JP2007101779A - Method for manufacturing optical component, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing optical components capable of improving the durability of the optical components by making hard coat layers hardly peelable to improve the adhesion of the hard coat layers and the base materials, and to provide an optical component manufactured by the manufacturing method. <P>SOLUTION: Spectacle lenses which are the optical components formed with base materials and the hard coat layers on the base materials are manufactured. The method includes an adjustment step of adjusting the pH value when the hard coat liquid containing inorganic oxide particles containing titanium oxide having a crystal structure of a rutile type and an organic silicon compound expressed by R<SP>1</SP>SiX<SP>1</SP><SB>3</SB>(where R<SP>1</SP>denotes an organic group having a polymerizable reaction group, and X<SP>1</SP>denotes a hydrolyzable group) is diluted 10 times with diluted water to 5.0 to 10.0 and a hard coat layer forming step of forming the hard coat layers by coating the surfaces of the base materials with the hard coat liquids adjusted in the pH value to 5.0 to 10.0. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical component manufacturing method and an optical component.

  Conventionally, plastic base materials have been used as base materials for optical components such as eyeglass lenses. A plastic substrate is lighter and more moldable than a glass substrate, but the surface is very easily damaged. Therefore, a hard coat layer is formed on a plastic substrate to improve the scratch resistance. In recent years, a material having a high refractive index has been used as a material for the substrate in order to further reduce the weight and thickness of the substrate.

  When using such a high refractive index base material, it is necessary to prevent the occurrence of interference fringes due to the difference in refractive index between the hard coat layer and the base material. It is necessary to increase the refractive index to the same level as the above.

  Therefore, a metal oxide sol mainly composed of titanium oxide having a high refractive index is used, and a metal oxide sol mainly composed of titanium oxide having a rutile-type crystal structure with high light resistance is used as a hard coat layer. Addition has been proposed (see Patent Document 1).

  In general, anatase-type titanium oxide has photoactivity, and when it receives light (ultraviolet rays), it decomposes organic substances (such as a silane coupling agent, which is a component forming a hard coat layer) with a strong oxidative degradation power. . As a result, there is a problem that cracks and film peeling occur and the durability of the optical component is lowered. However, since titanium oxide having a rutile-type crystal structure has lower photoactivity than anatase-type titanium oxide, the use of titanium oxide having a rutile-type crystal structure in the hard coat layer can produce organic matter (hard coat). The decomposition of the silane coupling agent, which is a component forming the layer, can be suppressed, and the durability of the optical component can be improved.

JP 11-310755 A (pages 3 to 10)

  As described above, when titanium oxide having a rutile-type crystal structure is used for the hard coat layer, durability is improved as compared with the case where anatase-type titanium oxide is used. However, it is difficult to reliably prevent the hard coat layer from peeling off, and it cannot be said that the durability is sufficient.

  Among them, the durability of the hard coat layer on a thiourethane-based or episulfide-based plastic substrate, which is a high refractive index material, is particularly insufficient, and further improvement in durability is strongly desired.

  The objective of this invention provides the manufacturing method of the optical component which can improve the durability of an optical component by improving the adhesiveness of the hard-coat layer with respect to a base material, and the optical component manufactured by this manufacturing method. That is.

An optical component manufacturing method according to the present invention includes a plastic base material and a hard coat layer formed on the base material and containing inorganic oxide particles containing titanium oxide having a rutile crystal structure. The hard coat layer is formed from a hard coat liquid containing the inorganic oxide particles and the following component (A), and an alkaline solution or an acidic solution is added to the hard coat liquid. By adding, the hard coat liquid is adjusted to a pH value of 5.0 or more and 10.0 or less when diluted 10 times with distilled water, and the hard coat liquid adjusted pH value, And a hard coat layer forming step of forming a hard coat layer by coating the surface of the substrate.
(A) General formula: organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms having a polymerizable reactive group, and X ¹ is hydrolyzable. Group)

  According to the present invention, a hard coat liquid containing inorganic oxide particles containing titanium oxide having a rutile-type crystal structure and the component (A) (so-called silane coupling agent) is added to distilled water. Then, after the pH value when diluted 10 times is 5.0 or more and 10.0 or less, the substrate surface is coated with a hard coat solution.

  By adjusting the pH value when the hard coat solution is diluted 10 times with distilled water to 5.0 or more and 10.0 or less, hydrolysis of the hydrolyzable group of the component (A) is promoted, and siloxane bond Can be sufficiently formed. (A) When the bond between components is insufficient, the hard coat layer may be peeled off from a weakly bonded part, and the adhesion is particularly good on thiourethane-based substrates and episulfide-based substrates. Often not available. As in the present invention, by sufficiently bonding the components (A), the hard coat layer can be made difficult to peel off, and the adhesion between the hard coat layer and the substrate can be improved.

  In addition, since the pH value of the hard coat liquid was conventionally less than 5.0, the hydrolysis of the hydrolyzable group of the component (A) is not sufficient, and the crosslinking reaction between the components (A) is insufficient. There was a tendency for the adhesion of the hard coat layer to be easily lowered.

  In addition, when the pH value when the hard coat solution is diluted 10 times with distilled water is made higher than 10.0, the condensation reaction of the component (A) is accelerated rapidly, Gelation tends to proceed, causing a problem in the pot life of the coating liquid.

In the present invention, examples of the method for adjusting the pH value of the hard coat solution when diluted 10 times with distilled water in the adjustment step to 5.0 or more and 10.0 or less include the following methods.
(1) In the adjusting step, after adding an alkaline solution or an acidic solution to a hard coat solution obtained by mixing the inorganic oxide particles and the component (A), the pH value of the hard coat solution The method of adjusting to 5.0 or more and 10.0 or less when diluted 10 times with distilled water.
(2) In the adjustment step, after adjusting the pH value of the sol in which the inorganic oxide particles are dispersed in advance by adding an alkaline solution or an acidic solution, the hard coat obtained by mixing the component (A) and the sol A method of adjusting the pH value to be 5.0 or more and 10.0 or less when the liquid is diluted 10 times with distilled water.

  In the method (1), an alkaline aqueous solution or the like is added to the hard coat solution containing the inorganic oxide particles and the component (A) so that the pH value of the hard coat solution is 5.0 or more and 10.0 or less. And since alkaline aqueous solution etc. are added after preparing a hard-coat liquid, the pH value of a hard-coat liquid can be adjusted to a desired value.

  In the method (2), the pH value of the sol in which the inorganic oxide particles are dispersed is adjusted, and the pH value of the hard coat liquid is set to 5.0 or more and 10.0 or less. Compared with the method (1) described above, fluctuation (variation) between sol lots can be suppressed, and when the dispersion stability of the sol itself is poor, the pH value is adjusted to improve the dispersion stability. Can do.

  Furthermore, in the present invention, the hard coat solution preferably contains acetylacetonate having Fe (III) as a central metal atom.

  Acetylacetonate having Fe (III) as a central metal atom serves as a curing catalyst for the hard coat layer.

  In the present invention, the pH value of the hard coat solution is set to 5.0 or more and 10.0 or less. The reason is that the pot life can be extended by the hard coat liquid in the pH range compared to the pH range other than the pH range. However, since the degree of hydrolysis of the hydrolyzable group of the component (A) is likely to change as the pH value of the hard coat solution varies, it is difficult to maintain a stable hard coat solution state.

  Therefore, in the present invention, by adding acetylacetonate having Fe (III) as a central metal atom to the hard coat solution, a stable hard coat solution state is maintained regardless of the pH value, and the pot The effect of extending life can be stably expressed.

  In the present invention, it is preferable to form an antireflection film on the hard coat layer.

The following two methods can be proposed as a method for forming the antireflection film.
(1) A method in which an inorganic antireflection film is formed on the hard coat layer, and the antireflection film forming step of forming the inorganic antireflection film by a dry method is performed after the hard coat layer forming step. .
(2) An organic antireflection film having a refractive index lower by 0.10 or more than that of the hard coat layer is formed on the hard coat layer, and the organic coating is formed by a wet method after the hard coat layer forming step. A method of performing an antireflection film forming step of forming an antireflection film.

  In the method (2), since the antireflection film is formed by a wet method, a large facility such as a vacuum apparatus is not required, and the manufacturing cost can be reduced.

  Further, if the method (2) is adopted, the hard coat layer and the antireflection film can be continuously formed by a wet method, so that no effort is required for the production of the optical component.

  Furthermore, compared with inorganic antireflective coatings mainly composed of inorganic substances formed by dry methods, organic antireflective coatings formed by wet methods have a thermal expansion with plastic substrates and hard coat layers. Since the rate difference is small, cracks due to heating are less likely to occur, so that an optical component with excellent heat resistance can be obtained.

In the case of forming an antireflection film by the method (2), the organic antireflection film comprises silica-based particles having internal cavities, R ² R ³ _n SiX ² _3-n (wherein R ² is An organic group having a polymerizable reactive group, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X ² is a hydrolytic group, and n is 0 or 1. It is preferable to contain.

  According to the present invention, since the silica-based particles have internal cavities, they can include gases and solvents having a refractive index lower than that of silica. Thereby, the silica-based particle having the internal cavity has a lower refractive index than the silica-based particle not having the internal cavity, and the refractive index of the organic antireflection film is decreased. By reducing the refractive index of the organic antireflection film, the difference in refractive index with the hard coat layer is increased, and the antireflection function can be improved.

  In the present invention, the substrate is preferably a thiourethane plastic having a thiourethane structure or an episulfide plastic produced by polymerizing and curing a compound having an episulfide group.

  When the base material is a thiourethane plastic having a thiourethane structure or an episulfide plastic produced by polymerizing and curing a compound having an episulfide group, the hard coat layer is generally easy to peel off. By forming the hard coat layer with the production method of the invention, the adhesion of the hard coat layer can be improved even when a thiourethane plastic or episulfide plastic substrate is used.

  The optical component of the present invention is manufactured by any one of the above-described optical component manufacturing methods.

  Such an optical component of the present invention is manufactured by any one of the optical component manufacturing methods described above, so that the hard coat layer is hardly peeled off, the adhesion between the hard coat layer and the substrate is improved, and the durability is improved. It has become improved.

  Embodiments of the present invention will be described below.

  The spectacle lens of the present embodiment includes a transparent base material, a hard coat layer formed on the base material, and an organic antireflection film formed on the hard coat layer.

(1. Base material)
The material of the substrate is not particularly limited as long as it is made of plastic, but it is preferable to use a material having a refractive index of 1.6 or more.

  For example, a polythiourethane plastic produced by reacting a compound having an isocyanate group or isothiocyanate group with a compound having a mercapto group, or a raw material monomer containing a compound having an episulfide group is produced by polymerization and curing. Episulfide plastics can be used as the base material.

  As the compound having an isocyanate group or an isothiocyanate group as a main component of the polythiourethane plastic, a known compound can be used without any limitation.

  Specific examples of the compound having an isocyanate group include ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate and the like. It is done.

  Moreover, a well-known thing can be used also as a compound which has a mercapto group. For example, 1,2-ethanedithiol, 1,6-hexanedithiol, aliphatic polythiol such as 1,1-cyclohexanedithiol, 1,2-dimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, etc. Aromatic polythiols are mentioned. In addition to the mercapto group, polythiol containing a sulfur atom is more preferably used to increase the refractive index of the plastic lens. Specific examples thereof include 1,2-bis (mercaptomethylthio) benzene, 1, Examples include 2,3-tris (mercaptoethylthio) benzene and 1,2-bis ((2-mercaptoethyl) thio) -3-mercaptopropane.

  Moreover, as a specific example of a compound having an episulfide group used as a raw material monomer for an episulfide plastic, a compound having a known episulfide group can be used without any limitation. Examples thereof include episulfide compounds obtained by replacing some or all of the epoxy groups of existing epoxy compounds with sulfur. In order to increase the refractive index of the plastic lens, a compound containing a sulfur atom in addition to the episulfide group is more preferable. Specific examples include 1,2-bis (β-epithiopropylthio) ethane, bis- (β-epithiopropyl) sulfide, 1,4-bis (β-epithiopropylthiomethyl) benzene, 2,5 -Bis (β-epithiopropylthiomethyl) -1,4-dithiane, bis- (β-epithiopropyl) disulfide and the like.

  The method for polymerizing the substrate in the present invention is not particularly limited, and a polymerization method generally used for production of a substrate can be used without any limitation. For example, when a vinyl monomer is used, a base material can be produced by performing thermosetting using a thermal polymerization initiator such as an organic peroxide. Moreover, a monomer can be hardened by irradiating an ultraviolet-ray using photoinitiators, such as a benzophenone, and a base material can also be manufactured.

  When a polythiourethane plastic produced by reacting a compound having an isocyanate group or an isothiocyanate group with a compound having a mercapto group is used as a material for the base material, the isocyanate group or the isothiocyanate group is added. It can be manufactured by mixing a compound having a compound and a compound having a mercapto group, and then adding and mixing a curing catalyst for urethane resin, followed by heat curing.

  Specific examples of the curing catalyst include amine compounds such as ethylamine, ethylenediamine, triethylamine, and tributylamine, dibutyltin dichloride, dimethyltin dichloride, and the like.

  When using an episulfide-based plastic obtained by polymerizing a raw material monomer containing a compound with an episulfide group as the base material, the compound with an episulfide group can be used alone or with an episulfide group. After mixing with other monomers, a curing catalyst for epoxy resin can be added and mixed, followed by polymerization and curing by heating.

  There are no particular limitations on the curing catalyst for the epoxy resin, but specific examples include tertiary amines such as dimethylbenzylamine, dimethylcyclohexylamine, diethylethanolamine, dibutylethanolamine, tridimethylaminomethylphenol, and ethylmethylimidazole. And imidazoles.

  Examples of other monomers copolymerizable with a compound having an episulfide group include a compound having a hydroxyl group, a compound having a mercapto group, a primary or secondary amine, and a compound having a carboxyl group.

  Specific examples of the compound having a hydroxyl group include alcohols such as isopropyl alcohol and n-hexyl alcohol, and polyhydric alcohols such as ethylene glycol, 1,6-hexanediol, pentaerythritol dimethacrylate, and pentaerythritol diacrylate. . Specific examples of the compound having a mercapto group include thiophenol, ethylthioglycolate, bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and the like.

(2. Hard coat layer)
The hard coat layer has at least the following component (A) and component (B). (A) Organosilicon compound represented by the general formula: R ¹ SiX ¹ ₃ (wherein R ¹ is an organic group having a polymerizable reactive group, and X ¹ represents a hydrolyzable group). (B) Inorganic oxide particles containing titanium oxide having a rutile-type crystal structure.

  The component (A) serves as a binder for the hard coat layer.

In the chemical formula of the component (A), R ¹ is an organic group having a polymerizable reactive group, and has 1 to 6 carbon atoms. R ¹ has a polymerizable reactive group such as vinyl group, allyl group, acrylic group, methacryl group, 1-methylvinyl group, epoxy group, mercapto group, cyano group, isocyano group, amino group and the like.

X ¹ is a hydrolyzable functional group, and 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.

  Examples of the organosilicon compound of component (A) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, and methacryloxypropyltrialkoxysilane. , Γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane and the like. Two or more kinds of the organosilicon compounds as the component (A) may be mixed and used.

  (B) The average particle diameter of the titanium oxide of a component is 1-200 nm, Preferably it is 5-30 nm. In addition, the inorganic oxide particles of component (B) may contain only titanium oxide, or may contain titanium oxide and other inorganic oxides.

  For example, a mixture of titanium oxide and metal oxides such as Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In may be used.

  Furthermore, the inorganic oxide particles of the component (B) may be composite particles of titanium oxide and other inorganic oxides.

  When using composite particles, for example, a composite of a metal oxide such as Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, and In and titanium oxide. Use it.

  When the component (B) is mixed with the component (A) to produce a hard coat liquid for forming a hard coat layer, the sol in which the component (B) is dispersed and the component (A) are mixed. It is preferable.

  (B) The inorganic oxide particle containing the titanium oxide which has a rutile type crystal structure which is a component is disperse | distributed to a dispersion medium, for example, water, alcohol, or another organic solvent. In order to increase the dispersion stability of the inorganic oxide particles, the surface of the inorganic oxide particles may be treated with an organic silicon compound or an amine compound.

  In this case, examples of the organosilicon compound used include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane.

  Examples of amine compounds include alkylamines such as ammonium, ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine. Can be illustrated.

  The addition amount of these organosilicon compounds and amine compounds is preferably in the range of about 1 to 15% with respect to the weight of the inorganic oxide particles.

  (B) Although the compounding quantity of a component is determined by the hardness of a hard-coat layer, a refractive index, etc., it is 5 to 80 weight% of solid content in a hard-coat liquid, Especially 10 to 50 weight%. It is preferable. If the blending amount is too small, the wear resistance of the hard coat layer becomes insufficient, and if the blending amount is too large, cracks may occur in the hard coat layer. Moreover, when dyeing | hardening a hard-coat layer, dyeability may fall.

  Furthermore, the hard coat layer may contain a polyfunctional epoxy compound as the component (C) as well as the component (A) and the component (B).

  The polyfunctional epoxy compound can improve the adhesion of the hard coat layer to the substrate and improve the water resistance of the hard coat layer.

  When the antireflection film on the hard coat layer is formed of an organic film, the film thickness of the antireflection film is often very thin, especially when silica-based particles having internal cavities are used in the antireflection film. In order to pass water, the hard coat layer needs to have water resistance.

  Examples of the multifunctional epoxy compound include 1,6-hexanediol diglycidyl 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 hydroxyhybalic acid ester Diglycidyl ether, trimethylolpropa Diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether , Pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanate, triglycidyl ether of tris (2-hydroxyethyl) isocyanate, etc. Compound, isophoronediol diglycidyl Ether, alicyclic epoxy compounds such as bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether And aromatic epoxy compounds such as phenol novolac polyglycidyl ether and cresol novolac polyglycidyl ether.

  Among them, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl) isocyanate Aliphatic epoxy compounds such as triglycidyl ether are preferred.

  Further, a curing catalyst may be added to the hard coat layer. Examples of the curing catalyst include perchloric acids such as perchloric acid, ammonium perchlorate, and magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (II), and Be (II). , Ce (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III) Acetylacetonate having a central metal atom such as Ce (IV), Zr (IV), V (IV), amino acids such as amine and glycine, Lewis acid, organic acid metal salts and the like.

  Among these, the most preferable curing catalyst includes acetylacetonate having magnesium perchlorate, Al (III), and Fe (III) as a central metal atom. Among them, it is preferable to use acetylacetonate having Fe (III) as a central metal atom.

  The addition amount of the curing catalyst is desirably in the range of 0.01 to 5.0% by weight of the solid content concentration of the hard coat liquid.

  The film thickness of the hard coat layer is preferably 0.05 to 30 μm. If it is less than 0.05 μm, the basic function of the hard coat layer for protecting the substrate cannot be exhibited, and if it exceeds 30 μm, the smoothness of the surface of the hard coat layer is impaired.

(3. Antireflection film)
The organic antireflection film is composed of a single-layer organic film, has a refractive index of 0.10 or more lower than that of the hard coat layer, and a film thickness of 50 to 150 nm.

  The refractive index of the organic antireflection film may be 0.10 or more lower than that of the hard coat layer, but is preferably 0.15 or more, more preferably 0.20 or more.

The organic antireflection film contains the following components (D) and (E). (D) General formula: R ² R ³ _n SiX ² _3-n (wherein R ² is an organic group having a polymerizable reactive group, and R ³ is a hydrocarbon group having 1 to 6 carbon atoms) , X ² is a hydrolyzable group, and n is 0 or 1) Organosilicon compound (E) Silica-based particles having an internal cavity.

(D) an organic group having a polymerizable reactive group R ² of component, for example, vinyl group, allyl group, acryl group, methacryl group, an epoxy group, a mercapto group, a cyano group, isocyano group, polymerization such as an amino group Has possible reactive groups.

Examples of the hydrocarbon group having 1 to 6 carbon atoms R ³ of component (D), a methyl group, an ethyl group, a butyl group, a vinyl group, a phenyl group, a perfluoroalkyl group or the like can be exemplified.

Furthermore, examples of X ² of the component (D) include alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

  Examples of the organosilicon compound of component (D) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, and methacryloxypropyltrialkoxysilane. , Methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N -Β (aminoethyl) -γ-aminopropylmethyl dialkoxysilane, perfluoroalkyltrialkoxysilane and the like. Two or more of these may be used in combination.

(E) It is preferable that the average particle diameter of the silica particle which has an internal cavity of a component is as follows.
(Average particle diameter) = (design wavelength (nm) / refractive index of antireflection film) × 1/4

  In addition to the above components (D) and (E), the organic antireflection film includes resins such as polyurethane resins, epoxy resins, melamine resins, polyolefin resins, urethane acrylate resins, epoxy acrylate resins, and raw materials for these resins. It is possible to add various monomers such as methacrylates, acrylates, epoxies, and vinyls.

  In addition to these components, if necessary, curing catalysts, surfactants, antistatic agents, UV absorbers, antioxidants, hindered amines, hindered phenols and other light stabilizers, disperse dyes, oil solubles. Dyes, fluorescent dyes, pigments and the like may be added to improve light resistance and coatability.

(4. Manufacturing method of spectacle lens)
The spectacle lens as described above is manufactured as follows.

(4-1. Adjustment process)
First, a hard coat liquid for forming a hard coat layer is produced.

  (A) The organosilicon compound of component (A) is dissolved in an organic solvent and hydrolyzed by adding water or hydrochloric acid to produce a hydrolyzate. A sol in which inorganic oxide particles of component (B) are dispersed is added to the hydrolyzate.

  Furthermore, a curing catalyst, a polyfunctional epoxy compound, etc. are added as needed.

  In this embodiment, acetylacetonate having Fe (III) as a curing catalyst as a central metal atom is added.

  In this manufacturing procedure, an alkaline solution such as an aqueous sodium hydroxide solution or an acidic solution such as hydrochloric acid is added to the hard coat solution to adjust the pH value of the hard coat solution. At this time, it is possible to adjust the pH during the preparation process of the hard coat solution, and the pH value when the hard coat solution is finally diluted 10 times with distilled water is 5.0 or more and 10.0 or less. Adjust so that

(4-2. Hard coat layer forming step)
A hard coat solution having a pH value of 5.0 or more and 10.0 or less is applied on the substrate.

  The coating method is arbitrary, and examples thereof include a dipping method, a spin coating method, a spray coating method, a roll coating method, and a flow coating method.

  In order to improve the adhesion between the base material and the hard coat layer, the base material may be subjected to an alkali treatment, an acid treatment, a surfactant treatment, a plasma treatment or the like before the hard coat liquid is applied.

  After the hard coat liquid is applied on the substrate, it is dried at 40 to 200 ° C. for several hours. As a result, a hard coat layer is formed.

(4-3. Antireflection film forming step)
(D) The organosilicon compound as a component is diluted with an organic solvent, and if necessary, water, hydrochloric acid or the like is added for hydrolysis. Thereafter, a sol in which silica-based particles having internal cavities as the component (E) are dispersed is added to the hydrolyzate. Moreover, you may add a curing catalyst, surfactant, an antistatic agent, etc. as needed. Thereby, the coating liquid of the organic antireflection film is completed.

  Thereafter, this coating solution is applied onto the hard coat layer. The coating method is arbitrary, and examples thereof include a dipping method, a spin coating method, a spray coating method, a roll coating method, and a flow coating method.

  Then, the antireflection film is completed by curing the coating liquid with heat, ultraviolet rays or the like. When the coating liquid is cured by heating, it is heated at 50 to 200 ° C.

(5. Effects of the embodiment)
According to this embodiment, the following effects can be achieved.

  (5-1) The organic component (A) serving as a binder agent by adjusting the pH value of the hard coat solution when diluted 10 times with distilled water to 5.0 or more and 10.0 or less. Hydrolysis of the hydrolyzable group of the silicon compound is promoted, and a siloxane bond can be sufficiently formed. (A) When the bonding between the components is insufficient, the hard coat layer may be peeled off from the weakly bonded portion, and in particular, a thiourethane-based plastic substrate and an episulfide-based plastic substrate In many cases, adhesion cannot be obtained. On the other hand, as in this embodiment, not only the hard coat layer can be made difficult to peel by reliably bonding the components (A), but also the adhesion between the hard coat layer and the substrate is improved. Can be made.

  (5-2) In the present embodiment, in the adjustment step, an alkaline solution or an acidic solution is added to the hard coat solution containing the inorganic oxide particles and the component (A), and the hard coat solution is distilled water. The pH value when diluted 10-fold is set to 5.0 or more and 10.0 or less, and an alkaline solution or an acidic solution is added in the preparation process of the hard coat solution, so the pH value of the hard coat solution is accurately adjusted. be able to.

  (5-3) In this embodiment, in the adjustment step, the pH value when the hard coat solution is diluted 10 times with distilled water is set to 5.0 or more and 10.0 or less. The reason is that the pot life can be extended by the hard coat liquid in the pH range compared to the pH range other than the pH range. However, since the degree of hydrolysis of the hydrolyzable group of the component (A) is likely to change as the pH value of the hard coat solution changes, it is difficult to maintain a stable hard coat solution state.

  Therefore, in the present invention, by adding acetylacetonate having Fe (III) as a central metal atom to the hard coat solution, a stable hard coat solution state is maintained regardless of the pH value, and the pot The effect of extending life can be stably expressed.

  (5-4) In this embodiment, since the organic antireflection film is formed by a wet method, a large-scale facility such as a vacuum device used in the dry method is not necessary, and the manufacturing cost can be reduced. Become.

  In the present embodiment, the organic antireflection film is formed by a wet method, and the hard coat layer and the antireflection film can be continuously formed by a wet method.

  (5-5) Furthermore, the organic antireflection film formed by the wet method has a smaller difference in thermal expansion coefficient from the hard coat layer than the antireflection film mainly composed of an inorganic material formed by the dry method. Therefore, generation of cracks due to heating is less likely to occur, so that a spectacle lens having excellent heat resistance can be obtained.

  (5-6) Since the silica-based particles that are the component (E) constituting the organic antireflection film have internal cavities, they can include gases and solvents having a refractive index lower than that of silica. As a result, the silica-based particles having the internal cavities have a lower refractive index than the silica-based particles having no internal cavities, and the refractive index of the organic thin film constituting the organic antireflection film is decreased. By reducing the refractive index of the organic thin film, the difference in refractive index with the hard coat layer is increased, and the antireflection function can be improved.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  For example, in the embodiment, when preparing the hard coat liquid, the organosilicon compound as the component (A) and the sol in which the inorganic oxide particles as the component (B) are dispersed are mixed, and if necessary, After adding a curing catalyst, a polyfunctional epoxy compound, etc., the pH value when the hard coat solution to which an alkaline aqueous solution was added was diluted 10 times with distilled water was set to 5.0 or more and 10.0 or less. For example, an alkaline solution such as an aqueous sodium hydroxide solution or an acidic solution such as hydrochloric acid is added to the sol in which the inorganic oxide particles of the component (B) are dispersed, and the pH value is adjusted. ) The pH value when the hard coat liquid obtained by mixing the components and the like is diluted 10 times with distilled water may be 5.0 to 10.0.

  Thus, by adjusting the pH value of the sol in which the inorganic oxide particles of the component (B) are dispersed, fluctuation (variation) between sol lots can be suppressed, and when the dispersion stability of the sol itself is poor, the pH is adjusted. The dispersion stability can be improved by adjusting the value. In addition, adjustment of pH value is useful not only using the compound which shows alkalinity, but adjusting to arbitrary pH values by using the compound which shows acidity. For example, when the sol itself is alkaline, it may be possible to adjust the pH using a compound that exhibits acidity as necessary. In this case, it is useful to use acidic compounds such as hydrochloric acid and acetic acid, and acidic compounds such as tartaric acid and malic acid.

Furthermore, in the said embodiment, although the anti-reflective film was an organic anti-reflective film comprised by the organic thin film of a single layer, not only this but an anti-reflective film is good also as what has an inorganic substance as a main component. For _{example, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O 3, SnO 2, MgF 2 , An inorganic antireflection film mainly containing an inorganic material such as WO ₃ may be formed. These inorganic substances may be used alone or in combination of two or more.

For example, an antireflection film having five layers of SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ in order from the substrate toward the atmosphere may be used.

  When forming such an antireflection film containing an inorganic substance as a main component, the antireflection film can be formed using a dry method such as a vacuum deposition method, an ion plating method, a sputtering method, or the like. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used.

  Furthermore, although the spectacle lens was manufactured in the said embodiment, it is not restricted to this.

[Example]
Next, examples of the present invention will be described.

(Example 1)
In Example 1, a spectacle lens having a hard coat layer and an antireflection film formed on a substrate was produced.

(Hardcoat liquid adjustment process)
Take 1000 parts by weight of butyl cellosolve in a stainless steel container, add 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane and stir well, then add 300 parts by weight of 0.1 mol / liter hydrochloric acid and stir all day and night. Subsequently, a silane hydrolyzate was obtained.

  On the other hand, sol of composite particles (inorganic oxide particles) mainly composed of titanium oxide (rutile-type crystal structure), tin oxide, and silicon oxide (manufactured by Catalytic Chemical Industry Co., Ltd .; trade name OPTRAIKE 1120Z 8RU-25 / A17) A 0.1 mol / liter sodium hydroxide aqueous solution was added to the solution to adjust the pH value. When the sol was diluted 10 times with distilled water, the pH value was 8.6.

  30 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name L-7001) was added to the silane hydrolyzate and stirred for 1 hour, and then 7300 parts by weight of the sol was added and stirred for 2 hours.

  Next, 250 parts by weight of an epoxy resin (manufactured by Nagase Kasei Co., Ltd .; trade name Denacol EX-313) was added and stirred for 2 hours, and then acetylacetate containing 5 parts by weight of magnesium perchlorate and iron (III) as a central metal atom. Nart 15 parts by weight was added and stirred for 1 hour.

  Further, 13 parts by weight of an antioxidant was added and stirred for 1 hour, followed by filtration with a 2 μm filter to obtain a hard coat solution. It was 7.6 when pH value when this hard coat liquid was diluted 10 times with distilled water was measured.

(Hard coat layer forming process)
Next, a base material made of thiourethane-based plastic (manufactured by Seiko Epson Corporation; trade name Seiko Super Sovereign Fabric) was subjected to alkali treatment. Specifically, the substrate is immersed in a 2.0 normal potassium hydroxide aqueous solution maintained at 50 ° C. for 5 minutes, washed with pure water, and then washed with 0.5 normal sulfuric acid maintained at 25 ° C. The substrate was neutralized by dipping for 1 minute. Thereafter, the substrate was washed with pure water, further dried and allowed to cool.

  Next, the base material is immersed in the hard coat solution, and the lifting speed is 30 cm / min. And then fired at 80 ° C. for 30 minutes, and then heated in an oven set at 125 ° C. for 3 hours to form a hard coat layer.

  The thickness of this hard coat layer is 2 μm.

(Antireflection film forming process)
Add 5000 parts by weight of propylene glycol monomethyl ether and 100 parts by weight of γ-glycidoxypropyltrimethoxysilane to a stainless steel container, add 299 parts by weight of 0.01 mol / liter hydrochloric acid while stirring, and continue stirring all day and night. A silane hydrolyzate was obtained.

  In a separate container, 100 parts by weight of a sol of silica-based particles having an internal cavity (manufactured by Catalyst Kasei Kogyo Co., Ltd.), 1 part by weight of a silicone surfactant (L-7001 by Nippon Unicar Co., Ltd.) and iron (III ) And 1 part by weight of acetylacetonate having a central metal atom was added and stirring was continued for a whole day and night, and then combined with the silane hydrolyzate and further stirred for a whole day and night. Thereafter, the mixture was filtered with a 3 μm filter to obtain a coating solution.

  Next, with respect to the base material on which the hard coat layer was formed in the above-described hard coat layer forming step, the surface of the hard coat layer was subjected to plasma (atmospheric plasma) treatment. Subsequently, it was immersed in the coating liquid, and after 30 seconds, the lifting speed was 10 cm / min. And heated in an oven set at 120 ° C. for 2 hours to form an organic antireflection film.

  The thickness of this antireflection film is 100 nm.

(Example 2)
In Example 2, the antireflection film was an inorganic antireflection film containing an inorganic substance as a main component. Other conditions are the same as those in the first embodiment.

(Inorganic antireflection film forming process)
The base material on which the hard coat layer is formed in the hard coat layer forming step is placed in a vapor deposition apparatus, heated to 85 ° C. while being evacuated, and subjected to ion gun treatment (carrier gas: oxygen, voltage: 400 eV, treatment time: 30 seconds). I did it.

Next, after evacuation was continued to a vacuum degree of 5.0 × 10 ⁻⁵ mbar, a deposition material was deposited by an electron beam heating method, and from the hard coat layer side, SiO ₂ (0.25λ) / TiO ₂ (0.12λ ) / SiO ₂ (0.05λ) / TiO ₂ (0.25λ) / SiO ₂ (0.25λ) to form an inorganic antireflection film (λ (design wavelength) = 550 nm).

Example 3
Also in Example 3, a spectacle lens having a hard coat layer and an antireflection film formed on a substrate was produced.

(Hardcoat liquid adjustment process)
Take 600 parts by weight of butyl cellosolve in a stainless steel container, add 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane and stir well, then add 300 parts by weight of 0.1 mol / liter hydrochloric acid and stir all day and night. Subsequently, a silane hydrolyzate was obtained.

  To this silane hydrolyzate, 30 parts by weight of a silicone surfactant (manufactured by Nihon Unicar Co., Ltd .; trade name L-7001) was added and stirred for 1 hour, and then 0.1 mol / liter sodium hydroxide-methanol. 500 parts by weight of the solution was added and stirred for 1 hour. This is a sol of composite particles (inorganic oxide particles) mainly composed of titanium oxide (rutile type), tin oxide, and silicon oxide (manufactured by Catalytic Chemical Industry Co., Ltd .; trade name OPTRAIK 1120Z 8RU-7 / A15) 7300 weight Part was added and mixed with stirring for 2 hours.

  Next, 250 parts by weight of an epoxy resin (manufactured by Nagase Kasei Co., Ltd .; trade name Denacol EX-313) was added and stirred for 2 hours, and then 15 parts by weight of iron (III) acetylacetonate was added and stirred for 1 hour. Further, 13 parts by weight of an antioxidant was added and stirred for 1 hour, followed by filtration with a 2 μm filter to obtain a hard coat solution. In addition, it was 5.0 when the pH value when this hard coat liquid was diluted 10 times with distilled water was measured.

(Hard coat layer forming process)
A base material made of thiourethane plastic (manufactured by Seiko Epson Corporation; trade name Seiko Super Sovereign Fabric) was alkali-treated. Specifically, the substrate was immersed in a 2.0 N aqueous potassium hydroxide solution maintained at 50 ° C. for 5 minutes, washed with pure water, and then washed with 0.5 N sulfuric acid maintained at 25 ° C. The substrate was immersed for neutralization for a minute.

  Thereafter, the substrate was washed with pure water, dried and allowed to cool, then immersed in the hard coat solution, and the lifting speed was 30 cm / min. And then fired at 80 ° C. for 30 minutes. Furthermore, it heated in the oven set to 125 degreeC for 3 hours, and formed the hard-coat layer. The thickness of this hard coat layer is 2 μm.

(Antireflection film forming process)
The antireflection film forming step was performed under the same conditions as in Example 1.

  The thickness of this antireflection film is 100 nm.

Example 4
In Example 4, the antireflection film was an inorganic antireflection film mainly containing an inorganic substance.

  The conditions for forming the antireflection film are the same as in Example 2.

  Other conditions are the same as in Example 3.

(Example 5)
In Example 5, the 0.1 mol / liter sodium hydroxide aqueous solution in Example 1 was changed to a 0.01 mol / liter acetic acid aqueous solution to adjust the pH value of the sol. At this time, the pH value when the sol was diluted 10 times with distilled water was 5.9, and the pH value when the obtained hard coat solution was diluted 10 times with distilled water was measured. 2. The formation conditions of the antireflection film are the same as those in Example 1.

(Comparative Example 1)
A spectacle lens having a hard coat layer and an antireflection film formed on a substrate was produced.

  It is the same as Example 1 except that the pH value when the hard coat solution is diluted 10 times with distilled water in the adjustment step of the hard coat solution is 4.9.

(Comparative Example 2)
A spectacle lens having a hard coat layer and an antireflection film formed on a substrate was produced.

  Example 2 is the same as Example 2 except that, in the adjustment process of the hard coat solution, the pH value when the hard coat solution was diluted 10 times with distilled water was set to 4.9.

(Comparative Example 3)
In the adjustment process of the hard coat solution of Example 1, the pH value when the hard coat solution was diluted 10 times with distilled water was set to 10.5. Other conditions are the same as those in the first embodiment.

(Evaluation methods)
The durability of the plastic lenses manufactured according to Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated by the following evaluation method. The results are shown in Table 1. The evaluation items are six items of scratch resistance, initial adhesion, moisture resistance, warm water resistance, light resistance and heat resistance.

  In the evaluation of scratch resistance, steel wool (# 0000) was applied to the surface of the plastic lens with a load of 1 kg, and after rubbing 10 times in a distance of 3 to 4 cm, the state of scratches that entered the sample lens surface was visually observed. confirmed. “◯” indicates that no scratches are visible, and “X” indicates that the scratches are clearly visible.

  In the evaluation of the initial adhesion, the surface of the plastic lens was cross-cut into a grid pattern at intervals of about 1 mm using a cutter knife. An adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Cerotape (registered trademark)”) was strongly attached to the cross-cut portion, and then the adhesive tape was rapidly peeled off. Then, the film peeling state of the grid was confirmed visually. “◯” indicates that there is no film peeling, and “×” indicates that there is film peeling.

  In the evaluation of moisture resistance, the plastic lens was left in a constant temperature and humidity furnace (60 ° C., 98 RH%) for 10 days, and then the sample lens was taken out from the constant temperature and humidity furnace and left at room temperature for 3 hours. An adhesion test was performed. The adhesion test was performed by the same method and the same evaluation criteria as the above initial adhesion.

  In the evaluation of hot water resistance, the plastic lens was immersed in warm water at 80 ° C. for 2 hours, and then the sample lens was taken out from the warm water and cooled with water, and then an adhesion test was performed. This adhesion test was also performed by the same method and the same evaluation criteria as the above initial adhesion.

  For evaluation of light resistance, the plastic lens was irradiated with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 200 hours, and the plastic lens was taken out of the sunshine weather meter and cooled with water, and then an adhesion test was performed. This adhesion test was also performed by the same method and the same evaluation criteria as the above initial adhesion.

  In the evaluation of heat resistance, a plastic lens was glazed according to the shape of the spectacle frame, then fitted into the spectacle frame, completely tightened with screws, and placed in a constant temperature bath at 60 ° C. for 30 minutes. Thereafter, the framed lens was taken out of the thermostatic bath, allowed to cool at room temperature for 1 hour, and then evaluated for occurrence of cracks. In the case where no cracks were generated, it was added to a constant temperature bath at 65 ° C. for 30 minutes, and then the presence or absence of cracks was evaluated. Thereafter, the temperature was increased by 5 ° C., and the temperature was further increased for 30 minutes, and the temperature at which cracks occurred was defined as the heat resistant limit temperature.

  In Examples 1 to 5 in which the pH value when the hard coat solution was diluted 10 times with distilled water was 5.0 or more and 10.0 or less, peeling of the hard coat layer and the antireflection film did not occur. In Comparative Examples 1 and 2 in which the pH value when the hard coat solution was diluted 10 times with distilled water was less than 5.0, peeling of the hard coat layer and the antireflection film occurred.

  As a result, it was possible to confirm the effect of the present invention that the durability of the optical component can be improved by making the hard coat layer difficult to peel off and improving the adhesion between the hard coat layer and the substrate. .

  In Comparative Example 3, the hard coat solution gelled and coating was impossible.

The present invention can be used in a method for manufacturing an optical component, for example, a spectacle lens.

Claims (8)

A method for producing an optical component comprising a plastic substrate and a hard coat layer containing inorganic oxide particles containing titanium oxide having a rutile-type crystal structure formed on the substrate,
The hard coat layer is formed from a hard coat liquid containing the inorganic oxide particles and the following component (A),
When an alkaline solution or an acidic solution is added to the hard coat solution, the pH value of the hard coat solution is 5.0 or more when measured by diluting the hard coat solution 10 times with distilled water. An adjustment step for adjusting to 0 or less;
A method of manufacturing an optical component comprising: a hard coat layer forming step of coating the surface of the base material with the hard coat liquid after the adjusting step to form a hard coat layer.
(A) General formula: Organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms having a polymerizable reactive group, and X ¹ is hydrolyzable. Group) In the manufacturing method of the optical component according to claim 1,
In the adjustment step, the pH value of the sol in which the inorganic oxide particles are dispersed is adjusted in advance by adding an alkaline solution or an acidic solution, and then the hard coat solution obtained by mixing the component (A) and the sol. The pH value of the optical component is adjusted to 5.0 or more and 10.0 or less when measured by diluting the hard coat solution 10 times with distilled water. In the manufacturing method of the optical component according to claim 1 or 2,
The method for producing an optical component, wherein the hard coat liquid contains acetylacetonate having Fe (III) as a central metal atom. In the manufacturing method of the optical component in any one of Claim 1 to 3,
A method for manufacturing an optical component, comprising performing an antireflection film forming step of forming an inorganic antireflection film on the hard coat layer by a dry method after the hard coat layer forming step. In the manufacturing method of the optical component in any one of Claim 1 to 3,
After the hard coat layer forming step, an antireflection film forming step is performed on the hard coat layer by a wet method to form an organic antireflection film having a refractive index lower than that of the hard coat layer by 0.10 or more. A method of manufacturing an optical component characterized by the above. In the manufacturing method of the optical component according to claim 5,
The organic antireflection film, silica-based particles having an internal cavity,
R ² R ³ _n SiX ² _3-n (wherein R ² is an organic group having a polymerizable reactive group, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, and X ² is a hydrolysis group) And an organic silicon compound represented by the formula (n is 0 or 1). In the manufacturing method of the optical component in any one of Claim 1 to 6,
A method for producing an optical component, wherein the base material is a thiourethane plastic having a thiourethane structure or an episulfide plastic produced by polymerizing and curing a compound having an episulfide group.   An optical component manufactured by the method for manufacturing an optical component according to claim 1.