JP2007025631A - Method for manufacturing optical component, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an optical component by which the abrasion resistance of an optical component such as a plastic lens can be improved, and to provide an optical component produced by the production method. <P>SOLUTION: A hard coat layer is formed by a hard coat layer forming process including: an application step of applying a hard coat liquid on a plastic substrate; a temporary firing step of preliminarily curing the hard coat liquid by a hydrolysis reaction; a moisturizing step of moisturizing the preliminarily cured hard coat layer; and a conclusive firing step of concluding the curing of the hard coat liquid by a further hydrolysis reaction. <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, generally, a hard coat layer is formed on a plastic substrate to improve the scratch resistance.
For example, a method is often used in which a hard coat layer is formed by applying a hard coat solution before curing to a plastic substrate and then curing it by a predetermined heat treatment. If this curing reaction is insufficient, the scratch resistance effect of the hard coat layer cannot be exhibited sufficiently.
In view of this, there has been proposed a method in which the process of curing the hard coat liquid (firing process) is divided into two stages of a pre-firing process and a main firing process to perform the curing reaction more completely (for example, Patent Document 1).

JP-A-5-019212 (page 7)

  However, even with the method of Patent Document 1, the hard coat solution is not completely cured, and thus it cannot be said that the scratch resistance of the optical component is sufficient. Further, since an antireflection layer is generally formed on the hard coat layer, if the hardness of the hard coat layer itself and the adhesion with the antireflection layer are not sufficient, the optical component was physically stimulated from the outside. In some cases, so-called film peeling may occur. In particular, when the organic antireflection film is formed on the hard coat layer, the surface is softer than the inorganic antireflection film, so that the hard coat layer is strongly influenced.

  SUMMARY OF THE INVENTION An object of the present invention is to provide an optical component manufacturing method capable of improving the scratch resistance of an optical component by sufficiently curing a hard coat liquid serving as a hard coat layer, and an optical component manufactured by this manufacturing method. Is to provide.

  The method for producing an optical component of the present invention is a method for producing an optical component comprising a plastic substrate and a hard coat layer formed on the substrate, wherein the hard coat layer comprises a hard coat solution. An application step of applying the coating onto the base material, a pre-baking step of obtaining a pre-hardened hard coat layer by pre-curing the hard coat liquid applied onto the base material after the application step by a hydrolysis reaction, and the pre-baking After the process, water is added to the pre-cured hard coat layer to obtain a water-containing pre-cured hard coat layer, and the water-containing pre-cured hard coat layer is cured by further hydrolysis reaction after the water addition process. And a main-coating step for forming a hard coat layer.

According to the present invention, since a provisional baking process for curing the hard coat liquid and a main baking process for completing the curing of the hard coat liquid, a water addition process for adding moisture to the hard coat layer is provided. Even when an antireflection film is formed on the hard coat layer after the main baking step, it is excellent in scratch resistance as an optical component.
The reason for this is not necessarily clear, but since the moisture is included in the hard coat layer after the preliminary firing step, the unreacted hard coat liquid component remaining in the hard coat layer reacts with the moisture in the main firing step and hardens. It is thought that the reaction was completed. As a result, it is presumed that the hardness of the hard coat layer itself is improved and the adhesion to the antireflection film and the plastic substrate is also improved, which contributes to scratch resistance.

In this invention, it is preferable that the said application | coating process includes the process of apply | coating the hard-coat liquid containing the inorganic oxide particle containing the titanium oxide of a rutile type crystal structure, and the following (A) component on the said base material.
(A) General formula: Organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein R ¹ is an organic group having a polymerizable reactive group, and X ¹ represents a hydrolyzable group)

Wherein, ^{R 1} is, for example, a hydrocarbon group having 1 to 6 carbon atoms.
According to the present invention, the hard coat liquid is composed of inorganic oxide particles containing titanium oxide having a rutile-type crystal structure and a predetermined organosilicon compound, so that it has sufficient hardness as a hard coat layer after curing. It is possible to improve the scratch resistance of the surface of the optical component.

In this invention, it is preferable that the moisture content W shown to following formula (1) of the said moisture containing pre-hardening hard-coat layer is 0.005-0.13 mass%.
W = {(B−B1) − (A−A1)} / (B−B1) (1)
(In the formula, A is the mass of the base material and the pre-cured hard coat layer after the pre-baking step in the above step. B is the base material and the water-containing pre-cured hard coat after the water addition step in the above step. The mass of the layer, A1 is the mass of the base material only, and B1 is the mass of the base material after passing only the base material directly through the water addition step.)
According to the present invention, since the moisture content of the hard coat layer after pre-baking is 0.005% by mass or more, the hard coat layer is sufficiently cured by the effect of adding water, and the scratch resistance is improved. Moreover, since this water content is 0.13 mass% or less, a crack is hard to be generated in the hard coat layer during firing, and the appearance as an optical component is excellent.

In this invention, it is preferable that the addition of the water | moisture content to the said pre-hardening hard-coat layer by the said water | moisture-content addition process is performed by immersing in water.
According to the present invention, since the addition of moisture is performed by immersing in water, the processing time for adding moisture can be shortened. The treatment time by immersion is preferably about 1 to 15 minutes. Here, if the water temperature is low, the moisture content of the hard coat layer is low, so that the curing reaction in the main baking step is not sufficient, and the scratch resistance of the hard coat layer is low. Conversely, if the water temperature is too high, cracks are likely to occur in the hard coat layer. Therefore, it is preferable to use hot water of 40 to 60 ° C. Moreover, it is desirable to perform immersion for a short time when the water temperature is high, and conversely for a long time when the water temperature is low. For example, 50 ° C. for 15 minutes to 60 ° C. for 10 minutes is suitable.

In this invention, it is preferable that the addition process of the water | moisture content to the said pre-hardening hard-coat layer by the said water | moisture-content addition process is performed in the humidity environment of 80% RH or more.
According to the present invention, since the addition of water is performed in an environment of 80% RH or more, there is no need to prepare a water tank for water immersion, and there is no need to immerse the substrate in the water tank. The addition process can be easily performed.
The temperature is preferably in the range of about 40 ° C to 60 ° C. If the temperature is low, the moisture content is low, and it takes time to increase the moisture content. If the temperature or the relative humidity is increased, the time required for the treatment can be shortened. However, if the temperature or the relative humidity is too high, or if the treatment is performed for a time longer than necessary, the hard coat layer may be cracked. A more preferable humidity range is 90 to 98% RH. For example, in the case of 40 ° C., it is preferable to perform the treatment at 90% RH for about 3 days, and in the case of 60 ° C., the water addition treatment is preferably performed at 98% RH for about 12 hours. That is, a range of 40 ° C. and 90% RH for 3 days to 60 ° C. and 98% RH for 12 hours is preferable.

In the present invention, it is preferable to carry out an antireflection film forming step of forming an organic antireflection film on the hard coat layer by a wet method after the hard coat layer formation step.
According to the present invention, since the antireflection film is formed by a wet method, a large facility such as a vacuum apparatus is not necessary, and the manufacturing cost can be reduced. In addition, since the hard coat layer and the antireflection film can be continuously formed by a wet method, no effort is required for the production of optical components.
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.
The organic antireflection film preferably has a refractive index lower than that of the hard coat layer by 0.10 or more in view of the antireflection effect.

In the present invention, the organic antireflection film comprises silica-based particles having an internal cavity,
R ² R ³ nSiX 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 hydrolyzable group) And n is 0 or 1).
According to the present invention, since the silica-based particles have internal cavities, they can include a gas or a solvent 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.

The optical component of the present invention is manufactured by any one of the above-described optical component manufacturing methods.
Since such an optical component of the present invention is manufactured by any one of the above-described optical component manufacturing methods, the adhesion between the hard coat layer, the base material, and the antireflection film is improved. Therefore, the hard coat layer is difficult to peel off from the substrate and the antireflection film, and the scratch resistance is improved.

Embodiments of the present invention will be described below.
The optical component of the present embodiment is, for example, a plastic lens for spectacles, and includes a transparent plastic base material, a hard coat layer formed on the base material, and an organic reflection formed on the hard coat layer. A prevention film and a water repellent film are provided.

(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 transparent 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 episulfide-based plastics obtained by polymerizing raw material monomers containing compounds with episulfide groups are used as the base material, compounds with episulfide groups can be used alone or copolymerized with episulfide groups 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.
In addition, the dyeing | staining process is given to the plastic base material mentioned above as needed.

(2. Hard coat layer)
The hard coat layer has the following component (A) and component (B).
(A) General formula: Organosilicon compound represented by 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 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 an alkoxy group such as a methoxy group, an ethoxy group, and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group.

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 polyfunctional 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. 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 antireflection film in this embodiment is an organic antireflection film, and is composed of a single-layer organic film. The refractive index is 0.10 or more lower than that of the hard coat layer, and the film thickness is 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). Silica-based particles having an internal cavity of an organosilicon compound (E)

The organic group having a polymerizable reactive group of R ² as component (D) is, for example, polymerization of vinyl group, allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, isocyano group, amino group, etc. 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, butyl group, vinyl group, phenyl group and the like.
The X ² further component (D), for example, a methoxy group, an ethoxy group, an alkoxy group such as methoxyethoxy group, chloro group, a halogen group such as bromo group, an acyloxy group, and the like.

  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 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. Water repellent film)
A water repellent film for repelling water droplets is formed on the organic antireflection film as described above. As the water repellent for forming the water repellent film, a fluorine-based water repellent is preferably used. Specific examples of the fluorine-based water repellent include TSL8233 and TSL8257 manufactured by GE Toshiba Silicone Co., Ltd. and OPTOOL DSX manufactured by Daikin Industries, Ltd.

(5. Manufacturing method of plastic lens)
The plastic lens as described above is manufactured as follows. Here, the steps after the hard coat layer forming step will be described in detail.
(5-1. Hard coat layer formation process)
In the present invention, the hard coat layer forming step is divided into an adjustment step, a coating step, a temporary baking step, a water addition step, and a main baking step as follows. In the present invention, a primer layer may be provided between the lens substrate and the hard coat layer for the purpose of improving impact resistance.

(5-1-1. 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. As the curing catalyst, acetylacetonate having Fe (III) as a central metal atom is preferable in that the pot life of the hard coat solution can be extended.

(5-1-2. Application process)
A method for applying the hard coat liquid onto the substrate is arbitrary, and examples thereof include a dipping method, a spin coat method, a spray coat method, a roll coat method, and a flow coat method.
In order to improve the adhesion between the substrate and the hard coat layer, the substrate 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.

(5-1-3. Temporary firing process)
After applying the hard coat solution, the hard coat solution is pre-cured and pre-baked to obtain a pre-cured hard coat layer. The heating means for this pre-baking is selected depending on the type of hard coat liquid, and there are hot air and infrared light.
The pre-baking temperature is preferably 60 to 100 ° C. The heating time is preferably 10 to 50 minutes. When the baking temperature is less than 60 ° C., curing is insufficient and handling is difficult when performing defect inspection and the like, and when it exceeds 100 ° C., there is a concern that appearance quality may deteriorate due to rapid evaporation of the solvent.

(5-1-4. Moisture addition process)
By this step, moisture is added to the pre-cured hard coat layer to obtain a water-containing pre-cured hard coat layer.
As a moisture addition treatment method, the plastic lens may be immersed in water at a predetermined temperature (hot water immersion method) or may be maintained at a predetermined temperature and relative humidity (humidification method).
In the case of the hot water immersion method, the temperature of water is preferably 40 to 60 ° C., and the treatment time by immersion is preferably about 1 to 15 minutes. Here, when the water temperature is low, the moisture content of the hard coat layer is low, so that the curing reaction in the main baking step is not sufficient, and the scratch resistance is low. On the contrary, if the water temperature is high, cracks are likely to occur in the hard coat layer. Moreover, it is desirable to perform immersion for a short time when the water temperature is high, and conversely for a long time when the water temperature is low. For example, 50 ° C. for 15 minutes to 60 ° C. for about 10 minutes is preferable.

In the case of the humidification method, the temperature is preferably in the range of about 40 ° C to 60 ° C. Moreover, it is preferable to perform a water addition process in an environment with a relative humidity (RH) of 80% or more, and more preferably 90% RH or more. In this humidification method, the addition of water is performed in an environment of 80% RH or higher, so there is no need to prepare a water bath for water immersion, and no need to immerse the substrate in the water bath. Processing can be performed easily.
If the temperature is low, the moisture content is low, and it takes time to increase the moisture content. If the temperature or relative humidity is increased, the time required for the treatment can be shortened. However, if the temperature or relative humidity is too high, or if the treatment is performed for a longer time than necessary, cracks occur in the hard coat layer during the main firing described later. Cause. For example, in the case of 40 ° C., it is preferable to perform the treatment at 90% RH for about 3 days, and in the case of 60 ° C., the water addition treatment is preferably performed at 98% RH for about 12 hours. That is, a range of 40 ° C. and 90% RH for 3 days to 60 ° C. and 98% RH for 12 hours is preferable.

Here, the moisture content of the hard coat layer is calculated by the following equation (1).
W = {(B−B1) − (A−A1)} / (B−B1) (1)
(In the formula, A is the mass of the base material and the pre-cured hard coat layer after the pre-baking step in the above step. B is the base material and the water-containing pre-cured hard coat after the water addition step in the above step. The mass of the layer, A1 is the mass of the base material only, and B1 is the mass of the base material after passing only the base material directly through the water addition step.)
In the present invention, it is preferable that the water content W of the water-containing pre-cured hard coat layer represented by the above formula (1) is 0.005 to 0.13 mass% after the water addition treatment.

(5-1-5. Main firing process)
The firing temperature is preferably 100 to 140 ° C. The heating time is preferably 60 to 120 minutes. When the firing temperature is less than 100 ° C., curing is insufficient and scratch resistance and adhesion cannot be obtained, and when it exceeds 140 ° C., the lens substrate is yellowed and transparency is lowered.

(5-2. Antireflection film formation process)
(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.

(5-3. Water repellent film forming process)
The plastic lens on which the organic antireflection film is formed is washed and subjected to water repellent processing. Prepare a water repellent treatment solution (for example, 0.1% perfluorohexane solution of OPTOOL DSX manufactured by Daikin Industries, Ltd.), immerse the plastic lens, pull it up for a predetermined time, leave it at room temperature, and dry it. Thus, a water repellent film is formed.

  According to the embodiment as described above, by providing the water addition step after the preliminary firing step, hydrolysis of the hydrolyzable group of the organosilicon compound of the component (A) is promoted during the main firing, and siloxane A sufficient bond can be 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, the adhesiveness between the hard coat layer and the base material / antireflection film can be improved by reliably bonding the components (A), and scratch resistance as a plastic lens can be achieved. Can be improved.

In this embodiment, since the organic antireflection film is formed by a wet method, the hard coat layer and the antireflection film can be continuously formed by a wet method, so that the plastic lens can be easily manufactured. Therefore, a large facility such as a vacuum apparatus used in the dry method is not necessary, and the manufacturing cost can be reduced.
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, and therefore cracks caused by heating. Therefore, the plastic lens can be made excellent in heat resistance.

  Since the silica-based particles that are the component (E) constituting the organic antireflection film have internal cavities, they can include a gas and a solvent 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, as a moisture addition treatment method, the substrate may be immersed in an appropriate organic solvent or emulsion containing moisture instead of the hot water immersion method. Thereby, the penetration rate of moisture into the hard coat layer can be controlled over a wide range.

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.

Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
[Example 1]
(Hardcoat liquid adjustment process)
A reaction vessel equipped with a stirrer was charged with 74.93 g of γ-glycidoxypropyltrimethoxysilane, 37.61 g of γ-glycidoxypropylmethyldimethoxysilane, and 38.2 g of 0.1N aqueous hydrochloric acid, and stirred for 60 minutes. did. Next, 275.11 g of distilled water was added and the mixture was further stirred for 60 minutes. Thereafter, a composite sol of rutile type titanium oxide / zirconium oxide / silicon oxide / tin oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIK 1120Z (11RU-7 / A8)”) 58.439 g, silicone surfactant (Nippon Unicar Co., Ltd., trade name “L-7604”) 0.30 g was added, Fe (III) acetylacetonate 1.64 g was added and sufficiently stirred, and then a hard coat solution was obtained.

(Hard coating liquid application process)
The hard coat liquid obtained by the above operation was applied by spin coating to the convex surface of a plastic spectacle lens substrate (manufactured by Seiko Epson Corporation, lens fabric for Seiko Super Sovereign, refractive index 1.66).

(Preliminary firing process)
The spectacle lens base material after the hard coat liquid was applied was placed in a hot air oven and pre-baked at 80 ° C. for 30 minutes.
(Moisture addition process)
The pre-baked spectacle lens substrate was immersed in warm water (temperature 50 ° C.) for 15 minutes. Moreover, the moisture content of the hard-coat layer was measured by the above-mentioned formula (1) after immersion.

(Main firing process)
The eyeglass lens substrate after the water addition treatment was placed in a hot air furnace and subjected to main baking at 120 ° C. for 1.5 hours.
(Organic antireflection film forming process)
First, a composition (coating liquid) for forming an organic antireflection film was prepared as follows. 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 silica-based fine particle sol having an internal cavity (manufactured by Catalyst Kasei Kogyo Co., Ltd.), 1 part by weight of a silicone surfactant (FZ-7001 made by Toray Dow Corning) and iron (III) 1 part by weight of acetylacetonate having a central metal atom was added and stirring was continued for a whole day and night. Then, the mixture was 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, the spectacle lens substrate on which the hard coat layer is formed in the above-described main baking step is immersed in the coating solution, and after 30 seconds, the eyeglass lens substrate is pulled up at a lifting speed of 10 cm / min, and further in an oven set at 120 ° C. for 2 hours. An organic antireflection film was formed by heating. The thickness of this antireflection film is 100 nm.
(Water repellent film forming process)
The water repellent treatment liquid used was Daikin Industries, Ltd. OPTOOL DSX. A 0.1% solution (solvent: perfluorohexane) was prepared, the spectacle lens substrate was immersed, left for 1 minute, and then pulled up at 10 cm / min. Thereafter, it was left at room temperature for 24 hours.

[Example 2]
Example 1 is the same as Example 1 except that the water addition treatment was performed by immersing in warm water at 60 ° C. for 1 minute. [Example 3]
Example 1 is the same as Example 1 except that the water addition treatment was performed by immersing in 60 ° C. warm water for 10 minutes.
[Example 4]
Example 1 is the same as Example 1 except that the water addition treatment was performed by immersing in warm water at 70 ° C. for 10 minutes.

[Example 5]
The water addition treatment was performed by placing the pre-fired spectacle lens base material in a constant temperature and humidity chamber set at 40 ° C. and 90% RH for 2 days. Others are the same as the first embodiment.
[Example 6]
The pre-baked spectacle lens substrate was placed in a constant temperature and humidity chamber set at 40 ° C. and 90% RH for 3 days. Others are the same as the first embodiment.
[Example 7]
The pre-baked spectacle lens substrate was placed in a constant temperature and humidity chamber set at 40 ° C. and 90% RH for 4 days. Others are the same as the first embodiment.
[Example 8]
The pre-sintered spectacle lens substrate was placed in a constant temperature and humidity chamber set at 60 ° C. and 100% RH for one day. Others are the same as the first embodiment.

[Comparative Example 1]
The eyeglass lens substrate coated with the hard coating solution was temporarily fired and then fired as it was, followed by water addition treatment after the firing. The moisture addition treatment was performed by immersing the spectacle lens substrate in warm water at 60 ° C. for 1 minute. Others are the same as the first embodiment.
[Comparative Example 2]
The eyeglass lens substrate coated with the hard coating solution was temporarily fired and then fired as it was, followed by water addition treatment after the firing. The moisture addition treatment was performed by placing the spectacle lens substrate in a constant temperature and humidity chamber set at 40 ° C. and 90% RH for 4 days. Others are the same as the first embodiment.
[Comparative Example 3]
The same as Example 1 except that the moisture addition treatment was not performed.

[Evaluation methods]
With respect to the obtained hard coat layer and spectacle lens with an antireflection film, the appearance and scratch resistance were evaluated by the following methods. The results are shown in Table 1.

(Appearance evaluation)
The appearance of the spectacle lens was visually observed and evaluated in the following stages.
○: No crack △: Some cracks occurred ×: Cracks occurred on the entire surface

(Abrasion resistance evaluation)
A load of 9.8 N was applied to the spectacle lens with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), the 10 reciprocating surfaces were rubbed, and the degree of scratching was visually evaluated in the following stages. In practice, the allowable range is up to C.
A: No scratch is observed in the rubbed area.
B: 1 to 10 scratches were in the above range.
C: 10 to 20 scratches were in the above range.
D: There are countless scratches, but a smooth surface remains.
E: There are innumerable scratches and no smooth surface remains.

[Evaluation results]
In Examples 1 to 8, both the appearance and the scratch resistance of the spectacle lens are at a level that causes no problem in practical use.
On the other hand, in Comparative Examples 1 and 2, a crack occurs on the entire spectacle lens, and the scratch resistance is also inferior. Moreover, since the comparative example 3 has not performed the water addition process, it does not generate | occur | produce a crack in a spectacle lens, but is inferior to scratch resistance.
That is, as apparent from the present invention, it is understood that a spectacle lens excellent in appearance and scratch resistance can be obtained for the first time by performing a water addition treatment on the hard coat layer under specific conditions.

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

Claims (8)

A method for producing an optical component comprising a plastic substrate and a hard coat layer formed on the substrate,
The hard coat layer is an application step of applying a hard coat solution onto the substrate;
A pre-baking step of obtaining a pre-cured hard coat layer by pre-curing the hard coat liquid coated on the substrate after the coating step by hydrolysis reaction;
A moisture addition step of adding moisture to the pre-cured hard coat layer after the pre-baking step to obtain a moisture-containing pre-cured hard coat layer;
A main baking step for completing the curing by further hydrolysis reaction of the moisture-containing pre-cured hard coat layer after the moisture addition step;
A method for producing an optical component, comprising: a hard coat layer forming step comprising: In the manufacturing method of the optical component according to claim 1,
An optical component characterized in that the coating step includes a step of coating a hard coat liquid containing inorganic oxide particles containing titanium oxide having a rutile-type crystal structure and the following component (A) on the substrate. Production method.
(A) General formula: Organosilicon compound represented by R ¹ SiX ¹ ₃ (wherein R ¹ is an organic group having a polymerizable reactive group, and X ¹ represents a hydrolyzable group) In the manufacturing method of the optical component of Claim 1 or Claim 2,
The water content W shown in the following formula (1) of the moisture-containing pre-cured hard coat layer is 0.005 to 0.13% by mass.
W = {(B−B1) − (A−A1)} / (B−B1) (1)
(In the formula, A is the mass of the base material and the pre-cured hard coat layer after the pre-baking step in the above step. B is the base material and the water-containing pre-cured hard coat after the water addition step in the above step. The mass of the layer, A1 is the mass of the base material only, and B1 is the mass of the base material after passing only the base material directly through the water addition step.) In the manufacturing method of the optical component in any one of Claims 1-3,
A method for producing an optical component, characterized in that the process of adding moisture to the pre-cured hard coat layer in the moisture adding step is performed by immersing in water. In the manufacturing method of the optical component in any one of Claims 1-3,
A method for producing an optical component, characterized in that the process of adding moisture to the pre-cured hard coat layer in the moisture adding step is performed in an environment having a humidity of 80% RH or higher. In the manufacturing method of the optical component in any one of Claims 1-5,
A method of manufacturing an optical component, comprising performing an antireflection film forming step of forming an organic antireflection film on the hardcoat layer by a wet method at a subsequent stage of the hardcoat layer forming step. In the manufacturing method of the optical component according to claim 6,
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 hydrolyzed) And an organic silicon compound represented by the formula (n is 0 or 1).   An optical component manufactured by the method for manufacturing an optical component according to claim 1.