpropane triglycidyl ether, Glycerol diglycidyl ether, Glycerol triglycidyl ether, Diglycerol diglycidyl ether, Diglycerol triglycidyl ether, Diglycerol tetraglycidyl ether, Pentaerythritol triglycidyl ether, Pentaerythritol tetraglycidyl ether , Dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanate, and the like, isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl Ether, etc. alicyclic epoxy compounds, resorci Diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether, phenol novolac polyglycidyl ether, aromatic epoxy compounds such as cresol novolac polyglycidyl ether.

  Among these, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, trimerolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl) Particularly preferred are aliphatic epoxy compounds such as triglycidyl ethers of isocyanates.

  The compounding amount of the polyfunctional epoxy compound is preferably 4 to 22% by weight, particularly 5 to 20% by weight, based on the solid content. If the compounding amount of the polyfunctional epoxy compound is too small, adhesion to the substrate, water resistance and flexibility will be reduced, and cracks will occur in the hard coat layer due to firing etc. when forming an antireflection film with a low refractive index. There is a case. On the other hand, if the amount is too large, the hardness of the hard coat layer may decrease.

Further, the coating composition for forming the hard coat layer, further, as the component (D), the general formula: It preferably contains an organic silicon compound represented by ^{_{R 2 n SiX 2 4-n}} .
In this general formula, R ² is a hydrocarbon group having 1 to 3 carbon atoms. Specific examples include vinyl group, allyl group, acrylic group, methacryl group, 1-methylvinyl group, epoxy group, mercapto group, cyano group. Group, isocyano group, amino group, methyl group, ethyl group, propyl group, vinyl group and the like. X ² 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 groups. Is mentioned. In the formula, n represents 0 or 1.
Specific examples of this silane compound include tetraalkoxysilane, vinyltrialkoxysilane, methyltrialkoxysilane, allyltrialkoxysilane and the like.

  This organosilicon compound as component (D) is effective in further improving the durability of the coating, particularly the scratch resistance. (D) As for the usage-amount of the organosilicon compound of a component, 2-15 weight% of solid content is preferable. That is, if it is less than 2% by weight, there is no effect of addition, and if it exceeds 15% by weight, the coating film tends to be clouded or cracked, which is not preferable. These compounds may be used alone or in combination of two or more. The organosilicon compound as component (D) is more effective when used after hydrolysis.

In addition, the coating composition for forming the hard coat layer further includes (E) component,
(E) the ^{_{formula: X 3 3-m -Si (}} R 3 m) -Y-Si (R 4 m) -X 4 3-m
It is preferable to mix | blend the disilane compound represented by these. In this general formula, R ³ and R ⁴ are each 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. X ³ and X ⁴ are hydrolyzable groups, 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 groups. Can be given. In the formula, m represents 0 or 1. Y is an organic group having a carbonate group or an epoxy group, and specific examples thereof include the following.

  These disilane compounds can be synthesized by a conventionally known method. For example, it can be obtained by subjecting diallyl carbonate to trichlorosilane or the like, followed by alkoxylation. Alternatively, it can be obtained by adding a trichlorosilane or the like to a compound having a substituent that can be added at both ends and further containing a functional group that can be epoxidized therein, followed by alkoxylation.

  By blending the disilane compound, the curing rate of the coating composition can be improved. Improving the curing rate and shortening the curing time can reduce the possibility of dust and impurities adhering to the coating surface in the coating film forming process, and improve the yield. In addition, the effect of improving the dyeability, the effect of reducing the blending amount of the polyfunctional epoxy compound, or the effect of making the presence of defects such as scratches present on the surface of the object to be coated inconspicuous Have

  The blending amount of the disilane compound is preferably in the range of 3 to 40% by weight, particularly 5 to 20% by weight of the solid content. If the blending amount is too small, the reaction promoting effect may not appear. On the other hand, if the blending amount is too large, the water resistance of the coating film may be deteriorated or the pot life of the coating solution may be shortened.

  Moreover, a curing catalyst can be mix | blended with the coating composition which forms a hard-coat layer. However, it can be cured without a curing catalyst. Preferred curing catalysts include perchloric acids such as perchloric acid, ammonium perchlorate, and magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (II), Be (II), and Ce. (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce Examples include amino acids such as acetylacetonate, amine, glycine, Lewis acid, organic acid metal salts and the like having (IV), Zr (IV), V (IV) and the like as a central metal atom. Among these, magnesium perchlorate, Al (III), and acetylacetonate of Fe (III) are more preferable in terms of curing conditions and pot life of the coating liquid. The addition amount is desirably within the range of 0.01 to 5.0% by weight of the solid content concentration.

  The coating composition for forming a hard coat layer thus obtained can be used after diluting in a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.

  In addition to the above components, a coating composition for forming a hard coat layer may contain a small amount of a metal chelate compound, a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, if necessary. , Oil-soluble dyes, pigments, photochromic compounds, hindered amines, hindered phenols and other light-resistant heat-resistant stabilizers, etc. are added to improve coating liquid coating properties, curing speed, and coating performance after curing. You can also.

  Further, in the application of the coating composition, the surface of the plastic lens substrate is previously subjected to alkali treatment, acid treatment, surfactant treatment, inorganic or organic fine particles for the purpose of improving the adhesion between the plastic lens substrate and the coating. It is effective to perform a peeling / polishing process, a primer process or a plasma process.

  The coating composition may be applied and cured by dipping, spin coating, spray coating, roll coating, or flow coating. After apply | coating the composition for coating, a film can be formed by heat-drying for several hours at the temperature of 40-200 degreeC.

  The film thickness of the hard coat layer is preferably 0.05 to 30 μm. That is, if the thickness is less than 0.05 μm, the basic performance cannot be realized, and if it exceeds 30 μm, the smoothness of the surface may be impaired or optical distortion may occur.

  The plastic lens of the present invention has an antireflection film on the hard coat layer. In the present invention, the antireflection film is an organic thin film having a refractive index lower by 0.10 or more than the refractive index of the hard coat layer and having a thickness of 50 nm to 150 nm.

  The organic thin film constituting the antireflection film is not limited as long as it has the above-mentioned refractive index and has the above-mentioned film thickness, but a resin such as silicone, acrylic, epoxy, urethane, melamine or the like A material formed by using raw material monomers alone or in combination with two or more of other resins and raw material monomers is preferable. When considering various properties such as heat resistance, chemical resistance, and scratch resistance as a plastic lens, it is preferable to use a low refractive index layer containing a silicone resin. In addition, it is more preferable to add a particulate inorganic substance for adjusting the refractive index. Examples of the fine inorganic particles include colloidally dispersed sols, and specific examples include silica sol, magnesium fluoride sol, calcium fluoride sol, and the like.

In particular, an organic thin film formed by a wet method using a coating composition containing the following components (F) and (G) can be preferably used.
(F) an organosilicon compound represented by the general formula: R ⁵ _r R ⁶ _q SiX ⁵ _4-qr ,
(In the formula, R ⁵ is an organic group having a polymerizable reactive group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, X ⁵ is a hydrolytic group, q is 0 or 1, and r is 0 or 1. .)
(G) Silica-based fine particles having an average particle diameter of 1 to 150 nm.

  An inorganic film formed by a dry process such as vapor deposition or sputtering has low heat resistance due to a large difference in thermal expansion coefficient from the hard coat layer of the underlying organic film, whereas an organic film formed by such a wet process. The antireflection film composed of a thin film has a small difference in coefficient of thermal expansion from the hard coat layer, so that it is difficult for cracks to occur due to heating and is excellent in heat resistance. Further, since it can be formed by a wet method, a vacuum apparatus or a large-sized facility is not necessary, and it can be easily manufactured.

Examples of the organic group having a polymerizable reactive group of R ⁵ in the general formula include a vinyl group, an allyl group, an acrylic group, a methacryl group, an epoxy group, a mercapto group, a cyano group, and an amino group. Specific examples of the hydrocarbon group having 1 to ⁶ carbon atoms of R ⁶ include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. Specific examples of the hydrolyzable functional group for X ⁵ include alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

  Specific examples of the organosilicon compound of component (F) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxy. Silane, methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl dialkoxysilane, tetraalkoxysilane and the like can be mentioned.

  Examples of the silica-based fine particles of component (G) include silica sol in which silica-based fine particles having an average particle diameter of 1 to 150 nm are colloidally dispersed in a dispersion medium such as water, alcohol-based or other organic solvents. In order to reduce the refractive index, for example, it is preferable to use a silica sol made of silica-based fine particles in which cavities or voids are formed. By including a gas or solvent having a refractive index lower than that of silica in the internal cavities of the silica-based fine particles, the refractive index is lower than that of silica-based fine particles having no cavities, and a low refractive index of the coating is achieved.

  The silica-based fine particles having internal cavities will be described in more detail. The silica-based fine particles are produced by the method described in JP-A-2001-233611. In the present invention, the average particle size is 20 It is desirable to use one having a refractive index in the range of ˜150 nm and a refractive index in the range of 1.16 to 1.39. Here, when the average particle size of the particles is less than 20 nm, the void ratio inside the particles becomes small and a desired low refractive index cannot be obtained. When the average particle size exceeds 150 nm, the haze of the organic thin film increases. This is not preferable.

  The silica-based fine particles having internal cavities as described above are suriria and recum, manufactured by Catalyst Kasei Kogyo Co., Ltd., which are dispersed sols containing hollow silica fine particles having an average particle diameter of 20 to 150 nm and a refractive index of 1.16 to 1.39. Etc.

  The coating composition for forming the antireflection film in the present invention includes, in addition to the components (F) and (G), a polyurethane resin, an epoxy resin, a melamine resin, a polyolefin resin, and a urethane acrylate resin. It is possible to add various resins such as epoxy acrylate resins and various monomers such as methacrylates, acrylates, epoxies, vinyls and the like as raw materials for these resins. Among them, it is preferable to add various fluorine-containing polymers or various fluorine-containing monomers in order to reduce the refractive index. The fluorine-containing polymer at this time is preferably a polymer obtained by polymerizing a fluorine-containing vinyl monomer, and preferably has a functional group copolymerizable with other components.

  Such a coating composition for a low refractive index layer can be used by diluting in a solvent, if necessary. As the solvent, solvents such as water, alcohols, esters, ketones, ethers and aromatics are used.

  The coating composition for the low refractive index layer containing the organosilicon compound of component (F) and the silica-based fine particles of component (G) can contain, in addition to these components, a small amount of a curing catalyst, Addition of surfactants, antistatic agents, UV absorbers, antioxidants, light stabilizers such as hindered amines and hindered phenols, disperse dyes, oil-soluble dyes, fluorescent dyes and pigments, etc. And the film performance after curing can also be improved.

  Specifically, a known method such as a dipping method, a spinner method, a spray method, or a flow method can be used as a method for forming a low refractive index antireflection film by a wet method. In consideration of forming a thin film with a thickness of 50 nm to 150 nm on a curved surface like a plastic lens among various film forming methods, a dipping method or a spinner method is preferable.

  When forming the low refractive index layer on the hard coat layer, it is preferable to pre-treat the hard coat layer surface. As a specific example of this pretreatment, a method of hydrophilizing the hard coat surface (contact angle θ 60 ° or less) such as surface polishing, ultraviolet ray-ozone cleaning, plasma treatment or the like is effective.

  A specific method of forming the antireflection film can be performed by the following procedure. First, the organosilicon compound of component (F) is diluted with an organic solvent, and then hydrolyzed by adding water, dilute hydrochloric acid, acetic acid or the like as necessary. Further, a product in which the silica-based fine particles of component (G) are dispersed in a colloidal form in an organic solvent at a fraction of 5 to 50% by weight is added. Thereafter, if necessary, a surfactant, an ultraviolet absorber, an antioxidant and the like are added, and after sufficiently stirring, used as a coating liquid. At this time, the concentration of the coating liquid diluted with respect to the solid content after curing is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight as the solid content concentration. When the solid content concentration exceeds 15% by weight, it is difficult to obtain a predetermined film thickness even if the pulling speed is reduced by the dipping method or the rotation speed is increased by the spinner method. It becomes thicker than necessary. If the solid content concentration is less than 0.5% by weight, the film thickness becomes thinner than necessary even if the pulling speed is increased by the dipping method or the rotation speed is decreased by the spinner method. It is difficult to obtain the film thickness. If the speed is too high or the rotational speed is too low, uneven coating on the lens tends to increase, and even when a surfactant or the like is added, the corresponding partition cannot be made.

  An antireflection film can be obtained by applying the coating liquid to a plastic lens and then curing it with heat or ultraviolet rays, but it is preferable to cure it by heat treatment. In this case, the heating temperature is appropriately determined in consideration of the composition of the coating composition, the heat resistance of the plastic lens substrate, etc., preferably 50 ° C. to 200 ° C., more preferably 80 ° C. to 140 ° C. is there.

  The thickness of the obtained antireflection film needs to be in the range of 50 nm to 150 nm. If it is too thick or too thin than this range, a sufficient antireflection effect cannot be obtained. In order to function as an antireflection film, the refractive index of the antireflection film is such that the difference in refractive index from the underlying hard coat layer is 0.10 or more, preferably 0.15 or more, more preferably 0.20 or more. It is necessary to. The specific refractive index is preferably in the range of 1.30 to 1.45.

Furthermore, it is as follows if the main part about the manufacturing method of the plastic lens which concerns on this invention is arranged and described.
(1) A method for producing a plastic lens according to the present invention comprises forming a hard coat layer on a plastic lens substrate from a coating composition containing at least the following components (A) and (B): Forming process;
(A) Inorganic oxide fine particles containing titanium oxide having a rutile crystal structure with an average particle size of 1 to 200 nm,
(B) the general formula: an organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein, R ¹ represents the number of carbon atoms having a polymerizable reactive group represents a 3 or more organic groups, X ¹ is a hydrolyzable group Represents)
An antireflection film forming step of forming an organic thin film having a refractive index lower by 0.10 or more than the refractive index of the hard coat layer on the hard coat layer and a film thickness of 50 nm to 150 nm. .
(2) The method for producing a plastic lens according to the present invention comprises forming a hard coat layer from a coating composition containing at least the following components (A) and (B) on a plastic lens substrate: Forming process;
(A) Inorganic oxide fine particles having an average particle diameter of 1 to 200 nm including a composite oxide having a rutile type crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide,
(B) the general formula: an organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein, R ¹ represents the number of carbon atoms having a polymerizable reactive group represents a 3 or more organic groups, X ¹ is a hydrolyzable group Represents)
An antireflection film forming step of forming an organic thin film having a refractive index lower by 0.10 or more than the refractive index of the hard coat layer on the hard coat layer and a film thickness of 50 nm to 150 nm. .
(3) The method for producing a plastic lens according to the present invention is a rutile type comprising (i) titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide as the inorganic oxide fine particles according to (2). The surface of the core particle of the complex oxide having a crystal structure is used (ii) coated with a coating layer of a complex oxide composed of silicon oxide and zirconium oxide and / or aluminum oxide.
(4) In the method for producing a plastic lens according to the present invention, the organic thin film formed in the antireflection film forming step is prepared by using the following (F) component and (G) component (F) general formula: R ⁵ _r R ⁶ _An organosilicon compound represented by _q SiX ⁵ _4-qr (wherein R ⁵ is an organic group having a polymerizable reactive group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, and X ⁵ is a hydrolysis group) And q is 0 or 1, and r is 0 or 1.),
(G) A coating composition containing silica-based fine particles having an average particle diameter of 1 to 150 nm is used.
(5) In the method for producing a plastic lens according to the present invention, the silica-based fine particles described in (4) are those having an internal cavity.
(6) The method for producing a plastic lens according to the present invention has an average particle diameter of 20 to 150 nm and a refractive index in the range of 1.16 to 1.39 as the silica-based fine particles according to (5). Use something.

Hereinafter, although the detail of this invention is demonstrated based on an Example, this invention is not limited to these.
Examples 1-8, Comparative Examples 1-5

  In Examples 1 to 8 and Comparative Examples 1 to 5 shown below, the effects of blending the components of the coating composition for forming the hard coat layer used in the plastic lens of the present invention were confirmed. In addition, evaluation of the obtained plastic lens was performed by the following method.

(1) Moisture resistance:
Although the surface condition is not changed at all after being left in a constant temperature and humidity chamber set at 60 ° C. and 100 RH% (manufactured by Davai Espec Co., Ltd .: PR-1G) for 7 days, a slight change is observed. Those that had no problem in practical use were considered good.

(2) Weather resistance:
After exposure to a sunshine weather meter (Suga Test Instruments Co., Ltd .: WEL-SUN-HC) using a xenon lamp for 80 hours, the degree of change in the surface condition was visually evaluated in the following stages.
A: Change is not recognized.
○: White turbidity occurred △: Cracks occurred ×: Cracks occurred

(3) Adhesiveness of surface treatment layer (hard coat layer and low refractive index layer):
The adhesion between the lens fabric and the surface treatment layer (hard coat layer and antireflection film) was evaluated. A cross-cut tape test was performed according to JIS D-0202. That is, using a knife, cuts are made on the substrate surface at intervals of 1 mm to form 100 squares of 1 mm square. Next, after strongly pressing a cellophane tape (trade name “Cerotape”, manufactured by Nichiban Co., Ltd.) onto the surface, the sheet was suddenly pulled away from the surface in the direction of 90 degrees, and the coating film remained. The squares were visually observed as an adhesion index.
A: The remaining area of the coating film is 100%.
○: Remaining area of the coat film is 95% to less than 100% Δ: Remaining area of the coat film is 50% to less than 95% X: Remaining area of the coat film is less than 50%

(4) Scratch resistance test:
Using a steel wool (No. 0000 manufactured by Nippon Steel Wool Co., Ltd.), the lens is rubbed with a load of 1 kg and 10 reciprocations, and the degree of damage is ranked in 10 stages by visual observation.
(1 (bad) to 10 (good))
A: 10 to 8
○: 7-6 △: 5-4
X: 3 to 1

(1) Preparation of hard coating layer coating liquid (H-1) Core of composite oxide having rutile crystal structure composed of 264 parts of propylene glycol methyl ether, titanium oxide, tin oxide and silicon oxide The surface of the particles is coated with a coating layer of a composite oxide composed of silicon oxide and zirconium oxide, and the inorganic oxide fine particles having an average particle diameter of 10 nm, which is surface-modified with a coupling agent, are dispersed in methanol. After mixing 1000 parts of a composite oxide sol (trade name “OPTRAIQUE 1120Z (11RU-7 / A8)” manufactured by Catalytic Chemical Industry Co., Ltd.), 226 parts of γ-glycidoxypropyltrimethoxysilane, glycero- 40 parts of Rupoliglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacoll EX-313”) was mixed. To this mixed solution, 62 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring. After further stirring for 4 hours and aging overnight, 3 parts of Fe (III) acetylacetonate, silicon surfactant (Nippon Unicar (Product name, “L-7001”) was added, and the mixture was stirred for 4 hours and then aged overnight. The coating solution for the hard coat layer obtained here is abbreviated as H-1.

(2) Preparation of coating liquid for hard coat layer (H-2) Nucleus of composite oxide having rutile type crystal structure consisting of 146 parts of propylene glycol methyl ether, titanium oxide, tin oxide and silicon oxide The surface of the particles is coated with a coating layer of a composite oxide composed of silicon oxide and zirconium oxide, and the inorganic oxide fine particles having an average particle diameter of 10 nm, which is surface-modified with a coupling agent, are dispersed in methanol. After mixing 1000 parts of a composite oxide sol (trade name “OPTRAIQUE 1120Z (11RU-7 / A8)” manufactured by Catalyst Kasei Kogyo Co., Ltd.), 226 parts of γ-glycidoxypropyltrimethoxysilane, tetramethoxy 101 parts of silane were mixed. 120 parts of 0.1N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was further stirred for 4 hours and then aged for 24 hours. Then, 2 parts of Fe (III) acetylacetonate, silicon surfactant (Nihon Unicar (Product name, “L-7001”) was added, and the mixture was stirred for 4 hours and then aged overnight. The coating liquid for the hard coat layer obtained here is abbreviated as H-2.

(3) Preparation of hard coat layer coating liquid (H-3) 178 parts of propylene glycol methyl ether, composite oxide having rutile crystal structure composed of titanium oxide, tin oxide and silicon oxide Solid content concentration in which inorganic oxide fine particles with an average particle diameter of 10 nm, coated with a composite oxide coating layer composed of silicon oxide and zirconium oxide, and surface-modified with a coupling agent are dispersed in methanol. After mixing 1000 parts of a composite oxide sol of 20 wt% (catalyst chemical industry Co., Ltd., trade name “Optlake 1120Z (11RU-7 / A8)”), 170 parts of γ-glycidoxypropyltrimethoxysilane, 101 parts of tetramethoxysilane, glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacol EX-313”) 40 It was mixed. To this mixed solution, 104 parts of 0.1N aqueous hydrochloric acid solution was added dropwise with stirring. After further stirring for 4 hours and aging overnight, 2.5 parts of Fe (III) acetylacetonate, silicon surfactant (Japan) 5 parts of Unicar Co., Ltd., trade name “L-7001”) was added and stirred for 4 hours and then aged overnight. The coating liquid for the hard coat layer obtained here is abbreviated as H-3.

(4) Preparation of hard coat layer coating liquid (H-4) 261 parts of propylene glycol methyl ether, composite oxide having rutile crystal structure composed of titanium oxide, tin oxide and silicon oxide Solid content concentration in which inorganic oxide fine particles with an average particle diameter of 10 nm, coated with a composite oxide coating layer composed of silicon oxide and zirconium oxide, and surface-modified with a coupling agent are dispersed in methanol. After mixing 1000 parts of a composite oxide sol of 20 wt% (catalyst chemical industry Co., Ltd., trade name “Optlake 1120Z (11RU-7 / A8)”), 170 parts of γ-glycidoxypropyltrimethoxysilane, 63 parts of disilane compound (manufactured by Tokuyama Corporation, trade name “NSK-100”), glycerol polyglycidyl ether (manufactured by Nagase Chemical Industries, Ltd.) Name "Denako - Le EX-313") were mixed 40 parts. To this mixture, 60 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring. After further stirring for 4 hours and aging overnight, 2.5 parts of Fe (III) acetylacetonate, silicon surfactant (Japan) 5 parts of Unicar Co., Ltd., trade name “L-7001”) was added and stirred for 4 hours and then aged overnight. The coating liquid for the hard coat layer obtained here is abbreviated as H-4.

(5) Preparation of hard coat layer coating liquid (H-5) 264 parts of propylene glycol methyl ether, composite oxide having rutile crystal structure composed of titanium oxide, tin oxide and silicon oxide Solid content concentration in which inorganic oxide fine particles having an average particle diameter of 8 nm, coated with a composite oxide coating layer composed of silicon oxide and zirconium oxide, and surface-modified with a coupling agent are dispersed in methanol. After mixing 1030 parts of a composite oxide sol of 20 wt% (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIK 1120Z (8RU-25 / A17)”), 226 parts of γ-glycidoxypropyltrimethoxysilane, 40 parts of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacoll EX-313”) were mixed. To this mixed solution, 62 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring. After further stirring for 4 hours and aging overnight, 3 parts of Fe (III) acetylacetonate, silicon surfactant (Nippon Unicar (Product name, “L-7001”) was added, and the mixture was stirred for 4 hours and then aged overnight. The coating liquid for the hard coat layer obtained here is abbreviated as H-5.

(6) Preparation of hard coating layer coating liquid (H-6) 264 parts of propylene glycol methyl ether, composite oxide having rutile crystal structure composed of titanium oxide, tin oxide and silicon oxide Solid content concentration in which inorganic oxide fine particles with an average particle diameter of 10 nm, which are coated with a composite oxide coating layer composed of silicon oxide and aluminum oxide and surface-modified with a coupling agent, are dispersed in methanol. After mixing 1000 parts of 20 wt% complex oxide sol (catalyst chemical industry Co., Ltd., trade name “OPTRAICK 1120AL (11RU-7 · A8)”), 226 parts of γ-glycidoxypropyltrimethoxysilane, 40 parts of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacoll EX-313”) were mixed. To this mixed solution, 62 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring. After further stirring for 4 hours and aging overnight, 3 parts of Fe (III) acetylacetonate, silicon surfactant (Nippon Unicar (Product name, “L-7001”) was added, and the mixture was stirred for 4 hours and then aged overnight. The coating liquid for the hard coat layer obtained here is abbreviated as H-6.

(7) Preparation of hard coat layer coating liquid (H-7) 264 parts of propylene glycol methyl ether, composite oxide having rutile crystal structure composed of titanium oxide, tin oxide and silicon oxide The solid particles were coated with a composite oxide coating layer composed of silicon oxide, zirconium oxide and aluminum, and inorganic oxide fine particles with an average particle size of 8 nm, which were surface-modified with a coupling agent, were dispersed in methanol. After mixing 1030 parts of a composite oxide sol having a partial concentration of 20 wt% (trade name “OPTRAICK 1120ZAL (8RU-25 • A8)” manufactured by Catalysts & Chemicals Industries, Ltd.) 226 of γ-glycidoxypropyltrimethoxysilane Part, 40 parts of glycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacoll EX-313”) was mixed. To this mixed solution, 62 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring. After further stirring for 4 hours and aging overnight, 3 parts of Fe (III) acetylacetonate, silicon surfactant (Nippon Unicar (Product name, “L-7001”) was added, and the mixture was stirred for 4 hours and then aged overnight. The coating solution for the hard coat layer obtained here is abbreviated as H-7.

(8) Preparation of Hard Coating Layer Coating Liquid (H-8) In the preparation of the hard coating layer coating liquid (H-1), the sol of the inorganic oxide fine particles was changed to titanium oxide. The average particle diameter of the surface of the core particle of the complex oxide consisting of anatase type silicon oxide and silicon oxide coated with a composite oxide coating layer consisting of silicon oxide and zirconium oxide, and surface modification with a coupling agent Except for using a composite oxide sol having a solid content concentration of 20 wt% in which inorganic oxide fine particles of 8 nm are dispersed in methanol (catalyst chemical industry Co., Ltd., trade name “OPTRAIK 1120Z (U-25 / A8)”) , Prepared in the same manner as H-1. The coating liquid for the hard coat layer obtained here is abbreviated as H-8.

(9) Preparation of hard coating layer coating liquid (H-9) In preparing the hard coating layer coating liquid (H-2), the inorganic oxide fine particle sol was oxidized with titanium oxide. The surface of the composite oxide core particle having an anatase type crystal structure composed of silicon is coated with a composite oxide coating layer composed of silicon oxide and zirconium oxide, and further surface-modified with a coupling agent. Except for using a composite oxide sol having a solid content concentration of 20 wt% in which inorganic oxide fine particles are dispersed in methanol (trade name “Optlake 1120Z (U-25 / A8)” manufactured by Catalyst Chemical Industry Co., Ltd.) -2 in the same manner. The coating liquid for the hard coat layer obtained here is abbreviated as H-9.

(10) Preparation of hard coating layer coating liquid (H-10) In preparation of the hard coating layer coating liquid (H-3), the inorganic oxide fine particle sol was oxidized with titanium oxide. The surface of the composite oxide core particle having an anatase type crystal structure composed of silicon is coated with a composite oxide coating layer composed of silicon oxide and zirconium oxide, and further surface-modified with a coupling agent. Except for using a composite oxide sol having a solid content concentration of 20 wt% in which inorganic oxide fine particles are dispersed in methanol (trade name “Optlake 1120Z (U-25 / A8)” manufactured by Catalyst Chemical Industry Co., Ltd.) -3. The coating solution for the hard coat layer obtained here is abbreviated as H-10.

(11) Preparation of Hard Coating Layer Coating Liquid (H-11) In the preparation of the hard coating layer coating liquid (H-4), the inorganic oxide fine particle sol was replaced with titanium oxide. The average particle diameter of the surface of the core particle of the complex oxide consisting of anatase type silicon oxide and silicon oxide coated with a composite oxide coating layer consisting of silicon oxide and zirconium oxide, and surface modification with a coupling agent Except for using a composite oxide sol having a solid content concentration of 20 wt% in which inorganic oxide fine particles of 8 nm are dispersed in methanol (catalyst chemical industry Co., Ltd., trade name “OPTRAIK 1120Z (U-25 / A8)”) , And prepared in the same manner as H-4. The coating liquid for the hard coat layer obtained here is abbreviated as H-11.

(12) Preparation of coating liquid (C-1) for low refractive index layer After mixing 18.8 g of propylene glycol monomethyl ether (hereinafter PGME) and 8.1 g of γ-glycidoxytrimethoxysilane, 0.1N hydrochloric acid aqueous solution 2.2 g was added dropwise with stirring and stirred for 5 hours. Silica sol having a solid content concentration of 20 wt% in which silica-based fine particles (hollow silica fine particles) having an average particle diameter of 60 nm and having cavities therein are dispersed in isopropanol is added to this liquid (catalyst chemical industry Co., Ltd., trade name “Thru rear 1420”) ) 20.7 g was added and mixed well, then 0.04 g of Al (C ₅ H ₇ O ₂ ) ₃ and 0.015 g of a silicon surfactant (Nihon Unicar L7604) were added and stirred as a polymerization catalyst. By dissolving, a coating stock solution having a solid content concentration of 20% was obtained. In order to dilute the coating solution, a PGME solution containing a 300 ppm silicon surfactant (Nihon Unicar L7604) was prepared, and 35.3 g of the coating stock solution was mixed with 114.7 g of the PGME solution containing the surfactant for dilution. The mixture was sufficiently stirred to prepare a coating solution for a low refractive index layer having a solid content concentration of about 4.7%. The coating liquid for the low refractive index layer obtained here is abbreviated as C-1.

(13) Preparation of coating liquid for low refractive index layer (C-2) After mixing 18.8 g of propylene glycol monomethyl ether (hereinafter PGME) and 8.1 g of γ-glycidoxytrimethoxysilane, 0.1N hydrochloric acid aqueous solution 2.2 g was added dropwise with stirring and stirred for 5 hours. 20.7 g of a silica sol having a solid content concentration of 20 wt% in which silica-based fine particles having an average particle diameter of 45 nm and having no voids are dispersed in isopropanol in this liquid (trade name “Oscar 1435” manufactured by Catalyst Chemical Industry Co., Ltd.) Is added and mixed sufficiently, and then 0.04 g of Al (C ₅ H ₇ O ₂ ) ₃ and 0.015 g of a silicon surfactant (Nihon Unicar L7604) are added as a polymerization catalyst and stirred and dissolved. As a result, a coating stock solution having a solid concentration of 20% was obtained. In order to dilute the coating solution, a PGME solution containing a 300 ppm silicon surfactant (Nihon Unicar L7604) was prepared, and 35.3 g of the coating stock solution was mixed with 114.7 g of the PGME solution containing the surfactant for dilution. The mixture was sufficiently stirred to prepare a coating solution for a low refractive index layer having a solid content concentration of about 4.7%. The coating liquid for the low refractive index layer obtained here is abbreviated as C-2.

Example 1
The above H-1 is used to immerse a plastic lens having a refractive index of 1.67 (manufactured by Seiko Epson Corporation, lens fabric for Seiko-Super-Sovereign, hereinafter abbreviated as SSV) (pulling speed of 35 cm / min). ).
After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 1 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

(Example 2)
Using the above H-2, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 120 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 2 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

(Example 3)
Using the above H-3, the coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 3 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

Example 4
Using the above H-4, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After the coating, it was air-dried at 80 ° C. for 20 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 4 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

(Example 5)
Using the above H-5, coating was performed on the SSV by a dipping method (pulling speed of 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 120 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 5 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

(Example 6)
Using the above H-6, coating was performed on the SSV by a dipping method (pulling speed of 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 120 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 6 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

(Example 7)
Using the above H-7, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 120 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 7 was satisfactory in terms of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance.

(Example 8)
Using the above H-1, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 120 minutes to form a 2.5 μm hard coat layer. The lens substrate thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-2 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.46.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Example 8 was satisfactory in all of moisture resistance, weather resistance, adhesion of the surface treatment layer, and scratch resistance. However, when compared with the lenses obtained in Examples 1 to 7, the reflectance measured at the bottom of the reflectance curve tended to be high.

(Comparative Example 1)
Using the above H-8, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Comparative Example 1 was satisfactory in terms of adhesion, scratch resistance and moisture resistance of the surface treatment layer, but was somewhat deficient in weather resistance.

(Comparative Example 2)
Using the above H-9, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After the coating, it was air-dried at 80 ° C. for 20 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Comparative Example 2 was satisfactory in terms of adhesion, scratch resistance and moisture resistance of the surface treatment layer, but was insufficient in terms of weather resistance.

(Comparative Example 3)
Using the above H-10, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Comparative Example 3 was satisfactory in terms of adhesion, scratch resistance and moisture resistance of the surface treatment layer, but was insufficient in terms of weather resistance.

(Comparative Example 4)
Using the above H-11, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens base material thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-1 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.37.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Comparative Example 4 was satisfactory in terms of adhesion, scratch resistance and moisture resistance of the surface treatment layer, but was insufficient in weather resistance.

(Comparative Example 5)
Using the above H-8, coating was performed on the SSV by the dipping method (pulling speed 35 cm / min). After coating, the coating was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 180 minutes to form a 2.5 μm hard coat layer. The lens substrate thus obtained was applied by the immersion method (pickup speed 10 cm / min) using the C-2 solution. After coating, firing was performed at 100 ° C. for 180 minutes to obtain a lens with a low refractive index layer. The film thickness at this time was 90 nm, and the refractive index of the low refractive index layer was 1.46.
The lens thus obtained was subjected to the moisture resistance test, the weather resistance test, the adhesion test of the surface treatment layer, and the scratch resistance test. The lens obtained in Comparative Example 5 was inferior in weather resistance and showed a tendency that the reflectance measured at the bottom of the reflectance curve was high.

Table 1 summarizes the compositions of the coating compositions for forming the hard coat layer prepared in the examples. Table 2 summarizes the evaluation results of Examples and Comparative Examples.

  As is clear from Table 2, the plastic lenses of Comparative Examples 1 to 5 having the hard coat layer using the inorganic oxide fine particles H-8 to H-11 containing anatase type titanium oxide are made of titanium oxide. Even in the form of a composite oxide having a structure in which the oxide and composite oxide fine particles are further covered with a coating layer, it is recognized that the weather resistance is poor. Further, the plastic lens of Example 8 having a low refractive index layer using silica-based fine particles C-2 having no cavity inside has a high reflectance measured at the bottom of the reflectance curve, and further anatase type oxidation. In the plastic lens of Comparative Example 5 having a hard coat layer using titanium-containing inorganic oxide fine particles H-8 and a low refractive index layer using silica-based fine particles C-2 that do not have cavities therein, reflection Not only is the reflectance measured at the bottom of the rate curve high, but the weather resistance is poor.

  Furthermore, the plastic lenses of Example 2 and Comparative Example 2 having a hard coat layer formed of a coating liquid that does not contain the (C) component polyfunctional epoxy compound are slightly inferior in moisture resistance. In addition, the plastic lenses of Examples 2 and 3 and Comparative Examples 2 and 3 having a hard coat layer formed of a coating liquid containing an organosilicon compound as the component (D) are particularly excellent in scratch resistance.

Examples 9-11, Comparative Examples 6, 7
In Examples 9 to 11 and Comparative Examples 6 and 7 shown below, a test for confirming the effect of the amount of the polyfunctional epoxy compound was performed by changing the amount of the polyfunctional epoxy compound. In addition, evaluation of the obtained plastic lens was performed by the following method.

(1) Heat resistance test (cracking temperature):
The prepared lens was put in a predetermined spectacle frame, and then the spectacle frame was placed in an oven at 40 ° C. and heated for 30 minutes. After taking out from the oven and leaving at room temperature for 30 minutes, the lens was visually checked for cracks for darkness. When no crack was generated, the temperature of the oven was increased by 10 ° C. and heated again for 30 minutes, the same evaluation was performed, and the test was performed up to 100 ° C. The temperature when a dark crack was generated was defined as the crack generation temperature, and was evaluated as follows.
A: Very high heat resistance (crack generation temperature is 100 ° C., or no crack occurs even at 100 ° C.)
○: High heat resistance (crack generation temperature is 80 ° C to 90 ° C)
×: Low heat resistance (crack generation temperature is 70 ° C. or less)

(2) Adhesion:
Adhesion between the lens fabric and the surface treatment layer (hard coat layer and low refractive index layer) is determined by exposure to sunshine weather (sunshine weather meter with xenon lamp for 120 hours) and constant temperature and humidity (constant temperature and humidity). Evaluation was made on samples left in a bath 60 ° C. × 99% atmosphere for 7 days. A cross-cut tape test was performed according to JISD-0202. That is, using a knife, cuts are made on the substrate surface at intervals of 1 mm to form 100 squares of 1 mm square. Next, after strongly pressing a cellophane tape (trade name “Cerotape”, manufactured by Nichiban Co., Ltd.) onto the surface, the sheet is abruptly pulled away from the surface in the direction of 90 °, and the coating film remains. The squares were visually observed as an adhesion index.
A: The remaining area of the coating film is 100%.
○: Remaining area of the coat film is 95% to less than 100% Δ: Remaining area of the coat film is 50% to less than 95% ×: Remaining area of the coat film is less than 50%

(3) Weatherproof cracks:
The crack generation state after 120 hours exposure to the sunshine weather meter was evaluated.

(4) Scratch resistance test:
Using a steel wool (No. 0000 manufactured by Nippon Steel Wool Co., Ltd.), the lens is rubbed with a load of 1 kg and 10 reciprocations, and the degree of damage is ranked in 10 stages by visual observation.
(1 (bad) to 10 (good))
A: 10 to 8
○: 7-6
Δ: 5-4
X: 3 to 1

Example 9
(1) Formation of a hard coat layer The surface of a core particle of a composite oxide having a rutile type crystal structure consisting of 88 parts of propylene glycol methyl ether, titanium oxide, tin oxide and silicon oxide is formed on silicon oxide and zirconium oxide. And a composite oxide sol having a solid content concentration of 20 wt%, in which inorganic oxide fine particles having an average particle diameter of 8 nm and coated with a coating layer of a composite oxide made of aluminum and surface-modified with a coupling agent are dispersed in methanol. 750 parts of Kogyo Co., Ltd., trade name OPTRAIQUE "1120Z (8RU-25 / A17)") were mixed, and then 106 parts of γ-glycidoxypropyltrimethoxysilane and glycerol polyglycidyl ether (Nagase Kasei Kogyo Co., Ltd.) ), Trade name Denacol EX313) 25 parts was mixed. To this mixed solution, 30 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours. After aging for a whole day and night, 1.6 parts of Fe (III) acetylacetonate, 0.3 part of silicone surfactant (product name L-7001, manufactured by Nihon Unicar Co., Ltd.), phenolic antioxidant (Kawaguchi Chemical) Industrial Co., Ltd. product name "ANTAGE CRYSTAL" 1.3 parts was added to prepare a hard coat layer coating solution.
This coating solution was applied to the lens by a dipping method (pulling speed of 35 cm per minute). After the coating, it was air-dried at 80 ° C. for 30 minutes and then baked at 120 ° C. for 90 minutes to obtain a hard coat layer having a thickness of 2.3 μm.
(2) Formation of antireflection film Next, the lens is set in a basket so that the convex and concave surfaces are sideways, and the degree of vacuum is 90 to 110 × 10 ⁻³ Torr, the current is 70 ± 10 mA, and the voltage is 0.6 ± 0. The plasma treatment was performed at 1 KV for 60 seconds. Thereafter, the above-described coating liquid for low refractive index layer (C-1) was applied by a dipping method (pickup speed of 10 cm per minute). After the coating, it was air-dried at 80 ° C. for 30 minutes and then baked at 100 ° C. for 180 minutes to obtain a low refractive index film having a thickness of about 100 nm. Further, this lens was water-repellent treated with a fluorine-based silane compound.

(Example 10)
(1) Formation of a hard coat layer 138 parts of propylene glycol methyl ether, the surface of a core particle of a complex oxide having a rutile type crystal structure composed of titanium oxide, tin oxide and silicon oxide is formed on silicon oxide and zirconium oxide. And a composite oxide sol having a solid content concentration of 20 wt%, in which inorganic oxide fine particles having an average particle diameter of 8 nm and coated with a coating layer of a composite oxide made of aluminum and surface-modified with a coupling agent are dispersed in methanol. 688 parts by trade name, manufactured by Kogyo Co., Ltd., trade name OPTRAIQUE "1120Z (8RU-25 / A17)"), 106 parts of γ-glycidoxypropyltrimethoxysilane, glycerol polyglycidyl ether (Nagase Chemical Industries, Ltd.) ), Product name Denacol EX313) 38 parts were mixed. To this mixed solution, 30 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours. After aging overnight, 1.8 parts of Fe (III) acetylacetonate, 0.3 parts of silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7001), phenolic antioxidant (Kawaguchi Chemical) Industrial Co., Ltd. product name "ANTAGE CRYSTAL" 1.3 parts was added to prepare a hard coat layer coating solution.
This coating solution was applied to the lens by dipping in the same manner as in Example 9 to form a hard coat layer.
(2) Formation of antireflection film Next, this lens was subjected to plasma treatment in the same manner as in Example 9, and then the above-described coating solution for low refractive index layer (C-1) was applied by a dipping method and baked. Further, this lens was water-repellent treated with a fluorine-based silane compound.

(Example 11)
(1) Formation of a hard coat layer 187 parts of propylene glycol methyl ether, a surface of a core particle of a complex oxide having a rutile type crystal structure composed of titanium oxide, tin oxide and silicon oxide is formed on silicon oxide and zirconium oxide. And a composite oxide sol having a solid content concentration of 20 wt%, in which inorganic oxide fine particles having an average particle diameter of 8 nm and coated with a coating layer of a composite oxide made of aluminum and surface-modified with a coupling agent are dispersed in methanol. After mixing 625 parts of Kogyo Co., Ltd., trade name OPTRAIQUE "1120Z (8RU-25 / A17)", 106 parts of γ-glycidoxypropyltrimethoxysilane, glycerol polyglycidyl ether (Nagase Kasei Kogyo Co., Ltd.) ), Trade name Denacol EX313) 50 parts was mixed. To this mixed solution, 30 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours. After aging for a whole day and night, 2.1 parts of Fe (III) acetylacetonate, 0.7 parts of magnesium perchlorate, 0.3 parts of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7001) Then, 1.3 parts of a phenolic antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “ANTAGE CRYSTAL”) was added to prepare a coating solution for a hard coat layer.
This coating solution was applied to the lens by the dipping method in the same manner as in Example 5 to form a hard coat layer.
(2) Formation of antireflection film Next, this lens was subjected to plasma treatment in the same manner as in Example 9, and then the above-described coating solution for low refractive index layer (C-1) was applied by a dipping method and baked. Further, this lens was water-repellent treated with a fluorine-based silane compound.

(Comparative Example 6)
(1) Formation of a hard coat layer 197 parts of propylene glycol methyl ether, the surface of a core particle of a complex oxide having a rutile type crystal structure composed of titanium oxide, tin oxide and silicon oxide is formed on silicon oxide and zirconium oxide. And a composite oxide sol having a solid content concentration of 20 wt%, in which inorganic oxide fine particles having an average particle diameter of 8 nm and coated with a coating layer of a composite oxide made of aluminum and surface-modified with a coupling agent are dispersed in methanol. After mixing 625 parts of Kogyo Co., Ltd., trade name OPTRAIQUE "1120Z (8RU-25 / A17)"), 88 parts of γ-glycidoxypropyltrimethoxysilane and glycerol polyglycidyl ether (Nagase Kasei Kogyo Co., Ltd.) ), Product name Denacol EX313) 63 parts were mixed. To this mixed solution, 24 parts of a 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours. After aging for a whole day and night, 2.2 parts of Fe (III) acetylacetonate, 0.7 parts of magnesium perchlorate, 0.3 part of silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name L-7001) Then, 1.3 parts of a phenolic antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “ANTAGE CRYSTAL”) was added.
This coating solution was applied to the lens by dipping in the same manner as in Example 9 to form a hard coat layer.
(2) Formation of antireflection film Next, this lens was subjected to plasma treatment in the same manner as in Example 9, and then the above-described coating solution for low refractive index layer (C-1) was applied by a dipping method and baked. Further, this lens was water-repellent treated with a fluorine-based silane compound.

(Comparative Example 7)
(1) Formation of a hard coat layer The surface of a core particle of a composite oxide having a rutile type crystal structure composed of 152 parts of propylene glycol methyl ether, titanium oxide, tin oxide and silicon oxide is formed on silicon oxide and zirconium oxide. And a composite oxide sol having a solid content concentration of 20 wt%, in which inorganic oxide fine particles having an average particle diameter of 8 nm and coated with a coating layer of a composite oxide made of aluminum and surface-modified with a coupling agent are dispersed in methanol. 625 parts of Kogyo Co., Ltd., trade name OPTRAIQUE "1120Z (8RU-25 / A17)") was mixed, and then 170 parts of γ-glycidoxypropyltrimethoxysilane and glycerol polyglycidyl ether (Nagase Kasei Kogyo Co., Ltd.) ), Product name Denacol EX313) 5 parts were mixed. To this mixed solution, 47 parts of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours. After aging for a whole day and night, 1.7 parts of Fe (III) acetylacetonate, 0.5 parts of magnesium perchlorate, 0.3 parts of silicone surfactant (trade name L-7001, manufactured by Nippon Unicar Co., Ltd.) Then, 1.3 parts of a phenolic antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “ANTAGE CRYSTAL”) was added.
This coating solution was applied to the lens by dipping in the same manner as in Example 9 to form a hard coat layer.
(2) Formation of antireflection film Next, this lens was subjected to plasma treatment in the same manner as in Example 9, and then the above-described coating solution for low refractive index layer (C-1) was applied by a dipping method and baked. Further, this lens was water-repellent treated with a fluorine-based silane compound.

Table 3 shows the weight ratio of the solid content after firing of the hard coat layers of the lenses produced in Examples 9 to 11 and Comparative Examples 6 and 7, and Table 4 shows the evaluation of the test.

When the blending amount of glycerol polyglycidyl ether, which is a polyfunctional epoxy compound as in Examples 9 to 11, is in the range of 4 to 22% by weight of the solid content, the scratch resistance is excellent and the hardness is sufficient. Is recognized. In addition, since the balance between water resistance and flexibility is good, it is possible to prevent the occurrence of cracks even when heat is repeatedly applied from the heat resistance test, and it is recognized from the weather resistance crack test that it has excellent weather resistance. It is done.
When the blending amount of the polyfunctional epoxy compound is small, the heat resistance and adhesion are lowered, and when too large, the hardness is lowered.

The plastic lens of the present invention can be used as a high-performance plastic spectacle lens because it is easy to see because reflection is prevented and has excellent scratch resistance and weather resistance.
Moreover, the manufacturing method of the plastic lens of this invention can be utilized for the use which manufactures such a high performance plastic lens.

Claims (15)

In a plastic lens having a plastic lens substrate, a hard coat layer formed on the plastic lens substrate, and an antireflection film formed on the hard coat layer, the hard coat layer is at least the following ( A) component and (B) component (A) inorganic oxide fine particles containing titanium oxide having a rutile crystal structure with an average particle size of 1 to 200 nm, (B) represented by the general formula: R ¹ SiX ¹ ₃ From a coating composition containing an organosilicon compound (wherein R ¹ represents an organic group having 2 or more carbon atoms having a polymerizable reactive group, and X ¹ represents a hydrolyzable group). A coating film formed, wherein the antireflection film is an organic thin film having a refractive index lower by 0.10 or more than a refractive index of the hard coat layer and having a thickness of 50 nm to 150 nm. Plastic lens to be butterflies. The plastic lens according to claim 1, wherein
The inorganic oxide fine particles include a composite oxide having an average particle diameter of 1 to 200 nm having a rutile crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. . The plastic lens according to claim 2,
The inorganic oxide fine particles include (i) titanium oxide and tin oxide, or a surface of a composite oxide core particle having a rutile-type crystal structure composed of titanium oxide, tin oxide and silicon oxide, and (ii) silicon oxide and A plastic lens comprising a coating of a composite oxide composed of zirconium oxide and / or aluminum oxide. In the plastic lens according to claim 1, wherein the antireflection film, the following component (F) and (G) component (F) the general ^formula: in _{^{R 5 r R 6 q SiX 5}} 4-q-r (Wherein R ⁵ is an organic group having a polymerizable reactive group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, X ⁵ is a hydrolyzable group, and q is 0) Or 1, r is 0 or 1.) (G) A plastic lens, which is an organic thin film formed from a coating composition containing silica-based fine particles having an average particle diameter of 1 to 150 nm. The plastic lens according to claim 4, wherein the silica-based fine particles have an internal cavity. The plastic lens according to claim 5, wherein
The plastic lens, wherein the silica-based fine particles have an average particle diameter of 20 to 150 nm and a refractive index in a range of 1.16 to 1.39. The plastic lens according to any one of claims 1 to 6, wherein the coating composition for forming the hard coat layer further comprises (C) a component (C) a polyfunctional epoxy compound. lens. In the plastic lens according to any one of claims 1 to 7, the coating composition for forming the hard coat layer further, (D) Component (D) the general ^formula: represented by _{R 2 n} ^SiX 2 _4-n An organic silicon compound (wherein R ² represents a hydrocarbon group having 1 to 3 carbon atoms, X ² represents a hydrolyzable group, and n represents 0 or 1). Plastic lens. 9. The plastic lens according to claim 1, wherein the coating composition for forming the hard coat layer further comprises (E) component (E) general formula: X ³ _3-m -Si (R ³ _{m ^{) -Y-Si (R 4 m}} ) -X 4 represented by disilane compound _3-m (wherein, ^{R 3} and ^{R 4} each represent a hydrocarbon group having 1 to 6 carbon atoms, ^{X 3} and ^{X 4} Represents a hydrolyzable group, Y represents an organic group containing a carbonate group or an epoxy group, and m represents 0 or 1). A hard coat layer forming step of forming a hard coat layer from a coating composition containing at least the following component (A) and component (B) on a plastic lens substrate; and (A) an average particle diameter of 1 to 200 nm Inorganic oxide fine particles containing titanium oxide having a rutile crystal structure, (B) an organic silicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ has a polymerizable reactive group) An organic group having 2 or more carbon atoms, and X ¹ represents a hydrolyzable group.) On the hard coat layer, the refractive index is 0.10 or more lower than the refractive index of the hard coat layer, and 50 nm. An antireflection film forming step of forming an organic thin film having a thickness of ˜150 nm. In the manufacturing method of the plastic lens of Claim 10,
The inorganic oxide fine particles include a composite oxide having an average particle diameter of 1 to 200 nm having a rutile crystal structure composed of titanium oxide and tin oxide, or titanium oxide, tin oxide and silicon oxide. Manufacturing method. The plastic lens according to claim 11, wherein
The inorganic oxide fine particles include (i) titanium oxide and tin oxide, or a surface of a composite oxide core particle having a rutile-type crystal structure composed of titanium oxide, tin oxide and silicon oxide, and (ii) silicon oxide and What is claimed is: 1. A method for producing a plastic lens, comprising a material coated with a complex oxide coating layer comprising zirconium oxide and / or aluminum oxide. In the manufacturing method of the plastic lens in any one of Claims 10-12,
The organic thin film formed in the antireflection film forming step is composed of an organic silicon represented by the following (F) component and (G) component (F) general formula: R ⁵ _r R ⁶ _q SiX ⁵ _4-qr Compound (wherein R ⁵ is an organic group having a polymerizable reactive group, R ⁶ is a hydrocarbon group having 1 to ⁶ carbon atoms, X ⁵ is a hydrolyzable group, q is 0 or 1, and r is 0 Or 1.)
(G) A method for producing a plastic lens, comprising forming a coating composition containing silica-based fine particles having an average particle diameter of 1 to 150 nm. In the manufacturing method of the plastic lens of Claim 13,
The method for producing a plastic lens, wherein the silica-based fine particles have an internal cavity. In the manufacturing method of the plastic lens of Claim 14,
The method for producing a plastic lens, wherein the silica-based fine particles have an average particle diameter of 20 to 150 nm and a refractive index in a range of 1.16 to 1.39.